US3809663A - Textile sizing,water and oil repellent composition - Google Patents

Textile sizing,water and oil repellent composition Download PDF

Info

Publication number
US3809663A
US3809663A US00631167A US63116767A US3809663A US 3809663 A US3809663 A US 3809663A US 00631167 A US00631167 A US 00631167A US 63116767 A US63116767 A US 63116767A US 3809663 A US3809663 A US 3809663A
Authority
US
United States
Prior art keywords
water
starch
oil
compositions
composition
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
US00631167A
Inventor
V Elkind
J Yurko
R Hunter
H Narder
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
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 Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US00631167A priority Critical patent/US3809663A/en
Priority to DE19681769112 priority patent/DE1769112A1/en
Priority to DK156168AA priority patent/DK124414B/en
Priority to AT03399/68A priority patent/AT291929B/en
Priority to CH535268A priority patent/CH476149A/en
Priority to CH1193268A priority patent/CH535317A/en
Priority to CH1193268D priority patent/CH1193268A4/xx
Priority to ES352792A priority patent/ES352792A1/en
Priority to NO01421/68A priority patent/NO129914B/no
Priority to GB08134/68A priority patent/GB1217590A/en
Priority to IE442/68A priority patent/IE31874B1/en
Priority to NL6805432A priority patent/NL6805432A/xx
Priority to BE713777D priority patent/BE713777A/xx
Priority to FR1561678D priority patent/FR1561678A/fr
Application granted granted Critical
Publication of US3809663A publication Critical patent/US3809663A/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
    • D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
    • D06M15/03—Polysaccharides or derivatives thereof
    • D06M15/11—Starch or derivatives thereof
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine

Definitions

  • a textile sizing or starching composition which also imparts water and oil-repellency and dry soil resistance containing a water-soluble starch and a fluoro polymer latex used, preferably, as an aerosol.
  • the present invention relates to a new and outstanding textile treating composition and particularly to compositions of the type normally used preparatory to ironing and textiles, such compositions serving primarily to size and/or stiffen the textile and in many instances to add gloss to the textile surface, and more particularly to sizing compositions, commonly referred to as laundry starch compositions, which in the present invention not only effect a sizing, stiffening and glossy surface but also impart to the treated textile outstanding waterand oilrepellency as well as excellent resistance to soiling.
  • starch as a size and stiffening agent for textile materials is probably as old as textiles themselves. It is only within the last several decades that the housewife has been offered such a product in an already prepared liquid form for application to the textile before ironing.
  • Such starching compositions are now available in a variety of forms and among the most popular is an aerosol type formulation. While starch, or starch derivatives, or modified starches form the major basis for the starching compositions presently available, there have been developed numerous non-starch, synthetic resinbased starching materials for the same general purposes.
  • starch refers to any suitable sizing material or stiffening composition which may be applied from a water dispersion (solution or suspension) as a preparatory treatment to an ironing step and while generally the natural starch materials are preferred, and this includes the numerous starch derivatives such as oxidized starches, acylated starches, starch ethers, hydrolyzed starches, enzyme-treated starches and the like, the compositions of the present invention encompass not only these natural and modified starches as a component thereof but the various synthetic products which are comparable and equivalent thereto.
  • the present invention provides a sizing or stiffening composition, i.e., a starch composition, which not only produces the desired degree of size and stiffness, which not only affords control by the consumer or housewife of these characteristics by virtue of the nondurability between washings of this finish, but also provides water and oil repellency which is durable in nature, which continues to build-up during the subsequent washings and treatments before ironing, and each build-up of permanence nevertheless does not interfere with the nondurability of the stiffening agent and does not produce a build-up of this component, notwithstanding the fact that all of these characteristics and effects are produced at one time from a single composition.
  • a starch composition which not only produces the desired degree of size and stiffness, which not only affords control by the consumer or housewife of these characteristics by virtue of the nondurability between washings of this finish, but also provides water and oil repellency which is durable in nature, which continues to build-up during the subsequent washings and treatments before ironing, and each build-up of permanence nevertheless does not interfere with the non
  • Another further object of this invention is to provide in aerosol form, compositions for treating textile materials preparatory to ironing same including therein a sizing starch and a fluorocarbon polymer.
  • Still another object of this invention lies in the provision of processes for treating textile materials to produce a sized and stiffened product and which is further characterized by water and oil repellency as well as resistance to staining by both water and oil-borne stains and still further by resistance by soiling.
  • compositions of the present invention comprise as the essential ingredients thereof, a water soluble or water dispersible sizing material, which is preferably a polyszccharide as exemplified by the various natural starches and the various starch derivatives which have been described above in combination with a thermo-plastic filmforming fluorocarbon polymer as hereinafter described.
  • a water soluble or water dispersible sizing material which is preferably a polyszccharide as exemplified by the various natural starches and the various starch derivatives which have been described above in combination with a thermo-plastic filmforming fluorocarbon polymer as hereinafter described.
  • additives which do not adversely effect the attainment of nondurable stiffening along with durable and permanent water and oil repellency.
  • additional materials include anti-stick agents such as the siloxane resins, polyethylene and the like; extenders for the fluorocarbon polymer such as urea-formaldehyde resins, acrylate and methacrylate polymers and copolymers and the like; additional water repellent materials such as long chain fatty quaternary ammonium compounds; anti oxidants; anti foamers; stabilizers; bacteriacides; surface active agents; coloring materials; perfumes; textile fiberreactive chemicals, e.g., formaldehyde, glyoxal; crease resistant and crease proofing agents, and the like.
  • compositions of this invention is a self-propelling liquid composition wherein the major carrier liquid is water and the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fiuorinated methanes, ethanes, and the like such as dichloro difluoro methane and the like.
  • the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fiuorinated methanes, ethanes, and the like such as dichloro difluoro methane and the like.
  • the nondurable size or stiffening component is preferably selected from the general class of starches and starch derivatives and among these the most preferred material is an acetylated amylopectin which is a thin boiling cook-up type starch and is illustrative of the preferred class of products of high fluidity i.e., 30 to 100 (intrinsic viscosity of from 1.0 to 0.3).
  • Other starch products which may be employed include the following: gelatinized corn starch, gelatinized wheat starch, gelatinized rice starch, gelatinized tapioca ethoxylated starch, gelatinized carboxymethyl starch, nitrogenated starch, oxidized corn starch, alkylated starch, dextrins and the like.
  • the amount of starch material which may be employed in the compositions of this invention may be varied widely, but in general from about 1% to about thereof based on the total weight of the aerosol formulation may be used. More important than the specific amount of sizing material is the ratio of the latter to the fluorocarbon polymer employed. in general, the ratio of these two components may vary from about 1:2 to 100:1 (size to fiuoro polymer) and within this range it is preferred to employ a ratio of from about 2:1 to 20: 1.
  • the fluoropolymer component of the compositions of this invention comprise a thermoplastic polymeric material in the form of a latex which is characterized by the ability to dry to a continuous cohesive film.
  • Fluoro polymers are well known but those which are preferred in the present invention comprise the general class of the perfluoro acrylates and alpha-substituted acrylates such as methacrylates.
  • the fiuoro polymers which may be used in the present invention, mention may be made of the following;
  • X is hydrogen, chlorine or fluorine.
  • X is hydrogen, lower alkyl (C to C or halogen and at least 70% but not less than 6 of the Xs are fluorine; interpolymers (i.e., copolymers and terpolymers of the aforementioned monomers, with polymerizable vinyl compounds, said interpolymer containing at least 25 mole percent of fluoro monomer (I).
  • Suitable comonomers include:
  • alkyl vinyl ketones ( alkyl C to C alkyl acrylates (alkyl C to C alkyl methacrylates (alkyl C to C vinylidene halides acrylic acid acrylonitrile acrylamide N- methylol acrylamide; N-methoxy methyl acrylamide styrene; alkyl styrenes 1,3-butadiene alkyl esters alkyl halides monoand di-acrylate esters of alkanediols monoand di-vinyl esters of alkanedioic acids,
  • a low molecular weight fluoropolymer latex which dries by itself to a brittle film.
  • Such products are prepared from similar monomers as described above but include a chain transfer agent, e.g., alkanethiol such as dodecyl mercaptan, to terminate the polymer.
  • resin emulsions may be added to the compositions of this invention to give special benefits.
  • Typical formulations of starch and fluoropolymers include the following:
  • concentrations are selected to give a solid pick-up based on the material treated of between 0.1% to 10% by weight. Since in order to obtain uniform treatment of a textile, it is desirable to have from about 1 to 200% and preferably from about 25 to 100% wet pick-up the concentrations of active components in the treating composition for the preferred pickup will vary from about 40% down to 0.1%. Clearly, such concentrations are not critical and are subject to the wide variation and great latitude indicated above.
  • the aqueous compositions are formulated with a suitable propellant.
  • propellants include trichloromonofluoromethane, dichlorotetrafluoroethane, dichloromonofluoromethane, monochlorotrifluoromethane, isobutane,
  • propellants are water-immiscible or only slightly soluble in water with vapor pressures at 70 F. of from about 0.2 to about 500 ps./g.
  • vapor pressures at 70 F. of from about 0.2 to about 500 ps./g.
  • the preferred propellants are the low density compounds and mixtures of low density which form a separate and upper liquid phase in the aerosol package providing thereby a three-phase system. While it is not intended to foreclose the use of higher density propellants (i.e., higher than the aqueous latex phase) in which case the propellant will be on the bottom in the aerosol package, this is not preferred because of the inadequacies of the mechanics of the package required for dispensing such compositions and further because other means for making such systems workable (i.e. shortened dip tube) create undesirable economic factors (eg cannot discharge a high percent of the active ingredients). In order to achieve the benefits of this invention, however, any technique aerosol or otherwise may be employed notwithstanding the fact that the optimum results may be obtained with certain specific formulations and techniques and these might, in general, be preferred especially by the housewife.
  • propellant as well as the specific one or ones used will vary depending upon the pressure limitations on the package and the spray pattern desired. Generally from 5 to 25 by weight of propellant circumscribes the practical range thereof, and as pointed out above, among these the low density, medium vapor pressure hydrocarbons such as isobutane are preferred.
  • compositions of this invention may be used in the compositions of this invention, some with particularly noteworthy results.
  • incorporation of a polyethylene emulsion in amounts ranging from 10% to 300% by weight based on the weight of fluoropolymer gives rise to unique ironing characteristics to textiles sprayed with such modified embodiments.
  • Siloxane emulsions for similar purposes are also contemplated.
  • Example 1 is repeated except that the fiuoropolymer used is a terpolymer containing 2.5% n-butyl acrylate and 0.5% N-methylol acrylamide. The results are somewhat superior to those of Example 1.
  • composition 3F lies in its unusual and unexpected improved laundering characteristics, as hereinafter demonstrated.
  • EXAMPLE 4 Swatches of 80 x 80 cotton are sprayed with the composition of Example 1 to give a 50% wet pick-up and ironed at 400 F. 33 sec./ft. to dryness. Excellent water and oil repellency results. The swatches are then artificially soiled as described below and then laundered. Untreated swatches are also soiled in a similar manner and laundered. The untreated samples launder better (i.e. as measured on a Photovolt Reflectance Meter) than the treated swatches.
  • Example 1 gives excellent water and oil rcpellency and as will be evident in further examples also gives excellent repellency to both water and oil borne stains, such treated materials, although more resistant to soiling nevertheless once they are soiled, do not launder as well as an untreated textile.
  • the soiling procedure is as follows:
  • the standardized soil is prepared by the method described in Salisbury et al. Soil Resistant Treatment of Fabric, American Dyestuff Reporter, Mar. 26, 1956, page 199.
  • the test using the standardized soils is as follows:
  • the end-over-end tumbling is carried out in a 6" diameter by 12' long cylindrical stainless steel jar rotating at 43 r.p.m.
  • Six (6) No. 8 Neoprene rubber stoppers (average weight 41.5+0.5 gram) are distributed evenly with the soil among the specimens. After tumbling, the specimens are removed and each shaken 15 times by hand to remove free soil by holding one corner 8 times and the diagonally opposite corner 7 times.
  • Each swatch is cut in half after repellency reflectance readings to produce two 5" x 3 /2" pieces (22 pairs total). Twenty-two swatches, one from each pair, are washed in an automatic Washer using 50 grams of Fab in the cotton cycle with 5 pounds additional dummy load and then dried 5 minutes in an automatic dryer at the high setting and lightly hand ironed.
  • the degree of soil before and after washing is determined with the Photovolt Reflectance Meter
  • the meter is standardized by placing the probe head on a block of MgCO (freshly ground against an identical block); then readings are taken on a porcelain plate used as a secondary standard. Readings using the Model 610Y probe with tri-blue filter and the Model 610D probe with tri-green filter have proved comparable with synthetic soil. Eight readings are taken with small probe and 6 readings with the large probe (610D) and the average value is reported.
  • Example 4 is repeated and instead of artificially soiling the swatches with the synthetic dry soil they are stained as follows:
  • the water-repellency is determined according to the AATCC Standard Test Method 221952.
  • test specimen fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal.
  • Two hundred and fifty milliliters of water at 80i2 F. is poured into a funnel attached above the spray nozzle.
  • the spray lasts 25 to seconds at the end of which time the hoop is taken 25 by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180.
  • the swatches treated in Example 4 are further characterized by a stiffness rating (Stiffness Handle-O-Meter 30 using a swatch 4" x 4") of 44.
  • An untreated, laundered swatch gives a value of 21 (befor laundering it is 34).
  • EXAMPLE 7 The treated swatches of Example 6 are laundered and a second treatment is given. The water repellency is found to be 100 both before and after another laundering and the oil repellency is 6 before and 5 after this other laundering.
  • a concomittant increase in stain repellency is also noted as follows:
  • Example 8 The procedure in Example 7 is repeated through sprays, each followed by an ironing and a laundering with a final oil repellency value of 7, a stiffness rating before the last laundering of 53.5 (note, again, no buildup of stiffness), stain, dry soil repellency, and stain and soil removal equivalent to that shown in Example 6.
  • Example 9 A composition employing the components of Example 6 is prepared as follows: (percent on an active basis) Percent Acetylated amylopectin 3.75 Terpolymer of Example 2 0.30 Interpolymer XVI 0.10 Polyethylene (Example 6) 0.28 Formaldehyde 0.35 Isobutane 6. 17 Water 89.00
  • This composition is outstanding for dispensing as an aerosol with an excellent spray pattern and no valve clogging. Upon application to fabrics the results are similar to what is described in the previous examples.
  • Oil repellency 5. Water repellency: 80.
  • Oil repellency 4. Water repellency: 80.
  • EXAMPLE 12 In the following table various aqueous compositions are set forth which give excellent oil and water repellency, outstanding dry soil resistance and a highly desirable stifiness to cotton textiles treated therewith. The balance of the composition is water. As in the previous example the polymers are in latex form.
  • Example 1 mer II. (D) 6% amylopectin 0.5% interpoly- 0.3% polyethylene, 1.0%
  • Example 1 mer XIII. urea-formaldehyde crease-proofing agent.
  • Example 9 is repeated except that the propellant and amount thereof is varied as follows: (with a corresponding change in percent water)
  • EXAMPLE 14- Example 1 is repeated using the following water-soluble carbohydrates in the indicated amounts. Where more or less than 2.7% is used, there is a corresponding change in the water present:
  • Example 9 Homopoly-1H,1H-perfluorodecyl methacrylate
  • Example 9 is repeated using in place of the terpolymer of Example 2 and interpolymer XVI, the following in the indicated amounts:
  • A Modified cornstarch-fluidity 60 2.2
  • B Modified cornstarch-fluidity 60 7.5
  • C Modified cornstarch-fluidity 75 5.0
  • E Thin boiling wheat starch-fluidity 87 5.0
  • F Oxyethylated starch-fluidity 65 3.75
  • G Gelatinized starch-fluidity 8O 2.5
  • compositions of this invention produce excellent sizing along with unique water and oil-repellency on textiles.
  • the compositions may be applied to the textile in any convenient manner although they are most superior when used in an aerosol form.
  • the package structure will, obviously, vary from those packages or container used with propellants which are less dense and form an upper, discrete liquid phase. Regardless of these variations, however, excellent properties are forthcoming in all instances.
  • compositions of this invention may be added to the compositions of this invention, as pointed out above, and as will be obvious to one skilled in the art, the parameters are extremely varied, particularly in view of the fact that none of the additives need be soluble either in water or the selected propellant.
  • a compound may be added as a solution in a suitable solvent and such solution added to the aqueous compositions producing in most instances a dispersion of the said compound in the compositions.
  • Many other variations will be apparent and it is clear that these may be resorted to without departing from the spirit and scope of this invention and that the specific embodiments 5 Out herein are in no way limitative thereof.
  • a containerized selfpropelling aqueous textile treating composition which imparts simultaneously stilfening and oil and water repellency which comprises (A) a water-soluble starch,
  • a terpolymer in the form of a latex comprising (1) a polymerizable thermoplastic perfluoroalkylethylmethacrylate of the formula wherein X is selected from the group consisting of hydrogen, C, to C alkyl, chlorine and fluorine; X is selected from the group consisting of hydrogen, chlorine and fluorine, n has a value of 3 to 30; and at least 70%, but at least 6, of the X's are fluorine; (2) butylacrylate, and (3) N-methylol acrylamide; and, (C) propellant selected from the group consisting of hydrocarbons, halogenated hydrocarbons, and mixtures thereof;
  • ratio of starch to terpolymer is 2:1 to 20:1, and wherein said water-soluble starch is from 1 to 10% and said propellant is from 5 to 25% by weight of total composition.
  • a composition as defined in claim 1 wherein also present in the form of a latex is a copolymer of perfluoroalkylethylmethacrylate and butyl acrylate prepared in the presence of a chain transfer agent, and wherein the ratio of terpolymer to copolymer is 3:1.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Abstract

