US3112241A - Process of imparting oil-repellency to solid materials, and materials thus produced - Google Patents

Process of imparting oil-repellency to solid materials, and materials thus produced Download PDF

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US3112241A
US3112241A US53884A US5388460A US3112241A US 3112241 A US3112241 A US 3112241A US 53884 A US53884 A US 53884A US 5388460 A US5388460 A US 5388460A US 3112241 A US3112241 A US 3112241A
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Prior art keywords
paper
oil
pulp
phosphate
repellency
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US53884A
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Mackenzie Alau Kenneth
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to US53884A priority Critical patent/US3112241A/en
Priority to US53885A priority patent/US3096207A/en
Priority to FI1530/61A priority patent/FI40279B/fi
Priority to DEP27822A priority patent/DE1260059B/de
Priority to GB31993/61A priority patent/GB939902A/en
Priority to FR872469A priority patent/FR1305612A/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81—Coating or impregnation
    • C04B41/82—Coating or impregnation with organic materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/466—Halogenated compounds, e.g. perfluor-compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/06—Phosphorus compounds without P—C bonds
    • C07F9/08—Esters of oxyacids of phosphorus
    • C07F9/09—Esters of phosphoric acids
    • C07F9/091—Esters of phosphoric acids with hydroxyalkyl compounds with further substituents on alkyl
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • C11D1/006—Surface-active compounds containing fluorine and phosphorus
    • 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts 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
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
    • 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
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/10—Phosphorus-containing compounds
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03—Non-macromolecular organic compounds
    • D21H17/05—Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/11—Halides

Definitions

  • polyfluoroalkyl phosphate linear cationic polymer Pulp slurry i Screen of paper machine Paper drier and finisher
  • solid material hereinabove I mean water-insoluble materials customarily employed in the manufacture of articles of utility, for instance textile fabric, textile yarns, leather, paper, plastic sheeting, wood, ceramic clays, as well as manufactured articles prepared therefrom such as articles of apparel, wall paper, paper bags, cardboard boxes, porous earthenware, etc.
  • oil repellency for the purpose of definiteness, I shall refer hereinafter to the quality of repelling, under the standard tests herein discussed, a light mineral oil such as a commercial liquid hydrocarbon or a vegetable oil such as peanut oil.
  • the materials treated according to this invention are found to possess repellency to oils, greases and fats generally, regardless of their origin (as for instance, mineral, vegetable or animal kingdom) or their consistency.
  • a special further object of this invention is to modify the mode of application of certain types of oil-repellency agents whereby to intensify their quality of exhausting from an aqueous treatment bath onto the solid material being treated.
  • a particular further object, which is in effect a corollary of the last mentioned object, is to provide a method for rendering paper oil-repellent which can be applied to the paper pulp prior to sheet formation, whereby a more uniform, more effective and more economical impregnation may be achieved.
  • Another corollary object is to provide as a novel article oil-repellent paper in which the oil-repellent factor is distributed essentially uniformly throughout the volume of the paper instead of being restricted to the surface or superficial layers thereof.
  • Oii-repellency in articles such as wearing apparel, cardboard boxes, paper bags or wrapping paper is a relatively young and not fully developed art.
  • the demand for such articles is perhaps old enough.
  • the advantages of having for instance grease-repellent overalls for mechanics, wallpaper that does not stain easily, oilrepellent paper bags for bakery goods, or-on the contrarycontainers which will keep the contents safe against contamination with greasy soil from the outside, are so obvious as not to require much elaboration. Hitherto, however, the solution to this problem has not been entirely satisfactory from the economical viewpoint.
  • Some of the oil-repellency agents hitherto used or suggested are complicated and costly chemicals. Others can be applied only from an organic solvent. Still others are relatively inefiicient and require application of large quantities thereof with respect to the Weight of the fiber or solid material being treated therewith.
  • m is an integer from 3 to 12
  • n is an integer from 6 to 12
  • y is a number of average value from 1.0 to 2.5
  • Z is a member of the group consisting of hydrogen and water-solubilizing cationic ions.
