US3736164A - Organophobic and hydrophobic surface coatings - Google Patents

Organophobic and hydrophobic surface coatings Download PDF

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Publication number
US3736164A
US3736164A US00163417A US3736164DA US3736164A US 3736164 A US3736164 A US 3736164A US 00163417 A US00163417 A US 00163417A US 3736164D A US3736164D A US 3736164DA US 3736164 A US3736164 A US 3736164A
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United States
Prior art keywords
fluorochemical
backside
composition
weight
surface coating
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US00163417A
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English (en)
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M Uffner
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Air Products and Chemicals Inc
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Air Products and Chemicals Inc
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Classifications

    • 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
    • D21H19/00—Coated paper; Coating material
    • D21H19/10—Coatings without pigments
    • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
    • 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
    • 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

Definitions

  • the present invention relates to novel mixtures of active fluorine-containing phosphate material, chelating agent and volatile solvent which can be used to impart oil, grease and solvent resistance to treated materials, particularly cellulosic packaging materials.
  • laminated packaging materials have been used in which a barrier coating of wax, plastic, or the like, which has thickness of approximately 0.0001 inch to 0.0015 inch, is laminated to the packaging material.
  • This laminating approach tends to diminish the economic advantages sought in the use of cellulosic packaging materials.
  • the laminated layer must be applied in a separate step and care must be taken to obtain uniformity in the laminated layer in cluding an absence of pinholes, tears and the like, and good adherence to the cellulosic materials.
  • fluorochemicals Since the commercial introduction of fluorochemical sizing agents, fluorochemicals have been used to provide oil resistance for cellulosic materials.
  • the use of such fluorochemicals has the advantage of eliminating the necessity of having to provide a separate barrier of plastic film, waxed paper or metal foil to obtain oil repellency characteristics.
  • the resulting surface When a surface is treated with fluorochemicals, the resulting surface has very low surface energy which prevents wetting of surface fibers by aqueous materials, most animal, vegetable and mineral oils, and by many solvents.
  • both the topside and backside of the cellulosic packaging materials are treated with fluorochemicals to obtain the desired barrier characteristics.
  • both sides can be treated with the same fluorochemical composition, typically the composition used for the topside and the backside are different because the resistance characteristics needed for each side are different.
  • the coating compositions used commercially are similar in the fact that the pH for such compositions lies in the range of 8.0 to 9.5 and the fluorochemicals employed for such coating compositions are linear fluorochemicals.
  • the backside fluorochemical coatings which have heretofore been used have been applied from either an aqueous fluorochemical solution, containing no additives, or in combination with a starch, typically oxidized starch.
  • a starch typically oxidized starch.
  • the starch is added to prevent curling of paperboard during drying.
  • the cellulosic material which is to be treated with fluorochemical coating is first primed with the pentasodium salt of diethylenetriaminepentaacetic acid from an alkaline aqueous solution. The results of such treatment have been erratic, have caused the treated paperboard to be tenderized, and have diminished the water resistance of the paperboard.
  • Another object of this invention is to provide novel surface coating compositions which result in imparting oil, water and solvent repellency to cellulosic materials.
  • Still another object of the present invention is to provide a method of treating cellulosic packaging material with surface coating composition of the present invention on the backside and treating the topside with a conventional surface coating composition in order to obtain improved oil, water and solvent resistance of both sides of the packaging material.
  • surface coating compositions are prepared by blending water with between 1 and 25 active parts by weight of fluorine-containing phosphate material, between 0.01 and 2 active parts by weight of chelating agent and 1 to 10% by Weight of solvent based on the total wet weight of the composition, including the active solids, water of dilution and solvent.
  • the resulting surface coating compositions are used to impart oil, water and solvent resistance to cellulosic materials, such as paper, cardboard, paperboard, etc.
  • the active fluorine-containing phosphate materials which can be used in accordance with the present invention have the formula (R L) Z [Formula I] where: R, is:
  • C F -EC F where C F represents a monosubstituted or disubstituted cyclohexane ring; b is 0 or 1; n is an integer between 0 and 10 when b is 1 and n is an integer between 4 and 20 when b is 0;
  • the preferred chelating agent is the disodium salt of ethylenediaminetetraacetic acid.
  • Preferred solvents include n-butanol and methyl ethyl ketone.
  • a binder can be added to the surface coating compositions.
  • the preferred binder is hydroxyethylated starch.
  • the resulting surface coating compositions have a pH less than or equal to 7.
  • the combination of the chelating agent and the solvent serve to wet the treated fibers thereby causing improved fluorochemical wicking.
  • the optional hydroxyethylated starch binder tends to prevent coated board from curling and also tends to improve the oil and solvent resistance of the coating composition.
  • the surface coating compositions of the present invention are prepared by mixing between 1 and 25 parts by weight of the composition of an active fluoride-containing phosphate material with between 0.01 and 2 parts by weight of chelating agent and between 1 and 10% of the total wet weight of solvent. Water is added to make'up the balance of the coating composition.
