US2641558A - Water repellence fixative treatment - Google Patents

Water repellence fixative treatment Download PDF

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Publication number
US2641558A
US2641558A US6725448A US2641558A US 2641558 A US2641558 A US 2641558A US 6725448 A US6725448 A US 6725448A US 2641558 A US2641558 A US 2641558A
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Prior art keywords
water
paper
fixative
repellence
fibrous
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Stephen F Urban
Warren B Blumenthal
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NL Industries Inc
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Nat Lead Co
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Priority to US6725448 priority Critical patent/US2641558A/en
Priority to GB2882949A priority patent/GB684686A/en
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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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/16—Sizing or water-repelling agents
    • 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
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/76—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon oxides or carbonates
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/76—Photosensitive materials characterised by the base or auxiliary layers
    • G03C1/775—Photosensitive materials characterised by the base or auxiliary layers the base being of paper
    • G03C1/79—Macromolecular coatings or impregnations therefor, e.g. varnishes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31971—Of carbohydrate
    • Y10T428/31993—Of paper
    • Y10T428/31996—Next to layer of metal salt [e.g., plasterboard, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2164—Coating or impregnation specified as water repellent
    • Y10T442/2197—Nitrogen containing

Definitions

  • the present invention relates to the treatment of fibrous materials such. as: textile fabrics and fibrous cellulosic sheet material, for instance, paper and cardboard, in order to render such fibrous material resistant to wetting and to penetration by Water. More particularly, the invention relates to a method for inducing water repellence in the fibrous material treated by the employment of a specific water soluble, alkaline zirconium compound, i. e., ammonium dicarbonato zirconylate, and the fixation of the zirconium compound, or a decomposition product thereof, upon the material so treated, whereby the effects of the water repellent treatment will endure through conditions which normally clestroy it, either partially or completely.
  • a specific water soluble, alkaline zirconium compound i. e., ammonium dicarbonato zirconylate
  • fixation of the zirconium compound, or a decomposition product thereof upon the material so treated, whereby the effects of the water repellent treatment will endure through conditions which normally clestro
  • the zirconium compound adheres to the fibrous material being treated and serves to bind to the surface thereof a film of fatty and/or waxy 2 material normally incorporated in the. solution of the water repellence compound.
  • This film then comprises the hydrophobic exterior of the fibers and is responsible for the water repellent quality.
  • the hydrophobic film thus formed on the material to which water repellent properties are to be imparted is then fixed or anchored on the fibers of that material by a subsequent treatment with a water soluble salt of a polyvalent metal selected from the groups 111', IV and VIII of the periodic system, or a mixture of such salts.
  • the anion of the salt of the polyvalent metal appears when used alone to furnish little or no fixative action, this property being induced only when it is used in conjunction with the polyvalent cation.
  • the fixative action is a general function of the polyvalent cations of the metals of the stated groups, it will generally be found advantageous to employ salts of such cat.- ions which produce colorless aqueous solutions as, for instance, zirconium, tin, aluminum, and others.
  • the fixative salt upon the fibrous material which has been treated with the soluble double ammonium zirconium carbonate the material may be rinsed without dislodging or destroying the water repeilence effect of the hydrophobic film.