  • the mixtures can be practicably separated, and where the intended use justifies the added cost of separation, the compounds wherein y equals 2 constitute the preferred agents.
  • the compounds defined have also the quality of versatility, being applicable to a wide variety of textile fibers, including cotton, viscose, cellulose acetate, wool, silk, nylon, acrylic fiber and polyester fiber. They are also 3 applicable to leather, paper, wood and unglazed earthenware.
  • a concentrated aqueous bath is generally employed.
  • the fabric is impregnated with the treatment bath and then squeezed until there remains a definite amount of the aqueous liquors in proportion to the weight of the fiber.
  • the fiber may be squeezed to a 100% pickup. In such event, the fiber picks up an equal weight of the treatment bath, and when the padded fiber is dried, there remains inside it (or on it) a percentage weight of the treating agent equal to its original concentration in the treatment bath.
  • the fabric generally extracts the treating agent from the bath, until the latter becomes essentially exhausted.
  • the quantity of agent absorbed by the fiber (provided a sufficient quantity of fiber has been used) is then essentially the entire quantity of agent that had been added to the bath.
  • the quantity of agent therefore, is independent of the quan- 4 tity of water picked up by the fiber (with or without squeezing). In such cases, the quantity of agent initially added to the bath is calculated in advance O.W.F., that is, on the weight of the dry fiber.
  • exhaust treatments are more economical than padding treatments; they permit the use of dilute aqueous baths and are often adapted for use in fields where padding procedures are inapplicable.
  • oil-repellency agent be now added in a quantity corresponding to a few percent by Weight of the paper pulp, it is obvious that its concentration in the aqueous mass will be exceedingly low. So unless the fiber has the quality of drawing the agent out of solution, it is clear that the desired percentage deposit on the fiber cannot practicably be achieved.
  • dialkylarnino alcohols coming into consideration for this purpose include 2(dimethylamino)ethanol, 2 (diethylamino)ethanol, 2-(dipropylamino)ethanol, 2- (N methyl N-cyclohexylamino)ethanol, 2-morpholinoethanol, 2 (diisobutylamino)ethanol, S-(diethylamino) propanol and 4-(diethylamino)butanol.
  • the esters are prepared according to the method set forth in U.S.P.
  • esters may also be converted to acid salts with acids such as acetic, formic or hydrochloric, and polymerized or copolym; erized by known procedure. (See for instance U.S.P. 2,138.762.)
  • Preferred cationic compounds of this group are the polymers derived from the dimethyl sulfate quaternization product or from the acetic acid addition salt of 2-dimethylamino-ethyl methacrylate and Z-diethylamino-ethyl methacrylate.
  • Item 17 Mono(Z-perfluorohexyl-ethyl) ester of phosphoric acid
  • Item .27 bis(l l-perfluoroheptyl-l-undecyl) ester of phosphoric acid
  • Phosphates of polyiluoroalcohols having the structure F(CF (CH OH where r is greater than 2 are prepared hy similar procedure, from l-iodopolyfiuoroalkanes Item Item Item and higher omega-alkenyl acetates such as 4-pentenyl acetate, IO-undecenyl acetate and the like.
  • Oil-Repellency P erccnt by Percent by Rating Volume Volume Iloptane N ujol No resistance to Nujol; i.e. penetration within 3 minutes
  • acceptable ratings are 70 and above, although beneficial effect to oil staining is sometimes obtained with ratings as low as 50.
  • Example 1 Four parts of dry bleached Kraft pulp are agitated vigorously in a vessel containing 300 parts of Water, and 4 parts of an aqueous 1% solution of polymerized 2-(diethylamino)ethyl methacrylate acetic acid salt are added (1% of the polymer on the dry weight of the pulp). Agitation is continued for five minutes (or more), and then 20 parts of an aqueous 1% solution of a mixture of monoand bis(1H,1HJH-dodecafluoroheptyl) phosphate, morpholine salt, having a y-value of about 1.5, are added.