  • active fluorine-containing phosphate materials which may be used in accordance with the present invention are the following materials:
  • FEC F EI-CH OPO (OH) 2 CF (CF CH OPO (OH) 2 2H(NCH CH OH)
  • the C F group of R; [in Formula I] can be in the 1, 2 or 3 position of the cyclohexane ring ⁇ C F
  • the alkali metal of the water-solubilizing cation M in Formula I is either sodium or potassium.
  • the substituted ammonium salts may be obtained using the commonly available, water-soluble, primary, secondary or tertiary amines, such as methyl amine, diethyl amine, monoethanol amine, diethanol amine, morpholine, triethanol amine and bis(3-hydroxypropyl)amine.
  • the preferred chelating agent is the disodium salt of ethylene-diaminetetraacetic acid.
  • Other chelating agents such as sodium hexametaphosphate, may be employed, but the results are not necessarily equivalent.
  • water soluble alcohols and ketones may be employed as a solvent.
  • the solvent is either n-butanol or methyl ethyl ketone.
  • the preferred binder is hydroxyethylated starch.
  • the amount of chelating agent is generally reduced.
  • composition with binder Parts by weight of composition With binder:
  • Chelating agent Binder Solvent 1 to 25 and preferably 5 to 10.
  • Solvent 1 to 10% of total Wet weight and preferably 2 to 6% of total wet weight.
  • Pigments include titanium dioxide, calcium carbonate, zinc oxide, hydrated alumina, barium sulfate, zinc sulfide, calcium sulfite, calcium sulfate, talc, etc.
  • Lubricants include sodium stearate, ammonium stearate, calcium stearate, aluminum stearate, and the like.
  • Effective coating means include air-knife coaters, brush coaters, cast coaters, flexible blade coaters, gravure coaters, reverse roll coaters, transfer roll coaters, and the like.
  • the resultant thin coatings are adequate for most applications.
  • the surface coating compositions of the present invention may be applied in two or more coatings or certain thickening additives may be incorporated, such as cellulose ethers.
  • the surface coating compositions of the present invention are aindried to useful continuous coatings, it will be understood that these coating compositions can be dried by any suitable means in order to reduce the drying time.
  • the resulting coatings exhibit good adhesion to paper and other cellulosic material and provide effective oil, water and solvent resistance.
  • the RC-338 Kit Test is a procedure for testing the degree of repellency and/or wicking characteristics of paper and paperboard which are treated with fluorochemical-type sizing agents.
  • the following apparatus, specimens and reagents are required:
  • Bottles a set of labeled glass stoppered bottles to serve as stock bottles for the Kit Number reagents.
  • Reagents (1) Castor oil, C.P. grade.
  • Mixtures of the aforementioned reagents are prepared in accordance with the following table and stored in the labeled glass-stoppered stock bottles.
  • test specimen is placed on a clear flat surface, testside up, with care being taken not to touch the area to be tested.
  • a drop of the test solution from an intermed ate Kit Number is dropped on the test area from a height of about one inch.
  • the timer is started simultaneously with the application of the test solution. After seconds, excess fluid is removed with a clean swatch of absorbent cotton. Repellency is determined by examination of the wetted area. A darkening of the specimen indicates that penetration has occurred.
  • the flat peanut oil holdout test provides an accelerated comparison of relative rates at which oils or greases found in materials contained by flexible packages may be expected to penetrate these packaging materials.
  • the following apparatus, specimens and reagents are used for practicing this test:
  • Apparatus 1 Tube of any rigid material, one inch inner diameter and not less than one inch height, the ends of which have been smoothed.
  • the samples are cut to a minimum of four by four inches.
  • Mixed reagent peanut oil is prepared by adding 1.0 gram of an oil soluble red dye to 100 milliliters of peanut oil.
  • the samples are preconditioned for 24 hours at 73 degrees F. ,and relative humidity.
  • Each sample is placed on a sheet of coated 80 pound book paper mounted to the glass plate. Half the number of samples are placed topside up; the other half backside up. Metal weights are placed around the periphery.
  • the tube is placed at the center of the sample and five grams of sand is poured into the tube. The tube is removed and using the pipette 1.1 milliliters of colored peanut oil is added to the sand.
  • the glass plate is placed over the oil saturated sand in order to insure intimate contact of the test sheet with the backup sheet. The resulting sample is then placed in 140 degree F. oven.
  • each sample is checked every fifteen minutes for the first hour, every thirty minutes for the next four hours, and then at convenient intervals. As soon as the first red stain appears on the absorbent paper, the time is noted. The time elapsed in hours between placing the sample in the oven and the appearance of the first red stain is recorded.
  • the flat peanut oil holdout is 2 hours at 60 degrees C. for the backside and 8 hours at 60 degrees C. for the topside.
  • Composition (a) Parts by weight (1) tap water 44.00
  • soya protein (Delta type) 7.75 (3) methylpolysiloxane (defoamer) .009 (4) borax 0.23 (5) 26 degree B aqua ammonia 0.93 (6) tap water 3.73
  • the blackside of the board was primed with 0.5% of the pentasodium salt of diethylenetriaminepentaacetic acid and then coated with the same linear fluorochemical used in Composition (b) in order to transfer 0.05 active fluorochemical on the weight of the board.
  • the coated paperboard was dried at degrees F. for 15 minutes.
  • the board was shown to contain a total of 0.1% linear fluorochemical on the weight of the board.
  • EXAMPLE II The procedure of the Example I was repeated except that the backside was not primed and the backside coating composition used was a combination of the linear fluorochemical, the 'pentasodium salt of diethylenetriaminepentaacetic acid and oxidizsed starch in accordance with the following backside coating composition.