A TEXTILE SIZING OR "STACHING" COMPOSITION WHICH ALSO IMPARTS WATER AND OIL-REPELLENCY AND DRY SOIL RESISTANCE CONTAIING A WATER-SOLUBLE STARCH AND A FLUORO POLYMER LATEX USED, PREFERABLY, AS AN AEROSOL.

Description

United States Patent 3,809,663 TEXTILE SIZING, WATER AND OIL REPELLENT COMPOSITION Vincent T. Elkind, Metuchen, Robert T. Hunter, Piscataway, Herman L. Narder, Plainfield, and Joseph A. Yurko, Bayonne, N.J., assignors to Colgate-Palmolive Company, New York, N.Y. N0 Drawing. Filed Apr. 17, 1967, Ser. No. 631,167 Int. Cl. C08b 25/02 U.S. Cl. 26017.4 ST 3 Claims ABSTRACT OF THE DISCLOSURE A textile sizing or starching composition which also imparts water and oil-repellency and dry soil resistance containing a water-soluble starch and a fluoro polymer latex used, preferably, as an aerosol.
The present invention relates to a new and outstanding textile treating composition and particularly to compositions of the type normally used preparatory to ironing and textiles, such compositions serving primarily to size and/or stiffen the textile and in many instances to add gloss to the textile surface, and more particularly to sizing compositions, commonly referred to as laundry starch compositions, which in the present invention not only effect a sizing, stiffening and glossy surface but also impart to the treated textile outstanding waterand oilrepellency as well as excellent resistance to soiling.
The use of starch as a size and stiffening agent for textile materials is probably as old as textiles themselves. It is only within the last several decades that the housewife has been offered such a product in an already prepared liquid form for application to the textile before ironing. Such starching compositions are now available in a variety of forms and among the most popular is an aerosol type formulation. While starch, or starch derivatives, or modified starches form the major basis for the starching compositions presently available, there have been developed numerous non-starch, synthetic resinbased starching materials for the same general purposes. In the present invention where the term starch is employed it is to be understood that this refers to any suitable sizing material or stiffening composition which may be applied from a water dispersion (solution or suspension) as a preparatory treatment to an ironing step and while generally the natural starch materials are preferred, and this includes the numerous starch derivatives such as oxidized starches, acylated starches, starch ethers, hydrolyzed starches, enzyme-treated starches and the like, the compositions of the present invention encompass not only these natural and modified starches as a component thereof but the various synthetic products which are comparable and equivalent thereto.
It is well known that in order to obtain a desirable stiffening of the textile material after washing, it is necessary after each washing and before each ironing to treat the textil with starching composition. Obviously, this is so because of the nondurable nature of the sizing compositions used. As a practical matter, it is necessary that the sizing or starching composition be nondurable and produce no build-up of stiffening action from one wash to another since this would lead to stiffening of the textile material to an undesirable degree in most instances. By virtue of the nondurable characteristics of the conventional starching compositions, it is possible for the housewife to control the degree of size and stiffening with each product at any given time.
It is also known to treat textile materials with various water and/ or oil-repellent compositions, and usually such ice operations are carried out in the mill during the manufacture of the base textile material although it is not by any means uncommon to find products which can be used for such purposes by the housewife and which are in fact so used on an individual basis to produce a water repellent or an oil repellent finish on the textile material. The products normally employed for producing water repellency and/or oil repellency do not produce any stiffening or sizing action on the textile and as a matter of fact it is not considered very desirable to offer such compositions which would additionally stiffen the textile. It is further to be noted, particularly with regard to the provision of an oil repellent characteristic to the textile material, that the presently available treatments are of limited durability and as a consequence thereof in order to maintain optimum properties in this area repeated treatments are necessary particularly after each cleansing operation on the textile material.
The present invention provides a sizing or stiffening composition, i.e., a starch composition, which not only produces the desired degree of size and stiffness, which not only affords control by the consumer or housewife of these characteristics by virtue of the nondurability between washings of this finish, but also provides water and oil repellency which is durable in nature, which continues to build-up during the subsequent washings and treatments before ironing, and each build-up of permanence nevertheless does not interfere with the nondurability of the stiffening agent and does not produce a build-up of this component, notwithstanding the fact that all of these characteristics and effects are produced at one time from a single composition.
It is, therefore, an object of this invention to provide a textile treatiing composition which imparts to textiles treated therewith stiffness as well as water and oil repellency.
It is another object of this invention to provide textile treating compositions to be employed prior to ironing which produces a nondurable stiffening action but a relatively permanent water and oil repellent surface thereon.
It is still another object of this invention to provide starching compositions which are particularly adaptable for treating textiles after washing and preparatory to ironing whereby and textiles so treated are sized and/or stiffened and at the same time rendered water and oil repellent.
It is still another further object of this invention to provide liquid starching compositions and particularly such compositions in an aerosol form which produce on the textile material treated therewith a nondurable stiffening action and a relatively permanent water and oil repellent surface thereon.
Another further object of this invention is to provide in aerosol form, compositions for treating textile materials preparatory to ironing same including therein a sizing starch and a fluorocarbon polymer.
Still another object of this invention lies in the provision of processes for treating textile materials to produce a sized and stiffened product and which is further characterized by water and oil repellency as well as resistance to staining by both water and oil-borne stains and still further by resistance by soiling.
Other objects will appear hereinafter as the description proceeds.
The compositions of the present invention comprise as the essential ingredients thereof, a water soluble or water dispersible sizing material, which is preferably a polyszccharide as exemplified by the various natural starches and the various starch derivatives which have been described above in combination with a thermo-plastic filmforming fluorocarbon polymer as hereinafter described. In
addition to the starch and fluoro polymer there may also be present in the compositions of this invention many other additives which do not adversely effect the attainment of nondurable stiffening along with durable and permanent water and oil repellency. Examples of such additional materials include anti-stick agents such as the siloxane resins, polyethylene and the like; extenders for the fluorocarbon polymer such as urea-formaldehyde resins, acrylate and methacrylate polymers and copolymers and the like; additional water repellent materials such as long chain fatty quaternary ammonium compounds; anti oxidants; anti foamers; stabilizers; bacteriacides; surface active agents; coloring materials; perfumes; textile fiberreactive chemicals, e.g., formaldehyde, glyoxal; crease resistant and crease proofing agents, and the like.
The preferred form of the compositions of this invention is a self-propelling liquid composition wherein the major carrier liquid is water and the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fiuorinated methanes, ethanes, and the like such as dichloro difluoro methane and the like.
The nondurable size or stiffening component is preferably selected from the general class of starches and starch derivatives and among these the most preferred material is an acetylated amylopectin which is a thin boiling cook-up type starch and is illustrative of the preferred class of products of high fluidity i.e., 30 to 100 (intrinsic viscosity of from 1.0 to 0.3). Other starch products which may be employed include the following: gelatinized corn starch, gelatinized wheat starch, gelatinized rice starch, gelatinized tapioca ethoxylated starch, gelatinized carboxymethyl starch, nitrogenated starch, oxidized corn starch, alkylated starch, dextrins and the like. The amount of starch material which may be employed in the compositions of this invention may be varied widely, but in general from about 1% to about thereof based on the total weight of the aerosol formulation may be used. More important than the specific amount of sizing material is the ratio of the latter to the fluorocarbon polymer employed. in general, the ratio of these two components may vary from about 1:2 to 100:1 (size to fiuoro polymer) and within this range it is preferred to employ a ratio of from about 2:1 to 20: 1. By the use of the aforementioned ratios and, particularly, the narrower range, it has been found that an outstanding nondurable stiffening action is obtained which not only does not interfere with the provision of excellent repellent characteristics but actually appears to enhance the performance of the fluoropolymer as will hereinafter be described.