  • Example 2 Example 3 Stock: Unbleached kraft pulp.
  • Cationic polymer Polymer of dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate. Quantity: 0.3% O.W.F.
  • Polyfiuoroalkyl phosphate Ammonium bis(lH,lH,9l-I- hexadecafluorononyl) phosphate. Quantity: 0.3% O.W.F.
  • Oil usedpeanut oil Penetration time-treated sample30 minutes.
  • Example 4 Bleached sulfite pulp beaten to a freeness of 480.
  • Cationic polymer Same as in Example 3. Quantity:
  • Polyfluoroalkyl phosphate A mixture of monoand bis- 1H,lH-pentadecafluorooctyl) phosphate containing 77.3% of the mono phosphate ester; 0.3% O.W.F. Oil penetration test:
  • Oil used--coconut oil Penetration timetreated sample-5 minutes. Controlwithin a few seconds.
  • Example 5 Stock: Unbleached kraft pulp. Cationic polymer: Same as in Example 3; 0.5% O.W.F. Polyiluoroalkyl phosphate: A mixture of monoand his (1H,1H,2H,2H-heptafluoropentyl) phosphate containing 20% of the mono ester; 5% O.W.F. Oil penetration test:
  • Oil usedpeanut oil Penetration timetreated paper-30 minutes.
  • Oil usedpeanut oil Penetration time-treated Control-immediately.
  • Cationic polymer A .polyethyleneimine of M.W. between 30,000 and 40,000, quaternized with dimethyl sulfate. (A commercial product.) Quantity: 2.5% O.W.F.
  • Oil used-peanut oil Penetration timetreated paper30 minutes. Controlimmediately.
  • Example 8 [omitting the cationic agent]
  • Four parts of dry bleached kraft pulp are agitated vigorously in a vessel containing 300 parts of water, and 8 parts of an aqueous 1% solution of ammonium bis (Z-perfluoroheptyl- -ethyl) phosphate (2% O.W.F.) are added.
  • the aqueous pulp is conveyed to the screen of a paper making machine, and the process of forming a paper sheet is proceeded with and finished in ordinary manner.
  • Test B using peanut oil, it takes about 30 minutes for the first observable penetration compared with essentially immediate penetration for an untreated control.
  • Example 9 100 parts of cotton fabric are dipped into an aqueous bath containing 1000 or more parts of water and 1 part by weight (i.e. 1% O.W.F.) of a polymer obtained from the dimethyl-sulfate quaternary salt of Z-diethylaminoethyl methacrylate. After agitating for 5 minutes or more, the fabric is removed, squeezed and reimrnersed in a bath containing 1000 parts or more of water and 1 part (i.e. 1.0% OWE.) of ammonium bis(1H,1H,9H-hexadecafiuorononyl) phosphate. After agitating in said bath for 5 minutes or more, the fabric is removed, squeezed and air-dried.
  • aqueous bath containing 1000 or more parts of water and 1 part by weight (i.e. 1% O.W.F.) of a polymer obtained from the dimethyl-sulfate quaternary salt of Z-diethylamin
  • Example 0 Six pounds of unbleached kraft stock was beaten to a Canadian Standard freeness of 450' and the pulp transferred to the machine chest of an 8%2-inch laboratory Fourdrin-ier paper machine. The concentration of fibers in the pulp in the chest was about 0.6%. A solution of 13.6 g. of ammonium bis(lH,lH,9H hexadecafiuorononyl) phosphate, [H CF 2 CH OJ P'( 0) ONH in about /2 gallon of water was added over a period of about 15 minutes to the pulp in the chest with agitation. The paper machine was then started and run at about 11 feet per minute to produce a sheet of 50 pounds (24" x 36" x 500) basis weight.
  • Paper so produced exhibited greater than 30 minutes holdout :to peanut oil.
  • a sheet run under similar conditions but containing no additives was found to have essentially no holdout to peanut oil.