  • the fabric or fiber sheet After rinsing, the fabric or fiber sheet is dried generally at an elevated temperature and will be found to possess very strong and sustained water repellence. For instance, fabrics so treated will exhibit a spray rating of to and paper will shed a spray of water. It will be noted that-water dropped upon horizontally placed'paper sheets so treated will form roundedglobules, whereas on untreated paper. the drops flatten out and wet the paper. Cloth rendered water repellent without the application of the fixative will withstand one to two launderingswith Ivory soap, without losing its water repellence, While similar cloth treated with the fixative can withstand four to eight such launderings. Furthermore, a single dry cleaning normally destroys the water repellent quality when no fixative is employed. How- .ever,. similar cloths made water repellent by including the fixative treatment of the present invention have been found to withstand sixdry cleanings.
  • Example I Anaqueousso1ution of ammonium dicarbonato zirconylate, (NH4),2ZrO(C'O3)2, containing one- 'this bath for one minute, then removed and rolled free of excess liquid. The so treated paper was then immersed for two minutes in a solution containing 1.9 gm. of basic zirconyl chloride (Z1'2O3C12.6H2O) dissolved in 100 ml. of Water. After removal from this solution, the material was rinsed thoroughly in water and dried at 90 C. (194 F.). It was rendered highly water repellent by this process.
  • Example II Same as Example I except that 3.0 gm. of stannous chloride was used in place of the basic zirconyl chloride.
  • Example III Same as Example I except that 2.5 gm. of ferrous sulfate was used in place of the basic zirconyl chloride.
  • the procedures of the present invention have particular application to improve water repellence treatments of fibrous fabrics and to successful water repellence treatments of fibrous cellulosic sheets as, for instance, paper sheets to be employed in the manufacture of sensitized photographic and print paper.
  • a process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato. zirconylate 4 and a water soluble soap, and thereafter immersing said so treated material in an aqueous solution containing a salt which yields a cation of a metal selected from the group of metals of groups three, four and eight of Mendeleefis periodic arrangement of the elements, then rinsing and dry ing the material.
  • Aprocess for inducing .water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble zirconium salt wherein zirconium is a cation, then rinsingand drying the material.
  • a process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble aluminum salt wherein aluminum is a cation, then rinsing and drying the material.
  • a process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous. bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble tin salt wherein tin is a cation, then rinsing and drying the material.
  • a process for inducing'water repellance in paper which comprises immersing the paper in an aqueous water repellance bath containing a water soluble soap and a water soluble alkaline double ammonium zirconium carbonate for a time sufficient to saturate the paper with the solution, thereafter immersing the so saturated paper in anaqueous solution of zirconyl chloride to fix-the water repellance materials upon the fibers of the paper, then rinsing and drying the paper.
  • a fibrous material having water repellance properties comprising a base of c'ellulosic fibrous material, a hydrophobic coating thereon of the reaction product of an aqueous solution of ammonium dicarbonato zirconylate and a water soluble soap and a fixative for said coating comprising a polyvalent metal cation selected from the group of metals consisting of groups three, four and eight of Mendeleefis periodic arrangement of the elements.
  • a paper sheet having water repellance properties and having on the surface thereof a hydrophobic coating of the reaction product of an aqueous solution of ammonium dicarbonato zirconylate and a water soluble soap and a fixative for said coating comprising a polyvalent metal cation selected from the group of metals consisting of groups three, four and eight of Mendeleeifs periodic arrangement ofthe elements.