The fluoropolymer component of the compositions of this invention comprise a thermoplastic polymeric material in the form of a latex which is characterized by the ability to dry to a continuous cohesive film. Fluoro polymers are well known but those which are preferred in the present invention comprise the general class of the perfluoro acrylates and alpha-substituted acrylates such as methacrylates. As illustrative of the fiuoro polymers which may be used in the present invention, mention may be made of the following;
Homopolymers of:
1H,lH-perfluorohexyl acrylate 1H,1H-perfluorooctyl acrylate l H,1H-perfluorodecyl acrylate 1H,lH-perfluorododecyl acrylate 1H,1H-perfluorohexyl methacrylate 1H, iH-perfluorodecyl methacrylate 1H,1'H-penfluorododecyl methacrylate 1H, lH-perfluorohexylu-fiuoroacrylate 1H,lH-perfluorodecyl-a-fiuoroacrylate 1H,1H,7H-perfl-uoroheptyl acrylate 1H,1H,1 lH-perfluoroundecyl methacrylate 1*H,1H,3H-perfluorooctyl acrylate the general formula of which may be presented as follows: i
Xi(CX2)n(CH2)m0(I:| COHg 0 wherein X is hydrogen, chlorine or fluorine. X is hydrogen, alkyl (C to C chlorine or fluorine, n has a value of 3 to 30, ml=1, 2 or 3. X is hydrogen, lower alkyl (C to C or halogen and at least 70% but not less than 6 of the Xs are fluorine; interpolymers (i.e., copolymers and terpolymers of the aforementioned monomers, with polymerizable vinyl compounds, said interpolymer containing at least 25 mole percent of fluoro monomer (I).
Suitable comonomers include:
vinyl esters of organic and inorganic acids e.g.
vinyl chloride vinyl bromide vinyl fluoride vinyl acetate vinyl propronate vinyl stearate vinyl benzoate vinyl ethers e.g.
methyl vinyl ether ethyl vinyl ether n-butyl vinyl ether decyl vinyl ether -octadecyl vinyl ether benzyl vinyl ether phenyl vinyl ether divinyl ether alkyl vinyl ketones( alkyl C to C alkyl acrylates (alkyl C to C alkyl methacrylates (alkyl C to C vinylidene halides acrylic acid acrylonitrile acrylamide N- methylol acrylamide; N-methoxy methyl acrylamide styrene; alkyl styrenes 1,3-butadiene alkyl esters alkyl halides monoand di-acrylate esters of alkanediols monoand di-vinyl esters of alkanedioic acids,
and the like.
In order to obtain the optimum properties in repellency characteristics without decreasing the dry soil launderability it has been found advantageous to include in the composition a low molecular weight fluoropolymer latex which dries by itself to a brittle film. Such products are prepared from similar monomers as described above but include a chain transfer agent, e.g., alkanethiol such as dodecyl mercaptan, to terminate the polymer.
Other resin emulsions may be added to the compositions of this invention to give special benefits. Thus one may add minor amounts -(up to about 300% of the weight of fluoropolymer) based on the weight of the total composition of any of the aforementioned nonfluorinated polymers among others, e.g., polysiloxane emulsions, polyethylene emulsions, polybutadiene emulsions, polystyrene emulsions, and the like.
Specific copolymers, terpolymers and interpolymers of particularly outstanding characteristics include the following monomers: (weight basis) (a) CF;(O F3)5CH1CHzOfiC=CHZ (b) 10% n-butyl acrylate (VII) (VIII) (XII) (XIII) C z(C FDsCHnCHgO (Ii-:011,
(b) n-butyl acrylate (a) 50% C Fz(C F2)5OH2CH1OC[C=CHI (b) 50% 2-ethy1hexyl methaerylate r (a) 25% C F;(C F;) CH;CH,O CC=OH:
(b) 70% 2-ethylhexyl methacrylate (c) 5% N-methylol aerylamide (a) 95% CHFKC rmcrno CC=CH1 (b) 5% n-butyl acrylate (a) 80% CHFKC FmCHnO C-C=CH1 (b) 5% n-butyl acrylate (c) 2-ethylhexyl methaerylate (d) 5% n-butyl methacrylate (b) 2% Z-ethyl hexylaerylate (a) 95% CHFAC FahCHgO CCH=CH;
(b) 7% 2-ethyl hexylacrylate (c) 1% N-methylol acrylamide (b) 2% n-butyl acrylate (c) 0.5% N-methylol acrylamide 32. 5% C F:(C F1)1CH:CH:O O C-C=C I 16. 2% C F ((J Fl)9CHzOHlO 0 CC=CH| (d) 2% n-butyl aerylate (e) 0. 5% N-methylol acrylamlde In addition to the fluorohomopolymer or interpolymer, there may be additionally used other resins and particularly low molecular weight fluorohomopolymers and fluoro interpolymers. These are prepared by emulsion polymerization in the presence of minor amounts of chain transfer agents. A typical low molecular weight product is prepared from the following: (polymerization run at 70 C. for 5 hours).
(XVI) CH;
parts CF3(CF1)5CH:CH10CC=CH| 2 parts n-butyl aerylate 2 parts oetadeeyl dimethylamine acetate 1.2 parts dodecyl mercaptan 200 parts water The polymer produced by this technique is of much lower molecular weight than that normally prepared in the absence of the chain transfer agent, dodecyl mercaptan.
It is, of course, to be understood that the low molecular weight fluoropolymers (i.e., chain terminated as above) are also excellent for the purposes of this invention although treatments therewith are not as permanent as with the other fiuoropolymers.
Typical formulations of starch and fluoropolymers include the following:
( 1) 3 parts acetylated amylopectin (National 1135 Starch) (2) 1.2 parts of a 25% solids latex (.3 part active polymer solids) of copolymer H (1) 3 parts acetylated amylopectin (National 1135 Starch) (2) 1.2 parts of a 25% solids latex of terpolymer III (1) 3 parts acetylated amylopectin (National 1135 Starch) (2) 1.6 parts of a 25 solids latex of interpolymer XV (1) 2.5 parts acetylated amylopectin (National 1135 Starch) (2) 1.5 parts of a 25% solids latex of interpolymer XV (3) .5 part chain terminated copolymer XVI as a 25 solids latex (0.125 part polymer solids) (1) 2 parts acetylated amylopectin (National 1135 Starch) (2) 4 parts of a 25% solids latex of copolymer II 1) 1 part acetylated amylopectin (National 1135 Starch) (2) 4 parts of a 25% solids latex of copolymer II (1) 15 parts acetylated amylopectin (National 1135 Starch) (2) 2 parts of a 25% solids latex of interpolymer XV (1) 20 parts acetylated amylopectin (National 1135 Starch) (2) 1 part chain terminated copolymer XVI as a 25% solids latex (1) 30 parts acetylated amylopectin (National 1135 Starch) (2) 1.5 parts of a 25% solids latex of interpolymer XV (3) 0.5 part chain terminated copolymer XVI as a 25 solids latex (1) 50 parts acetylated amylopectin (National 1135 Starch) (2) 1.5 parts of a 25% solids latex of interpolymer XV (3) 0.5 part chain terminated copolymer XVI as a 25% solids latex (1) 25 parts acetylated amylopectin (National 1135 Starch) (2) 1.5 parts of a 25% solids latex of interpolymer XV (3) 0.5 part chain terminated copolymer XVI as a 25% solids latex (1) 45 parts acetylated amylopectin (National 1135 Starch) (2) 1 part of a 25 solids latex of interpolymer XV (3) 0.5 part chain terminated copolymer XVI as a 25 solids latex (1) parts acetylated amylopectin (National 1135 Starch) (2) 60 parts of a 25 solids latex of interpolymer XV (3) 20 parts of a 25% solids latex of interpolymer XVI The above formulations may be used in any convenient concentration in a bath spray, roller padder or aerosol method of application. Generally concentrations are selected to give a solid pick-up based on the material treated of between 0.1% to 10% by weight. Since in order to obtain uniform treatment of a textile, it is desirable to have from about 1 to 200% and preferably from about 25 to 100% wet pick-up the concentrations of active components in the treating composition for the preferred pickup will vary from about 40% down to 0.1%. Clearly, such concentrations are not critical and are subject to the wide variation and great latitude indicated above.
In the preferred and most convenient method of application by the consumer of the compositions of this mention i.e., aerosol method, the aqueous compositions are formulated with a suitable propellant. These include trichloromonofluoromethane, dichlorotetrafluoroethane, dichloromonofluoromethane, monochlorotrifluoromethane, isobutane,
difluoroethane,
n-butane,
propane,
1 ,1, l-difluoro chloroethane, 1,1,1-cyclobutane,
carbon dioxide,
nitrous oxide.
In general the propellants are water-immiscible or only slightly soluble in water with vapor pressures at 70 F. of from about 0.2 to about 500 ps./g. The selection of a suitable propellant or mixture of propellants will, of
course, depend on the type of package to be used the specific nature of the composition to be dispensed and the spray pattern desired among others. Where lower pressures are to be maintained in the package it may be desirable to use a propellant of slight Water solubility to aid in dispensing the product after it leaves the nozzle.
The preferred propellants are the low density compounds and mixtures of low density which form a separate and upper liquid phase in the aerosol package providing thereby a three-phase system. While it is not intended to foreclose the use of higher density propellants (i.e., higher than the aqueous latex phase) in which case the propellant will be on the bottom in the aerosol package, this is not preferred because of the inadequacies of the mechanics of the package required for dispensing such compositions and further because other means for making such systems workable (i.e. shortened dip tube) create undesirable economic factors (eg cannot discharge a high percent of the active ingredients). In order to achieve the benefits of this invention, however, any technique aerosol or otherwise may be employed notwithstanding the fact that the optimum results may be obtained with certain specific formulations and techniques and these might, in general, be preferred especially by the housewife.
The amount of propellant as well as the specific one or ones used will vary depending upon the pressure limitations on the package and the spray pattern desired. Generally from 5 to 25 by weight of propellant circumscribes the practical range thereof, and as pointed out above, among these the low density, medium vapor pressure hydrocarbons such as isobutane are preferred.
