US2952580A - Process for the modification of fibrous materials - Google Patents

Process for the modification of fibrous materials Download PDF

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US2952580A
US2952580A US485313A US48531355A US2952580A US 2952580 A US2952580 A US 2952580A US 485313 A US485313 A US 485313A US 48531355 A US48531355 A US 48531355A US 2952580 A US2952580 A US 2952580A
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solution
gelatin
paper
fibrous
complex
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Herbert Manfred Freud D Frasch
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    • 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
    • D21H21/36—Biocidal agents, e.g. fungicidal, bactericidal, insecticidal 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
    • D06M11/32—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—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 oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
    • 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
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • 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
    • D21H17/63—Inorganic compounds
    • D21H17/70—Inorganic compounds forming new compounds in situ, e.g. within the pulp or paper, by chemical reaction with other substances added separately

Definitions

  • T102 titanium dioxide
  • the present invention also contemplates as an object thereof the production of relatively stable solution of cerium titanium and zirconium acid complexes.
  • the present invention contemplates methods of production of complex ceryl, titanyl and zirconyl-acid solutionsforthe-treatment of paper and the like.
  • the present invention also contemplates as an object thereof the production of relatively stable solutions of cerium, titanium and. zirconium-acid-gelatin complexes.
  • the present invention mainly consists in a method of improving the characteristics of a fibrous cellulose product, comprising the steps of applying to a fibrous cellulose stock an aqueous solution having a pH -7 of at least one water-soluble complex of monovalent radical-metal oxide-organic acid radical salts, the monovalent radical being selected from the group consisting of alkali metals and ammonium, the metal oxide being selected from the group consisting of ZrO TiO and CeO and the organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid, and lactic acid, the molecular ratio of the organic acid radical to the metal oxide being between 1:2 and 1:6, and precipitating a substance including the metal oxide from the applied solution while the fibrous cellulose stock is in contact therewith, whereby the precipitated substance is retained by the fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • the monovalent radical being selected from the group consisting of alkali metals and ammonium
  • the metal oxide being selected from the group
  • the solution may be applied to the fibrous cellulose stock by adding the solution to the paper-making waters, e.g. by addition of the solution to the beater or tub before or after the introduction of the fibrous stock.
  • the flocculation or precipitation of the complex including the metal oxide in the paper pulp may then be accomplished by lowering the pH of the solution sufiiciently to cause the flocculation, preferably by the addition of a polyvalent cation such as aluminum or thorium in the form of aluminum sulfate or thorium sulfate, for example.
  • ac cordance with the present invention by distributing the usual powdered filler, such as titanium dioxide, zinc sulfide, and the like in the solution of the complex, this powdered filler acting as adjunct to the complex in the solution and the filler filling the interstices between the fibers while the complex upon precipitation thereof is embedded in the fibers themselves.
  • the amount of filler distributed in the solution plus the amount of metal oxide itself in the solution in the form of a complex is always substantially less than the amount of powdered filler necessary according to the prior processes without the use of the complex while achieving at least the equivalent results of the prior processes. This, therefore, results in a considerable the presence of a polyvalent cation furnished by a salt l saving in the filler material which is of great importance economically in the paper industry.
  • zirconyl such as the sulfates, chlorides and the like, cannot be utilized because they cannot be brought to a pH of 5-7 since they already start to flocculate at a pH of about 2.
  • the solutions of the complexes according to the present invention may be prepared by taking a soluble salt of zirconium, titanium or cerium such as zirconyl sulfate or titanyl sulfate and dissolving as much as possible thereof in water. Any concentration of the soluble salt may be utilized, but for reasons of economy it'is most suitable to utilize saturated solutions.
  • the solutions are introduced into the heaters or vats before or after the introduction of the paper pulp, before, after or along with the introduction of filler materials, before or after the introduction of resinates, but in all cases before the introduction of the precipitating salt such as aluminum sulfate which acts as fiocculant for the solution which should first penetrate intimately into the fibers of the paper pulp before the flocculation is caused.
  • the precipitating salt such as aluminum sulfate which acts as fiocculant for the solution which should first penetrate intimately into the fibers of the paper pulp before the flocculation is caused.
  • the use of the solutions of the complexes in accordancewith the present invention may be combined with the use of known filler materials in powder form in orderto increase the whiteness and opacity of paper.
  • Whiteness Purity Opacity -It may, therefore, be seenthat the'precipitation of 130 g. of 210 in the fibers giveidentical and even superior results to 4 kg. of powdered 'TiO the difference between the amount of powdered TiO used in Test A EXAMPLE II Sodium citrate was added to a solution of titanium sulfate dissolved in 18 liters of water, the amounts being adjusted in such manner that the solution contained 1 kg. of Ti0 and so that the molecular ratio of citrate to TiO was about 1:6. Sodium carbonate was then added to the solution until the pH thereof was raised to about 6.5. Upon addition of the sodium carbonate a precipitate formed which, after a short time, redissolved by itself.
