US3281312A - Fibrous product containing resinous material and polyethylene oxide and process thereof - Google Patents

Fibrous product containing resinous material and polyethylene oxide and process thereof Download PDF

Info

Publication number
US3281312A
US3281312A US39759964A US3281312A US 3281312 A US3281312 A US 3281312A US 39759964 A US39759964 A US 39759964A US 3281312 A US3281312 A US 3281312A
Authority
US
United States
Prior art keywords
resin
polyethylene oxide
water
added
stock
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
Inventor
Robert A Fetters
Hanns F Arledter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mead Corp
Original Assignee
Mead Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mead Corp filed Critical Mead Corp
Priority to US39759964 priority Critical patent/US3281312A/en
Application granted granted Critical
Publication of US3281312A publication Critical patent/US3281312A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21CPRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02Working-up waste paper
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/53Polyethers; Polyesters
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/63Inorganic compounds
    • D21H17/66Salts, e.g. alums
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP 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
    • D21H23/00Processes or apparatus for adding material to the pulp or to the paper
    • D21H23/76Processes or apparatus for adding material to the pulp or to the paper characterised by choice of auxiliary compounds which are added separately from at least one other compound, e.g. to improve the incorporation of the latter or to obtain an enhanced combined effect
    • D21H23/765Addition of all compounds to the pulp
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/64Paper recycling

Definitions

  • This invention relates to the production of evenly distributed resin in resin-filled fibrous material and, more particularly, to uniformly dispersed resin-filled moldable pulp material and products thereof.
  • the primary object of this invention is to provide a process for incorporating and substantially uniformly dispersing resinous materials in fibrous webs, which can be done easily and economically on existing papermaking equipment and without the need for critical control of process variables.
  • Another object is to provide a process for incorporating resinous materials in fibrous webs in which the resinous materials .are substantially all retained and distributed substantially uniformly throughout the fibrous Web.
  • a further object of the invention is to produce a resinfilled paper or board which may be easily formed under heat and pressure, and may be subsequently decorated by printing, painting, or lacquering.
  • a still further object is to produce a resin-filled fibrous product in which the physical properties of the fibrous product may be altered as desired by proper choice of resin, polyvalent metal salt, and pulp, and by the ratio of resin to pulp.
  • Another object is to provide a process of incoporating resinous materials in fibrous webs in which process problems such as slow drainage on the wire, plugging of the wire and felts, and sticking to the wire, felts, and dryer drums are substantially eliminated.
  • This invention is predicated on the unexpected discovery and concept that the interaction of a polyvalent metal ion with a water or alkali soluble resinous material capable of being precipitated by a polyvalent metal ion, in intimate association with dispersed pulp fibers and the treatment of the resulting mixture with a dilute solution of a high molecular weight polyethylene oxide alone or in "ice combination with other additives will produce a substantially uniformly dispersed resin filled moldable material.
  • polyvalent means having a valence greater than unity.
  • the process for carrying out this invention comprises: the treatment of dispersed pulp fibers with a polyvalent metal ion in the form of a salt, the treatment of the resulting pulp-metal ion mixture with water or alkali resinous material in solution and the treatment of the resulting mixture with a dilute solution of a high molecular weight polyethylene oxide.
  • High molecular weight polyethylene oxides of the type herein referred to which have been found to be preferable for use in this invention have molecular weights ranging from at least 1,000,000 to 10,000,000 and preferably of the order of 3,650,000 and are sold by Union Carbide Chemicals Company, Division of Union Carbide Corporation, under their generally identifying trademark Polyox. And by reason 'of innovations in catalysis as well as manufacturing techniques, these high molecular weight polyethylene oxide materials are available which have molecular Weights ranging from about 50,000 to an excess of 10,000,000. Surprisingly, these high molecular weight materials are soluble in water and form relatively stable solutions at temperatures below C. Small amounts of these materials will thicken water so that it becomes a very viscous mass.