As previously pointed out many othe adjuvants may be used in the compositions of this invention, some with particularly noteworthy results. Thus incorporation of a polyethylene emulsion in amounts ranging from 10% to 300% by weight based on the weight of fluoropolymer gives rise to unique ironing characteristics to textiles sprayed with such modified embodiments. Siloxane emulsions for similar purposes are also contemplated.
The following examples will serve to illustrate the present invention without being deemed limitative thereof. Parts are by weight unless otherwise indicated.
EXAMPLE 1 Example 1 is repeated except that the fiuoropolymer used is a terpolymer containing 2.5% n-butyl acrylate and 0.5% N-methylol acrylamide. The results are somewhat superior to those of Example 1.
EXAMPLE 3 Example 1 is repeated using the following fluoropolymers (as 25 solids latex):
(a) 1H,1H-nonadecafluorodecyl methacrylate (b) n-butyl acrylate (5%) (a) 1H,lH,9H-hexadecafiuorononyl acrylate (98%) (b) 2-ethyl hexyl acrylate (2%) (a) 1H,1H,7H-dodecafiuoroheptyl methacrylate (95%) (b) n-butyl acrylate (a) 1H,H1H,2H,2H tridecafluorooctyl methacrylate (b) n-butyl acrylate (2%) (c) N-methylol acrylamide (0.5%)
(a) 1H,1H,2H,ZH-tridecafluorooctyl methacrylate (97%) (b) n-butyl acrylate (2%) (c) dodecyl mercaptan (1%) (a) 3 parts D (b) 1 part B The products A-D are of relatively high molecular Weight with K values of from about 30 to 50 while E is a chain terminatedrelatively low molecular weight material of K=12.
The results achieved with products A-F are comparable to Example 1 but upon subsequent laundering the textiles treated as in Examples 1, 2 and 3A-3D and 3F retain considerable oil and water repellent porperties albeit they are no longer crisp or sized with the starch while the textile treated with 3E loses most of its repellent characteristics.
This demonstrates the excellent water and oil repellent characteristics of the compoistions of this invention. The advantage of composition 3F lies in its unusual and unexpected improved laundering characteristics, as hereinafter demonstrated.
EXAMPLE 4 Swatches of 80 x 80 cotton are sprayed with the composition of Example 1 to give a 50% wet pick-up and ironed at 400 F. 33 sec./ft. to dryness. Excellent water and oil repellency results. The swatches are then artificially soiled as described below and then laundered. Untreated swatches are also soiled in a similar manner and laundered. The untreated samples launder better (i.e. as measured on a Photovolt Reflectance Meter) than the treated swatches. This demonstrates that while the composition of Example 1 gives excellent water and oil rcpellency and as will be evident in further examples also gives excellent repellency to both water and oil borne stains, such treated materials, although more resistant to soiling nevertheless once they are soiled, do not launder as well as an untreated textile. The soiling procedure is as follows:
No official test has been recognized for the purpose of testing the effect of particulate household articles and the effect of various treatments in resisting such a soil but it has been found that the following procedure employing a standardized synthetic soil provides reproducible results.
The standardized soil is prepared by the method described in Salisbury et al. Soil Resistant Treatment of Fabric, American Dyestuff Reporter, Mar. 26, 1956, page 199. The test using the standardized soils is as follows:
Locate the tumbling device 1 in a conditioning room. Use 4 replicates per treatment (usually four) and 3 each for Washed and Untreated Control cotton washed with commercially available detergent Fab Randomize by tumbling in unheated dryer. A total of twenty-two (22) conditioned specimens (5" x 7", 80 x 80 cotton) are tumbled 1320 revolutions with Synthetic Soil 1 Tumble Jar Dynamic Absorption Tester [See A ATCC Test Method (Tentative) 70B-1961T] Andrew Technical Supply Co. 2540 E. Wood, Evansto-n, I11.
2 Colgate-Palmolive Company, New York, N.Y.
8 Synthetic soil prepared by the method described by Salisbury et al., Soil Resistant Treatment of Fabric" American Dyestuif Reporter, Mar. 26, 1956, page 199,
O.W.F.). The end-over-end tumbling is carried out in a 6" diameter by 12' long cylindrical stainless steel jar rotating at 43 r.p.m. Six (6) No. 8 Neoprene rubber stoppers (average weight 41.5+0.5 gram) are distributed evenly with the soil among the specimens. After tumbling, the specimens are removed and each shaken 15 times by hand to remove free soil by holding one corner 8 times and the diagonally opposite corner 7 times. Each swatch is cut in half after repellency reflectance readings to produce two 5" x 3 /2" pieces (22 pairs total). Twenty-two swatches, one from each pair, are washed in an automatic Washer using 50 grams of Fab in the cotton cycle with 5 pounds additional dummy load and then dried 5 minutes in an automatic dryer at the high setting and lightly hand ironed.
The degree of soil before and after washing is determined with the Photovolt Reflectance Meter The meter is standardized by placing the probe head on a block of MgCO (freshly ground against an identical block); then readings are taken on a porcelain plate used as a secondary standard. Readings using the Model 610Y probe with tri-blue filter and the Model 610D probe with tri-green filter have proved comparable with synthetic soil. Eight readings are taken with small probe and 6 readings with the large probe (610D) and the average value is reported.
COMPOSITION OF SYNTHETIC SOIL Percent- Ingredrent age Supplier Peat moss 38 Michigan Peat, Inc. Capac, Mich. Cement 17 Portland Cement.
Kaolin clay, peerless 17 Silica (200 mesh) 17 Molacco furnace black.... 1. 75
Ave, N .Y
0. 50 0.1:. Williams 00., Easton ,Pa. 8.75 Standard Oil Co. of New Jersey, Elizabeth, NJ.
R11. Vanderbilt C0,, Park Ave, N.Y. Davidson Chem. Corp., Baltimore, Md. Columbia and Carbon, 380 Madison Red iron oxide N-1860- Mineral oil (Nujol) EXAMPLE 5 Example 4 is repeated and instead of artificially soiling the swatches with the synthetic dry soil they are stained as follows:
Resistance to common household staining materials was tested by the following method:
(a) The fabrics are stretched lightly on 12" x 31" frames. All or part of the frame area is used depending on the amount of fabric available. The frames are supported at both ends with the fabric about 8" above a bench-top surface. The fabric touches nothing.
(b) 3" medicine droppers are used to draw the stains from their containers. A 1 cc. calibration is established and marked on the exterior of the droppers. The stains are squeezed vertically downward from a height 2" above the cloth.
(0) After 5 minutes the unabsorbed stain is wiped off the fabric with two sweeps of facial tissue (Kleenex) and the stains rated as follows:
STAIN RATINGS Degree of stain: Numerical ratings 4 Kelvinator Home Automatic Washer. 5 Photovolt Corp., 1115 Broadway, New York, N.Y.
(d) Duplicate sets of stains are applied in separate areas so that one-half of the fabric can be washed. The washing is carried out using 50' grams Fab a cotton cycle and a dummy load to total 5 pounds in a Norge Home Automatic Washer.
(e) Stains used.
WATER-HORNE STAINS (1) Instant Tea, Tetley 1 (2) Sheafiers 232 Blue-Black Skrip (3) A&P Concord Grape Juice (4) Ann Page Salad Mustard (5) Bosco Chocolate Syrup TABLE I Water repellency Oil repellency Dry soilrepellency Example Before After Before After Before After Treated 90 80 4 4 30 77 Untreated 0 0 0 25 78 TABLE II Static stain resistance Repelleney Water- Oil- Example borne borne Total After laundering Total Treated 15 17 32 27 18 45 Untreated 3 8 4 6 From the above data it is evident that excellent, durable, water and oil repellencies are achieved with equally outstanding resistance to staining by both waterand oilborne stains. Further, ease of removal of the stains from the treated swatches is shown by the high total value (45 after laundering compared to the low total (10) of the untreated swatches, also after laundering. It will also be noted that dry soil repellencies improved although upon laundering the treated swatch does not quite come back to equal the untreated swacht.
The water-repellency is determined according to the AATCC Standard Test Method 221952.
This test is applicable to any textile fabric. It measures the resistance of fabrics to wetting by a water spray and the results depend primarily on the degree of hydrophobicity inherent in the fibers and yarns and subsequent treatments to which the fabric is subjected. Water is sprayed against the taut surface of a test specimen. Evaluation of the wetted pattern is readily brought about by 1 8 cc. dry Powder/200 cc. water applied at 160 F. B Melted and applied at 160 F. I
comparing the wetter pattern with standard wetting pattern pictures:
Characterized by: Rating No sticking or wetting of the upper surface 100 5 Slight random sticking or wetting of the upper surace 90 Wetting of the upper surface at spray points 8O Partial wetting of the whole of the upper surface 70 Complete wetting of the whole of the upper sur- 10 face 50 Complete Wetting of the whole of the upper and lower surfaces Test specimens of minimum size of 7" x 7" (seven 8 inches by seven inches) are conditioned at 70 F. and 65 percent relative humidity for a minimum of four hours before testing.
The test specimen, fastened securely and wrinkle-free in a metal hoop having a diameter of 6 inches, is placed and centered 6 inches under a standard spray nozzle at an angle of 45 to the horizontal. Two hundred and fifty milliliters of water at 80i2 F. is poured into a funnel attached above the spray nozzle. The spray lasts 25 to seconds at the end of which time the hoop is taken 25 by one edge and the opposite edge tapped smartly once against a solid object with the wet side facing the solid; this procedure is repeated with the hoop reversed 180.
The swatches treated in Example 4 are further characterized by a stiffness rating (Stiffness Handle-O-Meter 30 using a swatch 4" x 4") of 44. An untreated, laundered swatch gives a value of 21 (befor laundering it is 34).