  • sufiicient amount of water to have 5% of pulp dispersed in the water was added 18 liters of the solution of the titanium complex, prepared as above, the 18 liters containing 1 kg. of TiO
  • the T iO was precipitated from the solution by the addition of aluminum sulfate to the solution.
  • the resulting paper had a weight of 44 g. per square meter and had the following chardispersed in a acteristics:
  • an albuminoid gluej is dissolvedin the solution-of invention.
  • j the g; the, albuminoid glue. 7 than'lxetween 5 and 7,- and most preferably the pH should bebetween 5.75
  • the molecular ratio of citrate'to ZrO should be preferably between 1:2 .9 i
  • the pH of the sodium-Zro -citrate solution is always adjusted to between 5.5 and 7 by the addition of an alkali salt such as sodium carbonate before the incorporation of the albuminoid glue into the solution to prevent flocculation in the solution.
  • the solution On the other hand, if the pH of the solution is less than 5.5, the solution soon flocculates and is unusable, while if the pH is greater than 7, the solution is incapable of tanning the gelatin.
  • the gelatin is used in the the pH, it is possible to obtain stable solutions, that is to say, in which there is neither flocculation of the ZrO nor flocculation of gelatin, this double flocculation, however, being produced automatically and irreversibly (with the, formation of a gel-not of a. salt-which apparently is constituted by a mixture of complexes of zirconium; of tannedgelatin and of various alkali salts) when't'he concentration of the solution is increased above a certain value as will be explained infurther detail.
  • pise'fit' iiivention also comprises methodsof producing the-"solutions of the present inventiemtjhemetrtodeonsisting rm (m-Fornranen of aqueous solution of a soluble salt of zirconium and of citric acidbr' of an alkali metal or sari er ei "'dacid and adjusting the pH of the s lmionw-netweenss-and 7- by the addition of alkali hydroxide; carbonate-or bicarbonate; and
  • the carbonate is added either after the citrate or at the same time, in a proportion such that the pH of the final solution is between 5.5 and 7, and preferably between 5175 and fijf
  • Theproportion of the zirconium" saltin the solution is only limited bythe solubility of b the salt.
  • the process passes into a second stagethat is, the incorthe gelatin.
  • a whiteness form of a clear aqueous solution thereof having a pH of about 6. If the. pH of the gelatin is not between 5.5 and 7, the pH is adjusted by measured addition of a weak acid or a weak base.
  • the quantity of gelatin that may be incorporated into the defined complex solution varies on the one hand with the concentration of the zirconium salt of the solution, on the other hand with the quantity of citrate incorporated into the solution and, finally, with the dilucitrate-zirconium salt.
  • solutions 11, 25 and 34 are perfectly identical from the point of view of composition in zirconium salt and citrate-that is to say, each containing 1.1% Zr0 and 0.99% citrate. Nevertheless, in 100 cc. of solution 11 it is possible to add more than 367 cc. of the 5% gelatin solution without obtaining any nephelometric trouble. In solution 25, on the other hand, the nephelometric trouble is obtained with 26.4 cc. of the 5% gelatin solugelatin solution. It is therefore possible, according to the present invention, to prepare solutions containing variable quantities of gelatin for the same concentrations of zirconium, and while always obtaining satisfactory results.
  • solution 5 is preparedrlhatis to. say, a solution containing 1.1% 210 and 0.96% of citrate, and if only 20 cc. of 5% gelatin solution is added (1 g. of gelatin) in place of 147 cc., the solution will remain stable.
  • the resulting pH of the solution is 6.2.
  • this solution is titrated with a solution of 5% gelatin, it is necessary to utilize 52.8 'cc. of the gelatin solution in order to obtain the nephelometric trouble. /3 of this quantity, that is 17.6 cc., permits the obtention of a stable solution conforming to the invention.
  • the final mixture contains, therefor, for 1 liter of solution, 10.3 g. of ZrO 9.8 g. of citrate and 0.82 g. of gelatin, which is about 1% Zr0 1% citrate and 0.08% gelatin.
  • a piece of paper having a humidity content of 50% and a whiteness by opacity of 56% was treated with this solution by soaking and drying.
  • the resulting paper was out in many ways. The example above given mentions the case of soaking.
  • it is sufiicient to add to the pulp or to the suspension a quantity of solution which would be calculated by relation to the paper or the fiber or other material in suspension, the active elements of the solution having the tendency to fix themselves to the paper, fiber or other material.
  • This quantity could be determined in each case as a function of the objects to be obtained and the material to be treated. 1
  • the usual filler materials such as powdered TiO or powdered ZnS may be dispersed either in those solutions not containing the gelatin or in the gelatinoontaining solutions.
  • the powdered filler material remains in stable suspension in the solution which permits the use of lower quantities of the powdered filler and much more easily controllable conditions while obtaining the same results as in the known processes.
  • the process for the treatment of the paper or pulp may proceed either by: (a) first preparing a suspension of the powdered filler in the gelatin-zirconium complex solution and introducing this suspension into the beater, or (b-) introducing the solution of the gelatin-zirconium complex into the beater and then adding the filler, the suspension-according to the present invention-thus being prepared in situ.
  • new industrial products are actually produced, that is, fibrous materials such as paper containing ZrO (or CeO or TiO the white filler material such as the powdered TiO or ZnS, and the albuminoid glue as sizing.
  • Cylinder I This cylinder contained a suspension of 10% Ti by weight in water. After about one minute all of the TiO fell to the bottom of the cylinder and the supernatant water was clear.
  • Cylinder H This cylinder contained a suspension of 1% by weight of TiO in water. After about minutes the same phenomenon was observed as in cylinder 1.