  • Example 11 1000 pounds of bleached k-raft furnish was beaten to a vfreeness of 600. 0.25 oz. of a blue direct azo dye was added to tint or whiten the paper. The charge was dropped to the beater chest. The pulp consistency was about 3.5% and the pH 7.5. 15 lbs. of a 30% solution of polymerized dimethyl-sulfate-quaternized Z-diethylaminoethyl methacrylate were mixed with 50 gallons of water and the resultant solution was added over a 40- minute period to the pulp in the beater chest. The pulp pH was then 5.8. The stock was transferred to the beater chest through a jordan. 6 lbs.
  • ammonium bis(1H,1H,9H-hexadecafluoro-nonyl) phosphate were dissolved in 6 lbs. of acetone, diluted to 50 gallons with water, and the solution was added to the pulp in the beater chest over a 20-minute period. The pulp was again jordaned, diluted to machine consistency in the fan pump and fed to a l08-inch Fourdrinier machine.
  • the agents have been added in the form of 1% aqueous solutions, solutions of other concentrations may, obviously, be employed.
  • preparation of the aqueous solution may be facilitated by first dissolving the agent in an organic solvent, such as acetone, methanol, or ethanol, followed by dilution with water, or a solution of the free acid phosphate in an organic solvent as aforenoted may be diluted with an aqueous amine or ammonia solution.
  • an organic solvent such as acetone, methanol, or ethanol
  • the quantities of materials added may vary from 0.05 to 3% O.W.'F. for the cationic polymer and from 0.05 to 10% O.W.F. for the phosphate.
  • the optimum amount will depend upon such factors as the nature of the pulp, the particular nitrogen-containing polymeric material selected, the composition of the phosphate, and the degree of oil-repellency desired. As a rule, a given combination of agents in specified amounts produces a greater effect on unbleached kraft pulp than on bleached kralft or bleached sulfite pulp.
  • the ammonium salts or amine-addition products are more elfective than the free phosphoric acid, and the wF-compounds (Formula I) are more potent than the wH-compounds (Formula ll).
  • the bis-fluoroalkyl phosphates are enormous more effective than the mono compounds, and where mixtures are unavoidable, it is preferred to use such mixtures wherein the bis-fluoroalkyl compounds predominate (i.e. y has an average value greater than 1.5).
  • Fully alkylated phosphates i.e.
  • the wF-compounds may be generically referred to as (perfiuoroalkyl-alkyl) phosphates. It follows from the aforegoing discussion that the most potent compounds for the purposes or" this invention, and therefore the most desirable from the practical viewpoint, are the bis(perlluoroalkyl-alkyl)ammonium phosphates.
  • the wF-compounds possess the added advantage that they also impart water-repellence to the treated articles.
  • the order of treatment of the solid material with the two principal agents of this invention is immaterial, provided care is taken to eliminate or minimize contact between the two agents except when either of them is in contact with the solid material being treated.
  • the cationic agent may be applied first and after a little time, to allow for complete exhaustion of said agent onto the material being treated (say, an aqueous paper pulp), the polyfluoroalkyl phosphate may be applied.
  • the reverse sequence may be applied, with a suitable time interval to allow for maximum exhaustion of the phosphate compound onto the fiber.
  • the materials may be .fed simultaneously from separate pipes into the vessel or pipe containing the pulp, provided vigorous agitation (or turbulent flow in the case of a pipe) is applied to insure rapid contact of either agent with the pulp, thus minimizing the frequency and time of contact beiween the two agents when not in contact with the pu p.
  • the process of this invention may be applied to many types and grades of pulp. These include unbleached kraft pulp, unbleached sulfite pulp, bleached draft pulp, bleached sulfite pulp, alpha pulp or rag stock from cotton fibers, such pulps being used alone or in mutual admixture, or again in admixture with ground-wood pulps.
  • the novel paper thus produced itself has several important valuable qualities and advantages.
  • the paper may possess a high degree of oil-repellency, its appearance, feel, porosity and other physical qualities are not changed, and the paper may, further-more, be given customary finishing treatments such as sizing, coating and the like, to improve the surface for printing or to provide water repellency.