EXAMPLE 6 A composition similar to Example 2 is prepared but 35 there are additionally added 1.3% additional acetylated amylopectin 0.1% interpolymer XVI (from a 25% latex) and Stiffness rating=68.5
This demonstrates the superior oil and water repellent properties and improved static stain and dry soil resistance along with excellent stiffening.
EXAMPLE 7 The treated swatches of Example 6 are laundered and a second treatment is given. The water repellency is found to be 100 both before and after another laundering and the oil repellency is 6 before and 5 after this other laundering.
A concomittant increase in stain repellency is also noted as follows:
Before laundering:
Water-born stains 23.5 Oil-borne stains 23.5
Total 47.5
After laundering:
Water-borne stains 29 Oil-borne stains 25 Total 54 Stiifness rating is 51 indicating no buildup here.
EXAMPLE 8 The procedure in Example 7 is repeated through sprays, each followed by an ironing and a laundering with a final oil repellency value of 7, a stiffness rating before the last laundering of 53.5 (note, again, no buildup of stiffness), stain, dry soil repellency, and stain and soil removal equivalent to that shown in Example 6.
The aforedescribed examples clearly illustrate excellent oil and water-repellent properties, after treatment,
and slow buildup to, an, almost, optimum condition, after several treatments. Added advantages are to be seen from the excellent stain repellent properties as well as the superior ease of removal of any staining which does occur. Finally the lack of stifiness buildup, albeit, excellent stilfness after each treatment, is a decided plus factor.
EXAMPLE 9 A composition employing the components of Example 6 is prepared as follows: (percent on an active basis) Percent Acetylated amylopectin 3.75 Terpolymer of Example 2 0.30 Interpolymer XVI 0.10 Polyethylene (Example 6) 0.28 Formaldehyde 0.35 Isobutane 6. 17 Water 89.00
balanceminute amounts of surfactants (in fluoropolymer and polyethylene latices) and methanol (in formaldehyde).
This composition is outstanding for dispensing as an aerosol with an excellent spray pattern and no valve clogging. Upon application to fabrics the results are similar to what is described in the previous examples.
EXAMPLE The procedures of Examples 4 and 5 are repeated using the following compositions:
(A) Composition of Example 6 but amylopectin total is 3.3%.
(B) Composition of Example 6 but terpolymer of Example 2 concentration is .23% and interpolymer XVI concentration is 0.08%.
(C) Composition similar to Example 9 but in place of the terpolymer of Example 2 an equal weight of polymer XV is employed. Excellent results, comparable to what is obtained in the other example, are noted.
EXAMPLE 11 A composition is prepared containing:
Percent Amylopectin (of Example 1) 2.67 Polyethylene (of Example 9) 0.3 Interpolymer XVI 0.3 Isobutane 6.2
Balancewater.
Swatches are sprayed and ironed, then tested as in Examples 4 and 5 with the following results:
Oil repellency: 5. Water repellency: 80.
Water-borne strain repellency 15 Oil-borne stain repellency 19 Total 34 14 After laundering:
Water-borne stains 25 Oil-borne stains 20 Total 45 Additional sprayings anlaunderings are carried out until there have been 5 sprays and 4 launderings and a final ironing. The results are:
Oil repellency: 4. Water repellency: 80.
Water-borne stain repellency l6 Oil-borne stain repellency 17 Total 33 After laundering:
Water-home stain repellency 26 Oil-borne stain repellency 18 Total 44 This example demonstrates that the composition used gives excellent oil and water-repellency as well as fine stain resistance but no build up in these properties with repeated use and launderings between each application.
EXAMPLE 12 In the following table various aqueous compositions are set forth which give excellent oil and water repellency, outstanding dry soil resistance and a highly desirable stifiness to cotton textiles treated therewith. The balance of the composition is water. As in the previous example the polymers are in latex form.
Starch Fluoropolymer Other resins (A) 67 amylopectin 0.57 interpoly- 0.057 poly(n-butyl 8i Example 1. min XIII. methaerylate. (B) do dp 0.1% polystyrene. (C) 2% amylopectin 0.2% interpoly- 0.2% polystyrene.
of Example 1. mer II. (D) 6% amylopectin 0.5% interpoly- 0.3% polyethylene, 1.0%
of Example 1. mer XIII. urea-formaldehyde crease-proofing agent.
'EXAMPLE 13 Example 9 is repeated except that the propellant and amount thereof is varied as follows: (with a corresponding change in percent water) EXAMPLE 14- Example 1 is repeated using the following water-soluble carbohydrates in the indicated amounts. Where more or less than 2.7% is used, there is a corresponding change in the water present:
Percent (A) Thin boiling wheat starch--fiuidity 87 2.0 (B) Thin boiling wheat starch--fiuidity 87 5.2 (C) Thin boiling wheat starchfluidity 98 8.2 (D) Modified cornstarch-fluidity 3.1 (E) Modified cornstarchfluidity 75 6.2 (F) Sulfated amylopectin(l8 oz. starch) 7.0 (G) Oxyethylated starch-fluidity 2.8
The results are comparable to "Example 1.
1 5 EXAMPLE Example 1 is again repeated except that the fluoropolymer used and the amount thereof are as follows:
, Percent (A) Copolymer I 0.14 (B) Copolymer I 0.03 (C) Copolymer I 1.4
(D) Homopoly-1H,1H-perfluorodecyl methacrylate Example 9 is repeated using in place of the terpolymer of Example 2 and interpolymer XVI, the following in the indicated amounts:
Percent (A) Copolymer I 0.14 (B) Copolymer I 1 0.14+0.05 (C) Interpolymer XV 0.6 (D) Interpolymer XV .1 0.9 (E) Interpolymer XV 0.14 (F) Interpolymer XV-interpolymer XVI 0.6+0.4 (G) Interpolymer XV-interpolymer XVI 0.3+0.3 (I-I) Interpolymer XV 0.3+0.1
Chain terminated interpolymer similar to XVI but perfluoro compound is CHF2(CF2)7CH2O (Ill-0:011
2 Chain terminated homopolymer similar to XIV but absent the n-butyl acrylate.
EXAMPLE 17 Example 9 is repeated except that the aceylated amylopectin is replaced by the following carbohydrates in the recited amounts:
Percent (A) Modified cornstarch-fluidity 60 2.2 (B) Modified cornstarch-fluidity 60 7.5 (C) Modified cornstarch-fluidity 75 5.0 (DYModified cornstarch-fluidity 75 1.5 (E) Thin boiling wheat starch-fluidity 87 5.0 (F) Oxyethylated starch-fluidity 65 3.75 (G) Gelatinized starch-fluidity 8O 2.5
EXAMPLE 18 Examples 16A-16H are repeated using the starches of 17A-17G in the following amounts:
TABLEContinued Polymer example Example CHOU)! GGGGGGGGSSGGSGGGGSGS wown'emuomzwamuomem mu EXAMPLE 19 Example 9 is again repeated except that the ployethylene emulsion is replaced by the following in separate formulations:
Percent (A) Dimethyl silicone emulsion (30% solids) 1 (B) Vinyl acetate (70%): vinyl stearate (20%) co polymer emulsion (25% solids) 1.5 (C) Polybutadiene emulsion (10% solids) 1 (D) Poly-2,3-dichlorobutadiene latex (5% solids) 5 (E) Melamine-formaldehyde crease resistance composition (40% solids) 2 In each instance outstanding results are obtained.
As the above examples illustrate, the compositions of this invention produce excellent sizing along with unique water and oil-repellency on textiles. The compositions may be applied to the textile in any convenient manner although they are most superior when used in an aerosol form. Where the propellant in these compositions in denser than the aqueous components, the package structure will, obviously, vary from those packages or container used with propellants which are less dense and form an upper, discrete liquid phase. Regardless of these variations, however, excellent properties are forthcoming in all instances.
Many substances may be added to the compositions of this invention, as pointed out above, and as will be obvious to one skilled in the art, the parameters are extremely varied, particularly in view of the fact that none of the additives need be soluble either in water or the selected propellant. Where it is desired, a compound may be added as a solution in a suitable solvent and such solution added to the aqueous compositions producing in most instances a dispersion of the said compound in the compositions. Many other variations will be apparent and it is clear that these may be resorted to without departing from the spirit and scope of this invention and that the specific embodiments 5 Out herein are in no way limitative thereof.
We claim:
1. A containerized selfpropelling aqueous textile treating composition which imparts simultaneously stilfening and oil and water repellency which comprises (A) a water-soluble starch,
(B) a terpolymer in the form of a latex comprising (1) a polymerizable thermoplastic perfluoroalkylethylmethacrylate of the formula wherein X is selected from the group consisting of hydrogen, C, to C alkyl, chlorine and fluorine; X is selected from the group consisting of hydrogen, chlorine and fluorine, n has a value of 3 to 30; and at least 70%, but at least 6, of the X's are fluorine; (2) butylacrylate, and (3) N-methylol acrylamide; and, (C) propellant selected from the group consisting of hydrocarbons, halogenated hydrocarbons, and mixtures thereof;
wherein the ratio of starch to terpolymer is 2:1 to 20:1, and wherein said water-soluble starch is from 1 to 10% and said propellant is from 5 to 25% by weight of total composition.
2. A composition as defined in claim 1 wherein also present in the form of a latex is a copolymer of perfluoroalkylethylmethacrylate and butyl acrylate prepared in the presence of a chain transfer agent, and wherein the ratio of terpolymer to copolymer is 3:1.
3. A composition as defined in claim 2 wherein said starch is acetylated amylopectin and said chain transfer agent is dodecyl mecaptan.
References Cited OTHER REFERENCES R. W. Kerr: Chemistry and Industry of Starch, 2nd ed. Academic Press (1950).
WILLIAM H. SHORT, Primary Examiner E. A. NEILSEN, Assistant Examiner US. Cl. xx. 1 17-4 355
US00631167A 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition Expired - Lifetime US3809663A (en)