  • Cylinder III This cylinder contained a suspension of 0.1% by weight of TiO;,. The same phenomenon was observed as in the first two cylinders, but requiring 15 minutes.
  • Cylinder V This cylinder contained a suspension of 1% by weight of TiO in a solution containing 20 cc. per liter of the same gelatin-zirconium complex solution as in cylinder IV, that is, 0.0379% ZrO and 0.005% gelatin. After about 24 hours slightly less than half of the TiO fell to the bottom of the cylinder and the rest remained permanently in suspension.
  • Cylinder VI This cylinder contained a suspension of 0.1% of TiO in a solution containing 2 cc. per liter of the same solution of gelatin-zirconium complex as in cylinders IV and V, that is, containing 0.0037% ZrO 12 and 0.0005% of gelatin. The same results were obtained as in cylinder V.
  • Cylinder VII shows that very small quantities of gelatin-Zirconium complex, that is to say, in the order of several milligrams per liter, added to the suspension of TiO enormously increases the relative stability of the suspension.
  • a seventh cylinder was prepared containing a suspension of 1% of Tit); in a solution of 0.005% of gelatin (the same solution as in cylinder V but without any ZrO After about three hours half of the TiO fell to the bottom and in 12 hours all of the TiO; fell to the bottom, the supernatant water had become perfectly clear.
  • the combination, therefore, of the gelatin-zirconium complex solution with dispersed powdered filler material therefore permits in the paper industries ofavoiding practically completely any loss in the use of the filler (losses which in the case of TiO- for example, runs to about 50% of the TiO- introduced into the heaters). therefore, results in greatly lowering the price of the final product while obtaining equal whitenms and opacity with a. resistance increased as well as in providing a microbial and fungicidal action as previously described.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of monovalent radical-metal oxideorganic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consisting of ZrO TiO and CeO and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic aid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6; and precipitating a substance including said metal oxide from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance
  • said monovalent radical being selected from the group consisting of alkali metals and ammonium
  • said metal oxide being selected from the group consisting of ZrO TiO and CeO
  • said organic acid radical being selected from the group consisting of citric acid, mal
  • Lassa is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of sodium-ZrO -citrate salts, the molecular ratio of citrate to 210 being between 112.5 and 1:4, and precipitating a substance including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 57 of at least one watersoluble complex of sodium-TiO citrate salts, the molecular ratio of citrate to TiO being between 1:45 and 1:6; and precipitating a substance including said Ti from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having-a pH between 7 of at least one watersoluble complex of sodium-ZrO -citrate salts, the molecular ratio of citrate to ZrO being between 1:25 and 1:4, said solution containing between 26% by weight of ZrO and precipitating a substance including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, Wherebysaid precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of sodium-TiO -citrate salts, the molecular ratio of citrate to TiO being between 1:45 and 1:6, said solution containing between 26% by weight of 'IiO ,and precipitating a substance including said TiO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of monovalent radical-metal oxideorganic acid radical salts, said monovalent radical being selected from the group consisting of alkali nietals and ammonium, said metal oxide being selected from the group consisting of ZrO Ti0 and CeO and said or-, ganic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6, said solution having distributed therethrough at least one insoluble powdered filler; and precipitating a substance including said metal oxide from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance and said powdered filler are retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • monovalent radical being selected from the group consisting of
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 57 of at least one watersoluble complex of sodium-ZrO -citrate salts, the molecular ratio of citrate to ZrO being between 1:25 and 1:4, said solution having distributed therethrough powdered 14 TiO and precipitating a substance including said ZrC from said applied solution while said fibrous cellulose stock is in contact therewith, whereby said precipitated substance and said powdered TiO are retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 57 of at least one watersoluble complex of monovalent radical-metal oxideorganic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consisting of ZrO TiO and CeO and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6; and treating said applied solution while said fibrous cellulose stock is in contact therewith with a soluble salt of a polyvalent' metal and a mineral acid in a quantity sufiicient to lower the pH of said solution to precipitate a substance includ-' ing said metal oxide therefrom, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of monovalent radical-metal oxideorganic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from' the group consisting of ZrO TiO and CeO and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6; and treating said applied solution while said fibrous cellulose stock is in contact therewith with aluminum sulfate in a quantity sufiicient to lower the pH of said solution to precipitate a substance including said metal oxide therefrom, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • monovalent radical being selected from the group consisting of alkal
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5-7 of at least one watersoluble complex of monovalent radical-metal oxide-or ganic acid radical salts, said monovalent being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consistingof 'ZrO TiO and CeO and said organic acid radical being selected from thegroup consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6; and treating-said applied solution while said fibrous cellulose stock is in contact therewith with thorium sulfate in a quantity sufiicient to lower the pH of said solution to precipitate a substance including said metal oxide therefrom, whereby said precipitated substance is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • monovalent selected from the