  • customary finishing treatments such as sizing, coating and the like, to improve the surface for printing or to provide water repellency.
  • the paper is creased it does not produce a break in the oil-repellent film, as is the case with surface-treated paper.
  • Oil-repellent paper which has been produced from treated pulp according to this invention has been found to be excellently adapted for further treatment with tarry or waxy coatings, giving consistently a superior product in respect to adhesion of the coating, opacity of the paper and economy of the process compared to other papers which have not been made oil-repellent at all or papers which have been made oil-repellent by surface treatment of the paper sheet.
  • said water-soluble linear polymer containing cationic nitrogen atoms is a member selected from the group consisting of cationic urea-formaldehyde resins, cationic melamine-formaldehyde resins, quaternary salts and acid salts of polymerized ethyleneimine, cationic starches and quaternary salts and acid salts of polymerized dialkylaminoalkyl acrylates and methacrylates.
  • water-soluble linear polymer is the acetic acid salt of polymerized 2- diethylaminoethyl methacrylate.
  • water-soluble linear polymer is the dimethyl-sulfate quaternization product of polymerized Z-diethylaminoethyl methacrylate.
  • a process of producing an oil-repellent paper which comprises treating an aqueous paper pulp, in the stage prior to sheet formation, with an aqueous solution of a polyfiuoroalkyl phosphate containing from 3 to 12 CF groups per molecule whereby to exhaust onto said pulp from 0.05 to 3% of its weight of said polyfiuoroalkyl compounds, further treat-ing said aqueous pulp with an aqueous solution of a water-soluble linear polymer containing cationic N-atoms whereby to exhaust onto said pulp from 0.05 to 10% of its weight of said polymer, and forming paper sheet material from the pulp so treated.
  • polyfiuoro-alkyl phosphate selected is a mixed product in which the dominant component is a compound whose y-value is 2.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Textile Engineering (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Paper (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
US53884A 1960-09-06 1960-09-06 Process of imparting oil-repellency to solid materials, and materials thus produced Expired - Lifetime US3112241A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US53884A US3112241A (en) 1960-09-06 1960-09-06 Process of imparting oil-repellency to solid materials, and materials thus produced
US53885A US3096207A (en) 1960-09-06 1960-09-06 Process of imparting oil-repellency to solid materials
FI1530/61A FI40279B (de) 1960-09-06 1961-08-30
DEP27822A DE1260059B (de) 1960-09-06 1961-09-05 OElabweisendmachen von festen wasserunloeslichen Stoffen
GB31993/61A GB939902A (en) 1960-09-06 1961-09-06 Process for imparting oil-repellency to solid materials and materials thus produced
FR872469A FR1305612A (fr) 1960-09-06 1961-09-06 Procédé pour communiquer des propriétés oléofuges à des matières solides et matières ainsi obtenues

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US53884A US3112241A (en) 1960-09-06 1960-09-06 Process of imparting oil-repellency to solid materials, and materials thus produced
US53885A US3096207A (en) 1960-09-06 1960-09-06 Process of imparting oil-repellency to solid materials

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3468697A (en) * 1966-03-02 1969-09-23 Colgate Palmolive Co Method of treating textile articles which are usually laundered
JPS4969909A (de) * 1972-11-11 1974-07-06
US3953283A (en) * 1972-10-05 1976-04-27 Continental Can Company, Inc. Paperboard having improved oil resistance
US4064067A (en) * 1976-04-26 1977-12-20 E. I. Du Pont De Nemours And Company Fluorosurfactant leveling agent