Priority Applications (14)

Application Number Priority Date Filing Date Title
US00631167A US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition
DE19681769112 DE1769112A1 (en) 1967-04-17 1968-04-05 Textile treatment agents
AT03399/68A AT291929B (en) 1967-04-17 1968-04-08 TEXTILE TREATMENT PRODUCTS
DK156168AA DK124414B (en) 1967-04-17 1968-04-08 Means for stiffening textile material and for making it water and oil repellent.
CH1193268D CH1193268A4 (en) 1967-04-17 1968-04-09
CH1193268A CH535317A (en) 1967-04-17 1968-04-09 Process for starching and for the simultaneous water and grease repellent finishing of textile materials
CH535268A CH476149A (en) 1967-04-17 1968-04-09 Textile treatment agents
NO01421/68A NO129914B (en) 1967-04-17 1968-04-16
ES352792A ES352792A1 (en) 1967-04-17 1968-04-16 Textile sizing,water and oil repellent composition
IE442/68A IE31874B1 (en) 1967-04-17 1968-04-17 Textile sizing,water & oil repellent compositions
GB08134/68A GB1217590A (en) 1967-04-17 1968-04-17 Textile sizing, water & oil repellent compositions
NL6805432A NL6805432A (en) 1967-04-17 1968-04-17
BE713777D BE713777A (en) 1967-04-17 1968-04-17
FR1561678D FR1561678A (en) 1967-04-17 1968-04-17