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.5-7 of at least one watersoluble complex of monovalent radical-metal oxide-organic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consisting of ZrO ,-TiO and CeO and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6, said solution having dissolved therein an albuminoid glue in a predetermined amount below the amount at which flocculation of said albuminoid glue in said solution occurs; and precipitating said albuminoid glue and said complex including said metal oxide from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is retained by said fibrous cellulose stock, increasing the white
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a-fibrous natural cellulose stock an aqueous solution having a pH between 5.5-7 of at least one watersoluble complex of monovalent radical-metal oxide-organic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consisting of ZrO,, TiO; and :20;, and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occursyand precipitating said gelatin and said complex including said metal oxide from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.5 and 7 of water-soluble complex of sOdium-ZrO -citrate salts, the molecular ratio of citrate to Zr0 being between 1:2.9 and 1:3.4, said solution having dissolved therein gelatin.in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs; and precipitating said gelatin and said complex including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.75 and 6.5 of water-soluble complex of sodium-ZrO -citrate salts, the molecular ratio of citrate to ZrO being between 1:29 and 1:3.4, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs; and precipitating said gelatin and said complex including said 210 from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of spraying onto a fibrous natural cellulose stock an aqueous solution having a pH between 5.5 and 7 a water-soluble complex of sodium-ZrO -citrate salts, the molecular ratio of citrate to ZrO being between 122.9 and 1:3.4, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs; and evaporating water from said applied solution while said fibrous cellulose stock is in contact therewith so as to precipitate said gelatin and said complex including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is re- 16 tained by said fibrous celluose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of immersing a fibrous natural cellulose stock in an aqueous solution having a pH between 5.5 and 7 of water-soluble complex of SOdiUlIl-ZIOg-Clililifi salts, the molecular ratio of citrate to ZrO being between 1:29 and 1:3.4, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs; and removing the thus immersed fibrous cellulose stock from said solution and allowing the water of said applied solution to evaporate so as to precipitate said gelatin and said complex including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby molecular ratio of citrate to Zr0 being between 112.9
  • said solution having dissolved therein gelatin in a' predetermined amount below the amount at which flocculation of said gelatin in said solution occurs; and removing the thus immersed fibrous cellulose stock from said solution and allowing the water of said applied'solution to evaporate so as to precipitate said gelat'm and said complex including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate is retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.5-7 of at least one water-soluble complex of monovalent radical-metal oxideorganic acid radical salts, said monovalent radical being selected from the group consisting of alkali metals and ammonium, said metal oxide being selected from the group consisting of ZrO TiO and CeO and said organic acid radical being selected from the group consisting of citric acid, malic acid, tartaric acid and lactic acid, the molecular ratio of said organic acid radical to said metal oxide being between 1:2 and 1:6, said solution having dissolved therein an albuminoid glue in a predetermined amount below the amount at which flocculation of said albuminoid glue in said solution occurs, and said solution having distributed therethrough at least one insoluble powdered filler; and precipitating said albuminoid glue and said complex including said metal oxide from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitating
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.5-7 of a water-soluble complex of SOdium-ZrO -citrate salts, the molecular ratio of citrate to ZrO being between 1:2 and 1:6, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs, and said solution having distributed therethrough at least one insoluble powdered filler; and precipitating said gelatin and said complex including said ZrO from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate and said powdered filler are retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.
  • a method of improving the characteristics of a fibrous natural cellulose product comprising the steps of applying to a fibrous natural cellulose stock an aqueous solution having a pH between 5.5-7 of a water-soluble complex of sodium-TiO -citrate salts, the molecular ratio of citrate to Ti0 being between 1:2 and 1:6, said solution having dissolved therein gelatin in a predetermined amount below the amount at which flocculation of said gelatin in said solution occurs, and said solution having distributed therethrough at least one insoluble powdered filler; and precipitating said gelatin and said complex including said TiO- from said applied solution while said fibrous cellulose stock is in contact therewith, whereby the precipitate and said powdered filler are retained by said fibrous cellulose stock, increasing the whiteness and opacity thereof.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Pest Control & Pesticides (AREA)
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  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
US485313A 1954-02-02 1955-01-31 Process for the modification of fibrous materials Expired - Lifetime US2952580A (en)