US4118235A (en) * 1975-09-18 1978-10-03 Daikin Kogyo Co., Ltd. Mold release agent
US4380565A (en) * 1982-01-08 1983-04-19 Champion International Corporation Color preservation of wax-coated paperboard
US5120364A (en) * 1990-10-10 1992-06-09 Ciba-Geigy Corporation Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof
EP0683267A2 (de) 1994-05-18 1995-11-22 Minnesota Mining And Manufacturing Company Fluor enthaltende Phosphate, und ihre Verwendung in der Papierherstellung
EP0687533A1 (de) * 1994-06-14 1995-12-20 AUSIMONT S.p.A. Verfahren zur Oberflächenbehandlung von cellulosen, metallischen, glasartigen Materialien, oder Zemente, Marmor, Granit und dergleichen
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JPS63267792A (ja) * 1987-04-22 1988-11-04 Daikin Ind Ltd リン酸ジ（フルオロアルキル基含有基置換アルキル）塩の製法
EP0462063A1 (de) * 1990-06-13 1991-12-18 Ciba-Geigy Ag Fluoriertes Papierleimungsmittel
JP3030863B2 (ja) * 1990-12-25 2000-04-10 ダイキン工業株式会社 皮革改質剤、皮革の改質方法および改質なめし皮革
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US3468697A (en) * 1966-03-02 1969-09-23 Colgate Palmolive Co Method of treating textile articles which are usually laundered
US3953283A (en) * 1972-10-05 1976-04-27 Continental Can Company, Inc. Paperboard having improved oil resistance
JPS4969909A (de) * 1972-11-11 1974-07-06
JPS5545680B2 (de) * 1972-11-11 1980-11-19
US4118235A (en) * 1975-09-18 1978-10-03 Daikin Kogyo Co., Ltd. Mold release agent
US4308063A (en) * 1975-09-18 1981-12-29 Daikin Kogyo Co., Ltd. Mold release agent
US4064067A (en) * 1976-04-26 1977-12-20 E. I. Du Pont De Nemours And Company Fluorosurfactant leveling agent
US4380565A (en) * 1982-01-08 1983-04-19 Champion International Corporation Color preservation of wax-coated paperboard
US5120364A (en) * 1990-10-10 1992-06-09 Ciba-Geigy Corporation Heteroatom containing perfluoroalkyl terminated neopentyl sulfates and salts thereof
US5714266A (en) * 1994-05-18 1998-02-03 Minnesota Mining And Manufacturing Company Fluorine-containing phosphates
EP0683267A2 (de) 1994-05-18 1995-11-22 Minnesota Mining And Manufacturing Company Fluor enthaltende Phosphate, und ihre Verwendung in der Papierherstellung
EP0687533A1 (de) * 1994-06-14 1995-12-20 AUSIMONT S.p.A. Verfahren zur Oberflächenbehandlung von cellulosen, metallischen, glasartigen Materialien, oder Zemente, Marmor, Granit und dergleichen
US5691000A (en) * 1994-06-14 1997-11-25 Ausimont S.P.A. Process for surface treatment of cellulosic, metallic, vitreous materials, or cements, marbles, granites and the like
US5525261A (en) * 1994-10-18 1996-06-11 Henkel Corporation Anti-static composition and method of making the same
US7943567B2 (en) 2004-01-30 2011-05-17 E.I. Du Pont De Nemours And Company Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
US8318656B2 (en) 2007-07-03 2012-11-27 E. I. Du Pont De Nemours And Company Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
US20110257423A1 (en) * 2008-01-22 2011-10-20 Dupont Performance Elastomers Llc Process for producing fluoroelastomers
US20110303620A1 (en) * 2010-06-10 2011-12-15 Di Gao Superoleophobic and Superhydrophilic Fabric Filters for Rapid Water-Oil Separation
US8695810B2 (en) * 2010-06-10 2014-04-15 University of Pittsburgh—of the Commonwealth System of Higher Education Superoleophobic and superhydrophilic fabric filters for rapid water-oil separation
US20130210976A1 (en) * 2012-02-13 2013-08-15 E. I. Du Pont De Nemours And Company Fluorinated phosphates as surface active agents

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Publication number Publication date
FI40279B (de) 1968-09-02
FR1305612A (fr) 1962-10-05
DE1260059B (de) 1968-02-01
US3096207A (en) 1963-07-02
GB939902A (en) 1963-10-16

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