  • the backside coating composition was applied to Brown Companys bleached manila linear bending to yield a 0.05% fluorochemical pickup on the weight of board.
  • the resulting board was tested, as in Example I, with the following results:
  • Methylpolysiloxane (defoamer) 3.7 10% disodium salt of ethylenediaminetetraacetic acid 5.0 Methyl ethyl ketone 63.0 30% linear fluorochemical (anionic watersoluble mixture of the diethanolamine salts of the perfiuoroheptyl-carbinol esters of phosphoric acid) 26.2
  • This backside coating composition was applied to the bleached manila lined bending news to obtain the total 8 percent of fluorochemical content of the board, by analysis, of 0.1%. The following results were obtained:
  • Example V The topside coating procedure of Example I was employed to coat Rockford Paper Mill Companys 20 point Kraftback (72 pounds per ream).
  • the oxidized pearl starch was cooked for 15 minutes at a temperature between and degrees F.
  • the backside coating composition was applied to obtain analysis of the board of 0.1% fiuorochemical based on the weight of the board.
  • EXAMPLE X Following the procedure of Example I, the topside coating composition was prepared in which the cyclic fluorochemical (anionic water-soluble mixture of the diethanolamine salts of the 1,1-dihydroperfluorocyclohexylmethyl esters of phosphoric acid) and the linear fluorochemical (anionic water-soluble mixture of the diethanolamine salts of the perfiuoroheptyl carbinol esters of phosphoric acid) were substituted for each other.
  • the cyclic fluorochemical anionic water-soluble mixture of the diethanolamine salts of the 1,1-dihydroperfluorocyclohexylmethyl esters of phosphoric acid
  • linear fluorochemical anionic water-soluble mixture of the diethanolamine salts of the perfiuoroheptyl carbinol esters of phosphoric acid
  • the backside coating composition employed is set forth by the following table:
  • both the cyclic fluorochemical and the linear fluorochemical were substituted for each other as the fluorochemical used in the backside coating composition.
  • the surface coating compositions of the present invention comprising active fluorine-containing phosphate material, chelating agent and solvent in the indicated proportions, are superior to coating compositions of conventional fiuorochemical sizing agents.
  • the coating compositions of the present invention can be applied in a one-step application, thereby eliminating the necessity for two separate applications or even priming the surface before fiuorochemical overcoat is applied.
  • the fluorochemical coating compositions of the present invention are especially useful in improving the protection of label papers which are exposed to oils, protection of paperboard for both external stains and stains from internal oil contents and for the protection of cellulosic sheets which are to be Waxed.
  • While the present invention finds particular applicability to the treatment of cellulosic materials such as paper and paperboard, the invention is also applicable to other cellulosic materials, including cardboard, including corrugated board; construction boards, including insulating board; wet machine board, including binder board for book covers; laminated board, including board prepared pi a laminating glassine paper to paper board; and the Obviously, many modifications and variations of the invention as hereinbefore set forth may be made without departing from the spirit and scope thereof and therefore only such limitations should be imposed as are indicated in the appended claims.
  • R is:
  • C F is a monosubstituted or disubstituted cyclohexane ring, where b is 0 or 1, n is an integer between 0 and 10 when b is 1 and n is an integer of from 4 to 20 when b is 0;
  • x is the integer 1 or 2 and M is a Water solubilizing cation of the group consisting of alkali metal, ammonium and substituted ammonium when x is l, and each M is independently selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium when x is 2.
  • composition of claim 1 which also includes a binder.
  • composition of claim 6 in which the binder is hydroxyethylated starch in the amount between 25 and 200 parts by weight of the composition.
  • a coated cellulosic material having on at least one surface thereof a coating composition having a pH equal to or less than 7 consisting essentially of a fluorine containing phosphate material, a chelating agent and a solvent selected from water soluble alcohols and ketones, wherein the structural formula of the fluorine-containing phosphate material is R L Z,
  • R is:
  • C F is a monosubstituted or disubstituted cyclohexane ring, where b is or 1, n is an integer between -0 and 10 when b is 1 and n is an integer of from 4 to and b is 0; L is:
  • R is an alkyl group having 1 to 10 carbon atoms
  • a is the integer 1 or 2;
  • y is an integer of 1 or 2
  • Z is:
  • x is the integer 1 or 2 and M is a water solubilizing cation of the group consisting of alkali metal, ammonium and substituted ammonium when x is l, and each M is independently selected from the group consisting of hydrogen, alkali metal, ammonium and substituted ammonium when x is 2.
  • a process for treating cellulosic material which process comprises applying a surface coating composition having a pH equal to or less than 7 to the cellulosic material in order to deposit from 0.01 to 1% by weight of active fluorochemical on the weight of the cellulosic material and then drying the treated cellulosic material, wherein the coating composition is prepared by blending (a) l to parts by weight of composition of a fluorinecontaining phosphate material,
  • C F is a monosubstituted or disubstituted cyclohexane ring, where b is 0 or 1, n is an integer between 0 and 10 when b is 1 and n is an integer of from 4 to 20 when b is 0; L is:
  • R is an alkyl group having 1 to 10 carbon atoms
  • a is the integer 1 or 2;
  • y is an integer of 1 or 2
  • Z is:
  • x is the integer 1 or 2 and M is a water solubilizing cation of the group consisting of alkali metal, ammonium and substituted ammonium when x is 1, and each M is independently selected from the group consisting of hydrogen, alkali metal, ammoninth and substituted ammonium when x is 2.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • General Health & Medical Sciences (AREA)
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US00163417A 1971-07-16 1971-07-16 Organophobic and hydrophobic surface coatings Expired - Lifetime US3736164A (en)