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Textile Engineering (AREA)
  • Paper (AREA)

Description

Patented June 9, 1953 WATER REPELLENCE. FIXATIVE' TREATMENT 1 Stephen F; Urban, Kenmore, and Warren. B. Blumenthal, Niagara Falls, N. Y., assignors to National LeadCompany, New York, N. Y., a corporationof New Jersey No Drawing. Application December 24, 1948, Serial No. 67,254
7 Claims. (01. 117-454) The present invention relates to the treatment of fibrous materials such. as: textile fabrics and fibrous cellulosic sheet material, for instance, paper and cardboard, in order to render such fibrous material resistant to wetting and to penetration by Water. More particularly, the invention relates to a method for inducing water repellence in the fibrous material treated by the employment of a specific water soluble, alkaline zirconium compound, i. e., ammonium dicarbonato zirconylate, and the fixation of the zirconium compound, or a decomposition product thereof, upon the material so treated, whereby the effects of the water repellent treatment will endure through conditions which normally clestroy it, either partially or completely. In general, laundering and dry cleaning are examples of processes which destroy Water repellence effects. v I p So-called water repellence processes have little or no effect upon the normal porosity, texture, appearance and other perceptible qualities of the fabric or paper, aside from its resistance to wetting and penetration by water, and in this respect differ from Water-proofing processes wherein the fibers of the material are coated and the pores of the material are closed by the water-proofing composition. Fibrous materials having water re pellent surfaces, therefore, in general, merely resist wetting of the constituent fibers and the socalled water repellence does not prevent penetration of water into the pores under hydrostatic head. Water-proofing operations are generally more permanent than water repellent operations,
since the materials employed in the latter process are relatively more readily removed by ordinary laundering and dry cleaning operations.
It is an object of the present invention to provide a method of treating fibrous materials to obtain water repellence therein and more per- .manently to fix the water repellence material upon the fibers of the product so treated.
treating material with elimination of the excess solution.
The zirconium compound adheres to the fibrous material being treated and serves to bind to the surface thereof a film of fatty and/or waxy 2 material normally incorporated in the. solution of the water repellence compound. This film then comprises the hydrophobic exterior of the fibers and is responsible for the water repellent quality. The hydrophobic film thus formed on the material to which water repellent properties are to be imparted is then fixed or anchored on the fibers of that material by a subsequent treatment with a water soluble salt of a polyvalent metal selected from the groups 111', IV and VIII of the periodic system, or a mixture of such salts. The anion of the salt of the polyvalent metal appears when used alone to furnish little or no fixative action, this property being induced only when it is used in conjunction with the polyvalent cation. Although the fixative action is a general function of the polyvalent cations of the metals of the stated groups, it will generally be found advantageous to employ salts of such cat.- ions which produce colorless aqueous solutions as, for instance, zirconium, tin, aluminum, and others. Immediately, after th action of the fixative salt upon the fibrous material which has been treated with the soluble double ammonium zirconium carbonate, the material may be rinsed without dislodging or destroying the water repeilence effect of the hydrophobic film. After rinsing, the fabric or fiber sheet is dried generally at an elevated temperature and will be found to possess very strong and sustained water repellence. For instance, fabrics so treated will exhibit a spray rating of to and paper will shed a spray of water. It will be noted that-water dropped upon horizontally placed'paper sheets so treated will form roundedglobules, whereas on untreated paper. the drops flatten out and wet the paper. Cloth rendered water repellent without the application of the fixative will withstand one to two launderingswith Ivory soap, without losing its water repellence, While similar cloth treated with the fixative can withstand four to eight such launderings. Furthermore, a single dry cleaning normally destroys the water repellent quality when no fixative is employed. How- .ever,. similar cloths made water repellent by including the fixative treatment of the present invention have been found to withstand sixdry cleanings.
The following examples are given merely by way of illustration and are not to be deemed as limiting the scope of the invention but as merely illustrative of it as there will obviously be many variations of time, temperature and composition of bath, suitable'for employment in order to obtain the results of the invention.
