US3813359A - Starch-fluoro polymer textile sizing,water and oil repellent composition - Google Patents

Starch-fluoro polymer textile sizing,water and oil repellent composition Download PDF

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Publication number
US3813359A
US3813359A US00223735A US22373572A US3813359A US 3813359 A US3813359 A US 3813359A US 00223735 A US00223735 A US 00223735A US 22373572 A US22373572 A US 22373572A US 3813359 A US3813359 A US 3813359A
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US
United States
Prior art keywords
starch
water
oil
compositions
stain
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
US00223735A
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English (en)
Inventor
R Hunter
H Marder
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
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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
Priority to AT567569A priority Critical patent/AT299121B/de
Priority to GB30874/69A priority patent/GB1270029A/en
Priority to BE734734D priority patent/BE734734A/xx
Priority to CH932869A priority patent/CH514721A/de
Priority to FR6920276A priority patent/FR2011206B1/fr
Priority to NL6909363A priority patent/NL6909363A/xx
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Priority to US00223735A priority patent/US3813359A/en
Application granted granted Critical
Publication of US3813359A publication Critical patent/US3813359A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—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
    • 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

Definitions

  • the present invention relates to a new and outstanding textile treating composition and particularly to compositions of the type normally used preparatory to ironing textiles.
  • the compositions serve primarily to size and impart waterand oil-repellency.
  • sizing is meant the ability to stiffen the textile and in many instances to add gloss to the textile surface.
  • starch as a size and stiffening agent for textile materials is probably as old as textile 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.
  • 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 aifords control by the consumer of these characteristics by virtue of the non-durability between washings of this finish, but also provides Water and oil repellency which is non-durable in nature.
  • a starch composition i.e., a starch composition
  • compositions of the present invention comprise as the essential ingredients thereof, a Water soluble or water dispersible sizing material, which is a polysaccharide as exemplified by the various natural starches and the various starch derivatives such as oxidized starches, acylated starches, starch ether, hydrolyzed starches, enzyme-treated starches and the like.
  • the starch composition is in combination with a thermoplastic film-forming fluorocarbon polymer as hereinafter described.
  • thermoplastic film-forming fluorocarbon polymer as hereinafter described.
  • additives which do not adversely affect the attainment of non-durable stiffening along with non-durable water and oil repellency.
  • additional materials include anti-stick agents such as the siloxane resins, polyethylene 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 fiber-reactive 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 fluorinated methanes, ethanes, and the like, such as dichlorodifluoro methaneand the like.
  • the propellant is a suitable low boiling hydrocarbon or halogenated hydrocarbon as exemplified by methylchloride, methylenechloride, isobutane and the various chlorinated fluorinated methanes, ethanes, and the like, such as dichlorodifluoro methaneand the like.
  • the non-durable 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 cookup type starch and is illustrative of the preferred class of products of high fluidity, i.e., 30 to (intrinsic viscosity of from 1.0 to 0.3).
  • Other starch products which may be employed include the following: 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 10% thereof based on the total weight of the aerosol formulation may be used. More important than the specific amount of size 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 non-durable stiffening action is obtained which does not interfere with the provision of excellent repellent characteristics.
  • the fiuoropolymer component of the compositions of this invention comprise a thermoplastic polymeric material having a molecular weight of less than 3 0,000 in the form of an emulsion, known as 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 from monomers in the present invention comprise the general class of the perfluoro acrylates and alpha-substituted acrylates, such as methacrylates, all having in common the fact that they are of a low molecular weight.
  • fluoro polymers are prepared from the corresponding monomers but include a chain transfer agent, e.g., alkanethiol, such as dodecyl mercaptan, to terminate the polymer.
  • chain transfer agent e.g., alkanethiol, such as dodecyl mercaptan
  • 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 poly merizable vinyl compounds, said interpolymer containing at least 25 mole percent of fluoro monomer.
  • 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; decylvinyl ether; octadecyl vinyl ether; benzyl vinyl ether; phenyl vinyl ether; and divinyl ether;
  • alkyl vinyl ketones (alkyl C to C alkyl acrylates (alkyl C to C alkyl methacrylates (alkyl C to C vinyiidene halides acrylic acid acrylonitrile acrylamide N-methylol acryiamide; 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 alkanedieic acids and the like.