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FR1027050X 1954-02-02

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US (1) US2952580A (enrdf_load_stackoverflow)
DE (1) DE1027050B (enrdf_load_stackoverflow)
FR (2) FR1099015A (enrdf_load_stackoverflow)
GB (1) GB780513A (enrdf_load_stackoverflow)
NL (2) NL113652C (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3985611A (en) * 1971-07-15 1976-10-12 Comitate Nazionale Per L'energia Nucleare Wholly inoganic papers and membranes suitable for ion exchange made of thorium acid phosphate and process for preparing the same
US4115187A (en) * 1970-03-31 1978-09-19 Welwyn Hall Research Association Agglomerated fillers used in paper
US4756801A (en) * 1984-01-11 1988-07-12 Kemira Oy Paper-making method and a combination of ingredients to be used in it
US5223176A (en) * 1988-09-30 1993-06-29 Nissan Chemical Industries, Ltd. Zirconia sol and method for making the same
US5270076A (en) * 1991-04-11 1993-12-14 E. I. Du Pont De Nemours And Company Process for coating alkyl ketene dimer on titanium dioxide
US6579410B1 (en) * 1997-07-14 2003-06-17 Imerys Minerals Limited Pigment materials and their preparation and use

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0366934B1 (en) * 1988-09-30 1993-03-03 Nissan Chemical Industries Ltd. Zirconia sol and method for making the same
GB9321482D0 (en) * 1993-10-18 1993-12-08 Alcan Int Ltd Manufacture and use of a zirconium-protein system
RU2412296C1 (ru) * 2010-03-12 2011-02-20 Открытое акционерное общество "Центральный научно-исследовательский институт бумаги" (ОАО "ЦНИИБ") Способ получения бумажной массы

Citations (17)

* Cited by examiner, † Cited by third party
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US1692372A (en) * 1927-05-13 1928-11-20 Henry A Gardner Treating artificial silk
US1820987A (en) * 1928-03-27 1931-09-01 Titanium Pigment Co Inc Methods of precipitating titanium compounds
US1916236A (en) * 1928-03-27 1933-07-04 Titanium Pigment Co Inc Method of precipitating titanium compounds
US1935196A (en) * 1930-06-27 1933-11-14 Celotex Company Preservation of fibrous products
US1946141A (en) * 1932-04-01 1934-02-06 Riegel Paper Corp Wrapping paper
US2042338A (en) * 1934-02-03 1936-05-26 Merrimac Chemical Co Manufacture of pigmented paper
US2106039A (en) * 1935-12-12 1938-01-18 Gen Electric Condenser dielectric material
US2121343A (en) * 1935-04-12 1938-06-21 Dreyfus Henry Treatment of textile materials
US2193818A (en) * 1937-07-19 1940-03-19 Showa Sangyo Co Process for producing proteic coating or film upon fiber, textile, or the like
GB520701A (en) * 1937-10-27 1940-05-01 Fides Gmbh Improvements in or relating to the production of paper for electrical purposes
US2320771A (en) * 1939-12-19 1943-06-01 Strathmore Paper Company Paper sizing
US2416447A (en) * 1943-07-27 1947-02-25 Du Pont Weather resistant flameproof paper
US2482917A (en) * 1947-05-16 1949-09-27 Onyx Oil & Chemical Company Scrooping composition
US2503267A (en) * 1944-09-16 1950-04-11 Ecusta Paper Corp Cigarette paper
US2563656A (en) * 1946-09-18 1951-08-07 Du Pont Process for producing lustrous titanium impregnated yarns
US2641558A (en) * 1948-12-24 1953-06-09 Nat Lead Co Water repellence fixative treatment
US2692183A (en) * 1949-07-07 1954-10-19 Upson Co Method for treating cellulose and product thereof