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US00631167A US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition

Publications (1)

Publication Number Publication Date
US3809663A true US3809663A (en) 1974-05-07

Family

ID=24530056

Family Applications (1)

Application Number Title Priority Date Filing Date
US00631167A Expired - Lifetime US3809663A (en) 1967-04-17 1967-04-17 Textile sizing,water and oil repellent composition

Country Status (12)

Country Link
US (1) US3809663A (en)
AT (1) AT291929B (en)
BE (1) BE713777A (en)
CH (3) CH1193268A4 (en)
DE (1) DE1769112A1 (en)
DK (1) DK124414B (en)
ES (1) ES352792A1 (en)
FR (1) FR1561678A (en)
GB (1) GB1217590A (en)
IE (1) IE31874B1 (en)
NL (1) NL6805432A (en)
NO (1) NO129914B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070059537A1 (en) * 2003-11-21 2007-03-15 Peter Hupfield Polymeric products useful as oil repellents
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT299121B (en) * 1968-06-19 1972-06-12 Colgate Palmolive Co Preparations for finishing textiles and making them grease and water repellent
EP0079143A3 (en) * 1981-10-20 1984-11-21 Adnovum Ag Pseudoplastic gel transfer
US6159548A (en) * 1998-09-24 2000-12-12 Moody; Richard J. After-treatment method for oil-and water-repellency of fibrous substrates

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20070059537A1 (en) * 2003-11-21 2007-03-15 Peter Hupfield Polymeric products useful as oil repellents
US7645518B2 (en) * 2003-11-21 2010-01-12 Dow Corning Corporation Polymeric products useful as oil repellents
US7855264B2 (en) 2003-11-21 2010-12-21 Dow Corning Corporation Polymeric products useful as oil repellents
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9133584B2 (en) 2012-01-17 2015-09-15 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
US9499943B2 (en) 2012-01-17 2016-11-22 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom

Also Published As

Publication number Publication date
DE1769112A1 (en) 1971-06-03
GB1217590A (en) 1970-12-31
ES352792A1 (en) 1969-09-01
FR1561678A (en) 1969-03-28
NO129914B (en) 1974-06-10
NL6805432A (en) 1968-10-18
IE31874L (en) 1968-10-17
CH1193268A4 (en) 1972-10-13
IE31874B1 (en) 1973-01-24
CH535317A (en) 1973-03-31
CH535268A4 (en) 1969-09-15
AT291929B (en) 1971-07-15
CH476149A (en) 1969-09-15
BE713777A (en) 1968-09-16
DK124414B (en) 1972-10-16

Similar Documents

Publication Publication Date Title
US3356628A (en) Copolymers of perfluoro acrylates and hydroxy alkyl acrylates
US3462296A (en) Fluorinated oil- and water-repellent copolymer and process for treating fibrous materials with said copolymer
US3068187A (en) Process for preparing block and graft copolymers of perfluoroalkyl monomer and resulting product
CA1096098A (en) Copolymers containing perfluoroalkyl groups
US3393186A (en) Perfluoro-alkenylacrylates and polymers thereof
US6159548A (en) After-treatment method for oil-and water-repellency of fibrous substrates
CN111032816B (en) Water-repellent composition
US3329661A (en) Compositions and treated articles thereof
CN107709508B (en) Water repellent composition, method for producing water repellent composition, and article
US3459696A (en) Water-repellent compositions
CN101679834A (en) Antifouling composition, process for producing the same, and processed article
US3637614A (en) Solvent soluble dry soil resistant fluoropolymers
US3546187A (en) Oil- and water-repellent polymeric compositions
US3644241A (en) Antisoiling aerosol starch prepared from ethoxylated starch and a fluoroacrylate or fluoroalpha substituted acrylate polymer
JPS6042270B2 (en) Fluorinated products and their production methods
US3529995A (en) Fluorine-containing copolymer treated fabrics
US3849521A (en) Oil-and water-repellent composition comprising a polymer containing fluoroalkyl monomer units and an additive copolymer
US3595944A (en) Oil- and water-repellent fluorine-containing compositions
US3594353A (en) Novel ester polymers
US3809663A (en) Textile sizing,water and oil repellent composition
WO2013058334A1 (en) Fluorine-containing composition
US3090704A (en) Antistatic and antisoiling agent and process for treating synthetic linear textile therewith
JPS5947716B2 (en) Organic solution type water and oil repellent with excellent durability
JP5397521B2 (en) Fluorine-containing composition and fluorine-containing polymer
US3657173A (en) Oil and water repellent compositions