  • resin emulsions may be added to the compositions of this invention to give special benefits.
  • a typical low molecular weight fiuoro polymer product is prepared from the following: (polymerization run at 70 C. for 5 hours).
  • the formulations of the present invention 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 wet pick-up the concentrations of active components in the treating composition for the preferred pick up 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, dichlorotetrafiuoroethane, dichloromonofluoromethane, monochlorotrifluoromethane, rochloroethaue, 1,1,l-cyclobutane, car-bondioxide, nitrous oxide.
  • propellants are Water-immiscible or only slightly soluble in water with vapor pressures at 70 F. of from about 0.2 to about 500 p.s./g.
  • vapor pressures at 70 F. of from about 0.2 to about 500 p.s./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 ma 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 separate 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 (e.g., 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 3% 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 or poly 1,3-dichlorobutadiene emulsion in amounts ranging from to 300% by weight based on the weight of fluoropolymer gives rise to unique ironing characteristics to textiles sprayed with such modifiedembodiments as will be seen hereinafter.
  • EXAMPLE H 20 parts acetylated amylopectin (National 1135 starch) 1 part chain terminated copolymer as a 25% solids latex as produced at (A) above.
  • the resultant was compounded to produce an aqueous formulation of 10% starch, 5% fluoro polymer, 7% isobutane as the propellant.
  • Example VIII is considered a control so that in the following test method the tested swatches were not treated.
  • the fluoro polymer in the above was of the low molecular weight type produced in accordance with A in the above.
  • the acrylic emulsion used in Example III is further identified as Rhoplex B-15, a product of Rohm and Haas Co.
  • the aerosol preparations of Examples III to VII are used in the uniform spraying to wetness of white cotton 6. swatches having an x 80 count so that there is a 50% wet pick up. The swatches are heat cured in a conventional manner as by ironing at 400 F. at a rate of about 33 seconds/foot to dryness.
  • the test technique employs three water borne stains, namely, (1) chocolate milk, (2) black coffee, and (3) imitation Coke; and three oil borne stains, namely, (4) flue dyed corn oil, (5) French dressing, and (6) blue dyed petroleum oil.
  • the staining materials mentioned in the above have the following compositions:
  • the coffee solution is allowed to cool until it reaches 70*- 80 F.
  • the stain should not be kept for more than eight hours.
  • Coke syrup 50 Isopropanol 50
  • Water 4 Blue dyed corn oil 0.40 g. blue dye is added to 400 g. corn oil with stirring and heat in order to obtain a uniform solution.
  • Blue dyed petroleum oil 250 g. of oil are mixed with 0.1% blue dye by weight of the oil. The mixture is agitated and warmed in order to obtain a uniform solution.
  • the test in the instant case is a static stain repellency test in that the fabric surface is given a minimum disturbance.
  • the temperature of the stain materials is between 70-80 F.
  • a piece of white fabric approximately 7 inches by 7 inches is placed on blotting paper on a hard surface.
  • 1% cc. of each test stain is carefully placed (not dropped) in separate areas on the fabric.
  • the excess stain material, if any, is removed using a vacuum suction line without coming in physical contact with the stained surface.
  • the stained area is brushed twice lightly in opposite directions with a straight motion of a dry absorbent tissue to remove any unabsorbed stain material.
  • the stains are rated against the white background of a clean blotter. Ratings of 1 through 5 are arrived at strictly on size (relative spread) of an individual stain while rating 6 through 10 determines relative wetting as measured by intensity of the stain against a standard.
  • the three water borne stains are added together to give a possible maximum of 30.
  • the oil borne stains are added to give a maximum possibility of 30. These may then be totalled for a maximum of 60.
  • the stained fabrics are dried 24 hours. Laundering is then carried out by washing in an automatic washer with a quantity of a conventional detergent. The fabrics are then dried in an automatic dryer at the appropriate setting for the fabric type. They are then lightly dry ironed (stain side down) at the appropriate fabric setting.
  • the rating of launderability of stains is based on the same 1-10 system used for the static stain repellency tests. Again, it will be noted that the maximum rating after adding the results of the water borne stains will be 30, and similiarly 30 will be the total results regarding the oil borne stains. These two may be added together.
  • Example I 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:
  • compositions of I this invention produce excellent sizing along with unique waterand oil-repellency on textiles.
  • the compositions may be applied to the textiles in any convenient manner although they are most superior when used in an aerosol form.
  • the propellant in these compositions is more dense than the aqueous components
  • the package structure will, obviously, vary from those packages or containerused with propellants which are less dense than and form an upper discrete liquid phase. Regardless of these variations, however, excellent. properties are forthcoming in all instances.
  • a containerized, non-durable, aqueous aerosol textile treating composition for sizing and rendering a textile oil and water repellent consisting of,