Example I Anaqueousso1ution of ammonium dicarbonato zirconylate, (NH4),2ZrO(C'O3)2, containing one- 'this bath for one minute, then removed and rolled free of excess liquid. The so treated paper was then immersed for two minutes in a solution containing 1.9 gm. of basic zirconyl chloride (Z1'2O3C12.6H2O) dissolved in 100 ml. of Water. After removal from this solution, the material was rinsed thoroughly in water and dried at 90 C. (194 F.). It was rendered highly water repellent by this process.
A sample of cotton drill treated in the same fashion withstood eight launderings, while another sample withstood six dry cleaning operations before losing its water repellence characteristics.
Example II Same as Example I except that 3.0 gm. of stannous chloride was used in place of the basic zirconyl chloride.
Example III Same as Example I except that 2.5 gm. of ferrous sulfate was used in place of the basic zirconyl chloride.
' Example IV A strip of paper of the type used for application thereto of sensitized photographic gelatin,
I and in which it is desired to produce hydrophobic characteristics, was immersed in an aqueous solution of the double ammonium zirconium carbonate, i. e. ammonium dicarbonato zirconylate, containing about 12.3 gm. ZrO2, 13 gm. ammonium palrnitate, and 12.3 gm. dispersed wax. After immersion for one minute at 40 0., the paper was removed, dipped in water and then passed through rollers to remove excess of liquid.
The Water repellence ingredients of the bath Patent No. 2,457,853, granted January 4, 1949. It
will be understood that the usual fatty substances forming soa can be employed herein, i. e.,'the soluble salts of oleic acid, palmitic acid, stearic acid and the like, and that if waxes be added to the bath, other Waxes may be used in lieu of the paraffin wax employed in the illustrated examples,
The procedures of the present invention have particular application to improve water repellence treatments of fibrous fabrics and to successful water repellence treatments of fibrous cellulosic sheets as, for instance, paper sheets to be employed in the manufacture of sensitized photographic and print paper.
What is claimed is:
1. A process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato. zirconylate 4 and a water soluble soap, and thereafter immersing said so treated material in an aqueous solution containing a salt which yields a cation of a metal selected from the group of metals of groups three, four and eight of Mendeleefis periodic arrangement of the elements, then rinsing and dry ing the material.
2. Aprocess for inducing .water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble zirconium salt wherein zirconium is a cation, then rinsingand drying the material.
3. A process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble aluminum salt wherein aluminum is a cation, then rinsing and drying the material.
4. A process for inducing water repellance in cellulosic fibrous materials which comprises immersing the fibrous material in an aqueous. bath containing ammonium dicarbonato zirconylate and a water soluble soap, and thereafter immersing said material in an aqueous solution containing a soluble tin salt wherein tin is a cation, then rinsing and drying the material.
5. A process for inducing'water repellance in paper which comprises immersing the paper in an aqueous water repellance bath containing a water soluble soap and a water soluble alkaline double ammonium zirconium carbonate for a time suficient to saturate the paper with the solution, thereafter immersing the so saturated paper in anaqueous solution of zirconyl chloride to fix-the water repellance materials upon the fibers of the paper, then rinsing and drying the paper.
6. A fibrous material having water repellance properties comprising a base of c'ellulosic fibrous material, a hydrophobic coating thereon of the reaction product of an aqueous solution of ammonium dicarbonato zirconylate and a water soluble soap and a fixative for said coating comprising a polyvalent metal cation selected from the group of metals consisting of groups three, four and eight of Mendeleefis periodic arrangement of the elements.
'7. A paper sheet having water repellance properties and having on the surface thereof a hydrophobic coating of the reaction product of an aqueous solution of ammonium dicarbonato zirconylate and a water soluble soap and a fixative for said coating comprising a polyvalent metal cation selected from the group of metals consisting of groups three, four and eight of Mendeleeifs periodic arrangement ofthe elements.
STEPHEN F. URBAN. WARREN B. BLUMENTHAL.
References Cited in the file of this patent UNITED STATES PATENTS Number Name Date 1,799,949 Boughton' Apr. '7, 1931 2,165,265 Hubert et a1 July 11, 1939 2,323,387 Edelstein July 6, 1943 2,361,830 Edelstein Oct. 31, 1944 2,457,853 Van Mater Jan. 4, 1949