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US (1) US3736164A (fr)
CA (1) CA972106A (fr)
DE (1) DE2234711A1 (fr)
FR (1) FR2146266A1 (fr)
GB (1) GB1395640A (fr)
IT (1) IT961395B (fr)
NL (1) NL7209735A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183766A (en) * 1978-06-12 1980-01-15 Woodward Fred E Paper coating composition
US4898700A (en) * 1983-05-14 1990-02-06 Toho Rayon Co., Ltd. Process for producing preoxidized fibers from acrylic fibers
US5330622A (en) * 1991-07-25 1994-07-19 Aussedat-Rey Composition for rendering a paper or textile base resistant to water, oil and solvents, treated base and process for the production of the treated base
WO2000003089A1 (fr) * 1998-07-08 2000-01-20 Upm-Kymmene Corporation Papier adhesif de doublure

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4313978A (en) * 1978-12-20 1982-02-02 Minnesota Mining And Manufacturing Company Antistatic compositions and treatment
EP0296661B1 (fr) * 1987-06-23 1992-01-22 ENIRICERCHE S.p.A. Composition en une phase contenant une huile perfluorée et un ou plusieurs suractifs, utile en tant qu'excipient pour des formulations cosmétiques et dermatologiques, ainsi que pour des applications biomédicinales

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183766A (en) * 1978-06-12 1980-01-15 Woodward Fred E Paper coating composition
US4898700A (en) * 1983-05-14 1990-02-06 Toho Rayon Co., Ltd. Process for producing preoxidized fibers from acrylic fibers
US5330622A (en) * 1991-07-25 1994-07-19 Aussedat-Rey Composition for rendering a paper or textile base resistant to water, oil and solvents, treated base and process for the production of the treated base
WO2000003089A1 (fr) * 1998-07-08 2000-01-20 Upm-Kymmene Corporation Papier adhesif de doublure

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Publication number Publication date
FR2146266A1 (fr) 1973-03-02
CA972106A (en) 1975-08-05
IT961395B (it) 1973-12-10
DE2234711A1 (de) 1973-02-01
GB1395640A (en) 1975-05-29
NL7209735A (fr) 1973-01-18

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