  • one such commercial product utilized by applicants has an average viscosity of 3,000 centipoises in a 1% aqueous solution. This particular material has a molecular weight of approximately 3,000,000. Another such commercial product has an average viscosity, as a 1% solution, of approximately 7,000 centipoises with its average molecular weight being about 6,000,000.
  • Various techniques for producing the above type of polyethylene oxides are set forth in an article by F. N. Hill et al., entitled High Molecular Weight Polymers of Ethylene Oxide, appearing at pages 5-7 of volume 50, No. 1, January 1958 issue of Industrial and Engineering Chemistry. Particular reference is made to the paragraph entitled Polymerization on page 7 of this article.
  • the following general observations are submitted for carrying out the process so as to insure incorporating and substantially uniformly dispersing resinous materials in fibrous webs.
  • the ingredients added in each process step should be thoroughly mixed before the next ingredient is added.
  • the reaction time taken for each step is not critical, providing at least several seconds are available for complete flocculation.
  • Reasonable care should be exercised not to excessively agitate the stock after addition of the polyethylene oxide.
  • the resin solution may be added to the pulp prior to the addition of the polyvalent metal ion which should be added to the pulp fibers in the form of a soluble salt, preferably a chloride salt, although certain nitrates, acetates and sulfates have been successfully used.
  • Salts of the vallkaline earth metals are preferred, although the following salts have been successfully used in the process: calcium chloride, aluminum sulfate (paper makers alum), aluminum chloride, barium chloride, zinc sulfate, magnesium sulfate, beryllium nitrate, cadmium chloride, cobaltous chloride, cupric chloride, ferrous chloride, manganous chloride, mercuric acetate, nickelous chloride, stannic chloride, and strontium chloride.
  • the salts may be added as fine-1y divided solids, or in Water solution.
  • Suitable resinous materials are reaction products of an ous acid or fatty acid or combinations of same.
  • alkali hydroxide such as sodium hydroxide
  • resin- a resin-
  • reaction products are relatively water soluble and are used as aqueous solutions so that the resinous component will be intimately mixed with the pulp fibers.
  • the preferred resinous material is a mixture of the sodium salts of the acids present in tall oil and wood rosin, in a ratio of 85% tall oil and 15% rosin, hereinafter referred to as Resin A.
  • Other materials are the sodium salts of 1 wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic, oleic, stearic, and linoleic acids,.and mixtures of j these acids used per se or after chemical modification.
  • ammonium salts of shellac and the sodium salts of alkali soluble polyvinyl acetate copolymers are also acceptable;
  • the type of resinous material and polyvalent metal ion determine the melting point of the resinous component and to a considerable extent, thefinished properties of the resin filled product.
  • the high molecular weight polyethylene oxide has been found to be particularly effective as a means of controlling the floc size of the precipitated resin metal salts, and in improving retention of same. Flocculating agents other than polyethylene oxide have been tried, but with limited success.
  • the function of the polyethylene oxide appears to be one of controlled flocculation of the very fine precipitate for-med by the reaction of the polyvalent metal ions with the resinous material.
  • the polyethylene oxide appears to promote a high degree of uniform dispersion of the flocs in the fibrous mass. A range of from 0.002% to 0.1% of polyethylene oxide on resinfiber content has been found to be elfective in achieving this'result, depending on the consistency of the stock.
  • Defoamers may be added to control foam without materially aifecting the process.
  • Sulfuric acidand papermarkers alum have been added to control the pH of the takes to drain each sheet.
  • the temperature required to form or mold the resin-filled sheet of this invention can be adjusted by use of an acid or acid salt in combination with polyvalent metal ions.
  • an acid or acid salt in combination with polyvalent metal ions For example, addition of sulfuric acid or papermakers alum will reduce the temperature required to mold a paper board containing 20% of Resin A precipitated by calcium ion, the amount of molding temperature reduction amounting to about 20 F.
  • Such adjustment of molding temperature greatly increases the utility of the invention by adapting the product to existing molding presses of commerce.
  • the resin solution by acids or acid salts in combination with polyvalent metal ions presumably. gives a mixed resin precipitate comprising free resin acid admixed with metal salts of the resin acid.