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US00223735A 1968-06-19 1972-02-04 Starch-fluoro polymer textile sizing,water and oil repellent composition Expired - Lifetime US3813359A (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
AT567569A AT299121B (de) 1968-06-19 1969-06-16 Mittel zum Appretieren und Fett- und Wasserabweisendmachen von Textilien
GB30874/69A GB1270029A (en) 1968-06-19 1969-06-18 Textile sizing, water-and oil-repellent compositions
BE734734D BE734734A (cs) 1968-06-19 1969-06-18
CH932869A CH514721A (de) 1968-06-19 1969-06-18 Wässriges Textilbehandlungsmittel
FR6920276A FR2011206B1 (cs) 1968-06-19 1969-06-18
NL6909363A NL6909363A (cs) 1968-06-19 1969-06-19
US00223735A US3813359A (en) 1968-06-19 1972-02-04 Starch-fluoro polymer textile sizing,water and oil repellent composition

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US74043768A 1968-06-19 1968-06-19
US00223735A US3813359A (en) 1968-06-19 1972-02-04 Starch-fluoro polymer textile sizing,water and oil repellent composition

Publications (1)

Publication Number Publication Date
US3813359A true US3813359A (en) 1974-05-28

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US00223735A Expired - Lifetime US3813359A (en) 1968-06-19 1972-02-04 Starch-fluoro polymer textile sizing,water and oil repellent composition

Country Status (7)

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US (1) US3813359A (cs)
AT (1) AT299121B (cs)
BE (1) BE734734A (cs)
CH (1) CH514721A (cs)
FR (1) FR2011206B1 (cs)
GB (1) GB1270029A (cs)
NL (1) NL6909363A (cs)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6163771A (ja) * 1984-08-17 1986-04-01 ミネソタ　マイニング　アンド　マニユフアクチユアリング　コンパニー 耐汚染性および垢剥離性を有する洗濯可能な織物用サイジング
US8771470B2 (en) * 2012-01-17 2014-07-08 Agc Chemicals Americas, Inc. Method of preparing a treated article and treated article formed therefrom
CN117487083A (zh) * 2023-11-24 2024-02-02 南通和顺兴纺织科技有限公司 一种纺织浆料组合物及其制备方法和应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000061697A1 (fr) * 1999-04-12 2000-10-19 Daikin Industries, Ltd. Repulsif en poudre pour eau-huile : procede de fabrication et utilisations

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3809663A (en) * 1967-04-17 1974-05-07 Colgate Palmolive Co Textile sizing,water and oil repellent composition

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6163771A (ja) * 1984-08-17 1986-04-01 ミネソタ　マイニング　アンド　マニユフアクチユアリング　コンパニー 耐汚染性および垢剥離性を有する洗濯可能な織物用サイジング
US4624889A (en) * 1984-08-17 1986-11-25 Minnesota Mining And Manufacturing Company Launderable textile sizing having stain resistance and soil release
EP0172017A3 (en) * 1984-08-17 1988-07-06 Minnesota Mining And Manufacturing Company Launderable textile sizing having stain resistance and soil release
JPH0641669B2 (ja) 1984-08-17 1994-06-01 ミネソタ マイニング アンド マニユフアクチユアリング コンパニー 耐汚染性および垢剥離性を有する洗濯可能な織物用サイジング
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
CN117487083A (zh) * 2023-11-24 2024-02-02 南通和顺兴纺织科技有限公司 一种纺织浆料组合物及其制备方法和应用

Also Published As

Publication number Publication date
CH932869A4 (cs) 1971-12-15
FR2011206A1 (cs) 1970-02-27
GB1270029A (en) 1972-04-12
FR2011206B1 (cs) 1974-02-01
BE734734A (cs) 1969-12-01
AT299121B (de) 1972-06-12
NL6909363A (cs) 1969-12-23
CH514721A (de) 1971-12-15

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