Claims (1)

1. A PROCESS FOR INDUCING WATER REPELLANCE IN CELLULOSIC FIBROUS MATERIALS WHICH COMPRISES IMMERSING THE FIBROUS MATERIAL IN AN AQUEOUS BATH CONTAINING AMMONIUM DICARBONATO ZIRCONYLATE AND A WATER SOLUBLE SOAP, AND THEREAFTER IMMERSING SAID SO TREATED MATERIAL IN AN AQUEOUS SOLUTION CONTAINING A SALT WHICH YIELDS A CATION OF A METAL SELECTED FROM THE GROUP OF METALS OF GROUPS THREE, FOUR AND EIGHT OF MENDELEEFF''S PERIODIC ARRANGEMENT OF THE ELEMENTS, THEN RINSING AND DRYING THE MATERIAL.
US6725448 1948-12-24 1948-12-24 Water repellence fixative treatment Expired - Lifetime US2641558A (en)

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GB2882949A GB684686A (en) 1948-12-24 1949-11-10 Improvements in or relating to a process for treating fibrous materials to render them water repellent

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767104A (en) * 1953-10-23 1956-10-16 Cravenette Company Metal-coated cloth and composition and method for making the same
US2952580A (en) * 1954-02-02 1960-09-13 Herbert Manfred Freud D Frasch Process for the modification of fibrous materials
US2978347A (en) * 1956-12-21 1961-04-04 Union Carbide Corp Organo-zirconium derivatives
US3242028A (en) * 1961-01-17 1966-03-22 Oxford Paper Co Insolubilized proteinaceous films
US3418073A (en) * 1965-10-18 1968-12-24 Nat Lead Co Production of ammonium zirconyl carbonate
US3615172A (en) * 1969-02-12 1971-10-26 Nl Industries Inc Preparation of crystalline carbonatozirconates of ammonium and potassium
US4061720A (en) * 1972-10-13 1977-12-06 Magnesium Elektron Limited Preparation of ammonium and potassium zirconium carbonates
US4097430A (en) * 1971-10-22 1978-06-27 Magnesium Elektron Ltd. Aqueous polymeric dispersions made thixotropic by certain ammonium or potassium zirconium carbonates
CN102776803A (en) * 2012-04-20 2012-11-14 深圳市瑞成科讯实业有限公司 Preparation method for preparing potassium-zirconium-carbonate water repellent agent

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1799949A (en) * 1922-12-15 1931-04-07 Bennett Box Co Art of stiffening
US2165265A (en) * 1935-05-12 1939-07-11 Ig Farbenindustrie Ag Process of imparting hydrophobic properties to cellulose fibers
US2323387A (en) * 1939-12-04 1943-07-06 Pond Lily Company Process of producing water repellent textile material
US2361830A (en) * 1941-07-15 1944-10-31 Pond Lily Company Water repellent textile and process of producing the same
US2457853A (en) * 1944-09-20 1949-01-04 Nat Lead Co Treatment of textiles and composition therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1799949A (en) * 1922-12-15 1931-04-07 Bennett Box Co Art of stiffening
US2165265A (en) * 1935-05-12 1939-07-11 Ig Farbenindustrie Ag Process of imparting hydrophobic properties to cellulose fibers
US2323387A (en) * 1939-12-04 1943-07-06 Pond Lily Company Process of producing water repellent textile material
US2361830A (en) * 1941-07-15 1944-10-31 Pond Lily Company Water repellent textile and process of producing the same
US2457853A (en) * 1944-09-20 1949-01-04 Nat Lead Co Treatment of textiles and composition therefor

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767104A (en) * 1953-10-23 1956-10-16 Cravenette Company Metal-coated cloth and composition and method for making the same
US2952580A (en) * 1954-02-02 1960-09-13 Herbert Manfred Freud D Frasch Process for the modification of fibrous materials
US2978347A (en) * 1956-12-21 1961-04-04 Union Carbide Corp Organo-zirconium derivatives
US3242028A (en) * 1961-01-17 1966-03-22 Oxford Paper Co Insolubilized proteinaceous films
US3418073A (en) * 1965-10-18 1968-12-24 Nat Lead Co Production of ammonium zirconyl carbonate
US3615172A (en) * 1969-02-12 1971-10-26 Nl Industries Inc Preparation of crystalline carbonatozirconates of ammonium and potassium
US4097430A (en) * 1971-10-22 1978-06-27 Magnesium Elektron Ltd. Aqueous polymeric dispersions made thixotropic by certain ammonium or potassium zirconium carbonates
US4061720A (en) * 1972-10-13 1977-12-06 Magnesium Elektron Limited Preparation of ammonium and potassium zirconium carbonates
CN102776803A (en) * 2012-04-20 2012-11-14 深圳市瑞成科讯实业有限公司 Preparation method for preparing potassium-zirconium-carbonate water repellent agent

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