  • the process of this invention was developed primarily for use on paper or board machines. However, this process is readily applied to the preparation of resin filled pulp stock for making resin-pulp preforms and the like, as by the usual pulp molding methods.
  • the resin-pulp stock containing the additives was poured into a British Sheet Machine filled with water up to the wire, and a handsheet was made without any further addition of water. The handsheet was then couched and dried. Several handsheets were made for each set of sheets, recording the time in seconds it Control sheets were made from the pulp stock without resin or other additives. All
  • EXAMPLE 3 Using the pulp stock of Example 1, three sets of handsheets were made in which the 6.35 ml. of 0.1% water solution of Kymene 557 of Sheets l-G reported in Table I were replaced with similar amounts of Parez 607, Amerex 8850, or polyethyleneimine.
  • Parez 607 is a cationic melamine formaldehyde produced by American Cyan amid Company.
  • Amerez 8850 is a liquid polyamide resin produced by American Marietta Company. The results for each of these sets of sheets is given in Table III.
  • Table 111 Materials added to the stock Drainage Percent White Handsheet and the order of addition pH time, sec. resin water retention III-A Resin A, CaClz, Parez 607, Poly- 8. 1 2. 8 93. 6 Almost clear.
  • EXAMPLE 4 Using a 1% consistency pulp prepared from double kraft lined corrugated cuttings in the manner illustrated in Example 1, a series of handsheets was made to illustrate the effects of various polyvalent metal salts on the retention of Resin A with and without the addition of polyethylene oxide.
  • the handsheets as shown in Table II illustrate the effect of the order of addition of materials to the pulp stock. It is observed that if the polyethylene oxide is added last, as in the ease of II-A and lL-C though II-F, there is substantially no difference in retention of Resin A. However, adding the polyethylene oxide before the Resin A, as in Sheet IIB, reduced the resin retention, and the white water was cloudy, indicating the presence of precipitated resin in the white water. Drainage times again mild agitation, and 3.15 ml. of 0.1% polyethylene oxide in water was added, where indicated in Table IV. In the case of handsheet IVDD (Table IV), 6.35 ml. of 0.1% Kymene 557 solution was also added following the addition of the aluminum sulfate.
  • Table IV 1 Materials added to the stock Drainage Percent Floccu- Handsheet and the order of addition pH time, sec. resin lation retention Resin A, BaClz 7- 6 5 82. Fair. Resin1 A, 13301:, Polyethylene 7. 9 2. 96. 4 Excellent.
  • Resin A CaClzn 6- 5 2- 2 79.1 Fair.
  • Resin1 A CaClz, Polyethylene 7. 8 2. 7 91. 6 Excellent.
  • Resin A C0011 6. 9 4. 0 87. 0 Fair.
  • Resin1 A 00011, Polyethylene 7. 2 3. 4 94. 2 Excellent.
  • Resin A Hg (Ac): 9 8. 4 84. 7 Fair.
  • Resini A Hg (Ach, Polyethylene 4. 6 4 0 98. 6 Excelle t.
  • Resin A NiOli 7 1 5 6 86. 1 Good.
  • Resin1 A NiCl Polyethylene 7. l 8. 8 94. 1 Excellent.
  • the degree of flocculations EXAMPLE 9 was determined by observations of the flocs and clarity of the Water phase. In each case, the polyethylene oxide substantially increased the retention of the Resin A, and in most cases the drainage time was decreased by the addition of the polyethylene oxide.
  • Example 6 The procedure of Example 5 was repeated using 100 grams of abietic acid and grams of sodium hydroxide.
  • EXAMPLE 7 The procedure of Example 5 was repeated using 50 grams of abietic acid, 50 grams of oleic acid and 20 grams of sodium hydroxide.
  • EXAMPLE 8 The procedure of Example 5 was repeated using 100 grams of linoleic acid and 20 grams of sodium hydroxide.