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Publication number Priority date Publication date Assignee Title
US2080437A (en) * 1934-10-15 1937-05-18 Raffold Process Corp Paper manufacture
NL43300C (enrdf_load_stackoverflow) * 1935-05-02
US2399873A (en) * 1940-12-28 1946-05-07 Stanco Inc Process of coating with preservative compositions

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1692372A (en) * 1927-05-13 1928-11-20 Henry A Gardner Treating artificial silk
US1820987A (en) * 1928-03-27 1931-09-01 Titanium Pigment Co Inc Methods of precipitating titanium compounds
US1916236A (en) * 1928-03-27 1933-07-04 Titanium Pigment Co Inc Method of precipitating titanium compounds
US1935196A (en) * 1930-06-27 1933-11-14 Celotex Company Preservation of fibrous products
US1946141A (en) * 1932-04-01 1934-02-06 Riegel Paper Corp Wrapping paper
US2042338A (en) * 1934-02-03 1936-05-26 Merrimac Chemical Co Manufacture of pigmented paper
US2121343A (en) * 1935-04-12 1938-06-21 Dreyfus Henry Treatment of textile materials
US2106039A (en) * 1935-12-12 1938-01-18 Gen Electric Condenser dielectric material
US2193818A (en) * 1937-07-19 1940-03-19 Showa Sangyo Co Process for producing proteic coating or film upon fiber, textile, or the like
GB520701A (en) * 1937-10-27 1940-05-01 Fides Gmbh Improvements in or relating to the production of paper for electrical purposes
US2320771A (en) * 1939-12-19 1943-06-01 Strathmore Paper Company Paper sizing
US2416447A (en) * 1943-07-27 1947-02-25 Du Pont Weather resistant flameproof paper
US2503267A (en) * 1944-09-16 1950-04-11 Ecusta Paper Corp Cigarette paper
US2563656A (en) * 1946-09-18 1951-08-07 Du Pont Process for producing lustrous titanium impregnated yarns
US2482917A (en) * 1947-05-16 1949-09-27 Onyx Oil & Chemical Company Scrooping composition
US2641558A (en) * 1948-12-24 1953-06-09 Nat Lead Co Water repellence fixative treatment
US2692183A (en) * 1949-07-07 1954-10-19 Upson Co Method for treating cellulose and product thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115187A (en) * 1970-03-31 1978-09-19 Welwyn Hall Research Association Agglomerated fillers used in paper
US3985611A (en) * 1971-07-15 1976-10-12 Comitate Nazionale Per L'energia Nucleare Wholly inoganic papers and membranes suitable for ion exchange made of thorium acid phosphate and process for preparing the same
US4756801A (en) * 1984-01-11 1988-07-12 Kemira Oy Paper-making method and a combination of ingredients to be used in it
US5223176A (en) * 1988-09-30 1993-06-29 Nissan Chemical Industries, Ltd. Zirconia sol and method for making the same
US5270076A (en) * 1991-04-11 1993-12-14 E. I. Du Pont De Nemours And Company Process for coating alkyl ketene dimer on titanium dioxide
US6579410B1 (en) * 1997-07-14 2003-06-17 Imerys Minerals Limited Pigment materials and their preparation and use

Also Published As

Publication number Publication date
FR1099015A (fr) 1955-08-29
DE1027050B (de) 1958-03-27
NL194436A (enrdf_load_stackoverflow)
NL113652C (enrdf_load_stackoverflow)
GB780513A (en) 1957-08-07
FR1114001A (fr) 1956-04-06

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