  • a paste of sodium palmitate was prepared in the laboratory by heating grams of palmitic acid with 17.1 grams of sodium hydroxide in enough water to make a total batch weight of 500 grams. The reacted paste was then dissolved in water and diluted to 3.90% solids. A portion of this solution was reacted with calcium chloride and this mixture was dried and the Parr Bar stick point was determined on the dried resin.
  • Example 10 The procedure of Example 9 was repeated using 100 grams of K wood rosin and 14.63 grams of sodium hydroxide.
  • Example 11 The procedure of Example 9 was repeated using 100, grams of WW wood rosin and 14.63 grams of sodium hydroxide.
  • Example 12 The procedure of Example 9 was repeated using 100 grams of a distilled tall oil fatty acid containing 5% rosin acids, and 15.14 gramsof sodium hydroxide.
  • Example 13 The procedure of Example 9 was repeated using 100 grams of stearic acid and 14.06 grams of. sodium hydroxide.
  • EXAMPLE 14 100 grams of a commercial grade of alkali soluble vinylacetate copolymer were added to a solution of 5.5 grams of sodium hydroxide in 900 grams of water. The
  • a handsheet was made in the oxide was added, and the stock was mixed using a manner described in Example 1 and the data obtained minimum of agitation.
  • the pH of the stock was 5.4. are reported in Table V. 20 Using this stock, a resin-fiber board having a basis weight of 68 pounds per thousand square feet was pro- EXAMPLE 15 quizzed on a Fourdrinier machine at a speed of 1.95 feet 50 81331113 Of an Orange Shellac Were addefi to 450 grams per minute.
  • a resin fiber board having a basis weight of 83 pounds per thousand square feet was produced on a Fourdrinier paper machine without difiiculty at a speed of 2.37 feet per minute.
  • flocculation was controlled in the chest by the addition of small amounts of 1% polyethylene oxide during the trial. Formation and drainage of the sheet on the wire were good, and there was no evidence of plugging the wire or felts or sticking to the press or felts. The calculated resin retention was 99.9%.
  • EXAMPLE 20 To prepare a 46.8%-53.2% fiber board, 3240 grams of double kraft lined cuttings were furnished to a beater and beaten to a TAPPI freeness of 562. The pulp stock was then dropped to a chest, and 2812 grams of dry Resin A were added as a dilute water solution. Additional water was added to the resin-fiber stock in the chest to give a resin-pulp consistency of 0.8%.
  • the board product was laminated to a 3 ply thickness with a heat setting adhesive.
  • the laminated board when presteamed for 60 seconds was easily formed in a press heated to a temperature of 160 F.
  • EXAMPLE 22 400 grams of double kraft lined corrugated cuttings Were dispersed in 20,000 ml. of Water in a laboratory disintegrator and blended for a period of at least 60 minutes. The pulp stock was then reduced to 0.76% consistency and had a TAPPI freeness of .500 to 550 ml. To 95 ml. portions of the 0.76% pulp stock were added 286 ml. of a 3.0% Resin A solution, stirring the solution in slowly. Dilution water was added to give a subsequent total volume of 1188 ml, including all the desired additives. This corresponds to a resin-pulp consistency of approximately 0.8%. Additional ingredients were added in the following manner. The calcium chloride was added as ml.
  • the resin-filled board of the examples of this invention may be formed under heat and pressure into a Widevariety of useful products. Luggage, automobile panels,
  • trays, mannequins, containers and the like may be prethose skilled in the art that the procedures described and the resultant products are adaptable to the use of any of a wide range of fibers.
  • Chemical wood pulps and cellulosic fibers from other sources, inorganic fibers, both natural and manufactured, such as fibers from glass, as bestos fibers, synthetic organic fibers and the like may be used Without departing from the scope of the invention.
  • the product of the invention may be adapted toa wide range of uses by choice of resin, precipitating ion, amount of resin, density of the resin-fiberboard, and other obvious variations evident. to those skilled inthe art.
  • the surface of the resinfiberboard of this invention may be treated with sizings and/ or coatings to serve as a base for further decorative treatments.
  • fibrous, relatively resin-free surface layers may be provided by employment of the process 1 of the invention on the middle cylinders of a multicylinder machine while the liner cylinders operate on resin-free pulp stocks.
  • multiple layers of the resin-filled board can be assembled, as by pasting, to provide thicker sections as may be desired.
  • a new article of manufacture consisting essentially of a fibrous product having resinou material incorporated and substantially uniformly distributed therethrough, said product containing from about 15% to about 90% resinous material and from about 10% to about 85 fiber, said resinous material being present in the form of a polyvalent metal salt derived by the precipitation of the soluble alkali salt of the resinous material with a polyvalent metal ion, said fibrous product including a fiocculant for said resinous material of about 0.002% to 0.1% high molecular weight polyethylene oxide based on the resin-fiber content, said soluble alkali salt of the resinous material being selected from the group consisting of sodium salts of the acids present in tall oil and wood rosin; sodium salts of wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic, oleic, stearic, linoleic acids; the ammonium salt of shellac and the sodium salt of alkali soluble polyvinyl acetate copolymers.
  • the fibrous product of claim 1 wherein the resinous material is a mixture of sodium salts of the acids present in tall oil and wood rosin in the ratio of 85% tall oil and 15 rosin.
  • a process for preparing a fibrous product containing from about 15% to about 90% resinous material and from about 10% to about 85% fiber which comprises the steps of preparing an aqueous dispersion of fibrous material with a polyvalent metal ion, said metal ion being in the form of a water-soluble salt selected from the group consisting of calcium, barium, magnesium, strontium and aluminum and present in an amount up to three times the stoichiometric amount required, treating the resulting fiber-metal ion solution with an alkali soluble salt of a resinous material to precipitate said material in the form of a polyvalent metal salt, said alkali soluble salt of the resinous material being selected from the group consisting of sodium salts of the acids present in tall oil and wood rosin; sodium salts of wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic acid, stearic, linoleic acids; the ammonium salt of shellac and the sodium salt of alakali soluble polyvinyl
  • a process for preparing a fibrous product having a range of about 72.6% to substantially resin retention which comprises preparing an aqueous dispersion of fibrous material, interacting a polyvalent metal ion with a water soluble resinous material capable of being precipitated by a polyvalent metal ion, in intimate association with said dispersion of fibrous material, said polyvalent metal ion being in the form of a water-soluble salt selected from the group consisting of calcium, barium, magnesium, strontium and aluminum and present in an amount up to three times the stoichiometric amount required, thereafter treating the resulting mixture with a a solution of high molecular weight polyethylene oxide whereby said polyethylene oxide is capable of effecting the flocculation of said precipitated water soluble resinous material.

Description

United States Patent FIBROUS PRODUCT CONTAINING RESINOUS MA- TERIAL AND POLYETHYLENE OXIDE AND PROCESS THEREOF Robert A. Fetters and Hanns F. Arledter, Chillicothe, Ohio, assignors to The Mead Corporation, Dayton, Ohio, a corporation of Ohio No Drawing. Filed Sept. 18, 1964, Ser. No. 397,599
13 Claims. (Cl. 162-168) This application is a continuation-in-part of Serial No. 121,821 filed July 5, 1961, now abandoned.
This invention relates to the production of evenly distributed resin in resin-filled fibrous material and, more particularly, to uniformly dispersed resin-filled moldable pulp material and products thereof.
It is recognized that the use of additives, such as various resins, in the making of paper is nearly as old as the making of paper. For example, rosin materials in small amounts have heretofore been added to paper fibers to size them against water penetration. Larger amounts of resinous materials have been added to plasticize paper. However, w-hen the resinous material exceeds 4% of the papermaking pulp stock, desirable even distribution of the resinous material throughout the fibrous mass is not easily attainable commercially.
Numerous methods have been proposed in the patented art which attempt to obtain substantially even distribution of various resinous materials in fibrous webs. For example, cationic coupling agents have been proposed to adhere certain resins to fibers and the use of a cationic melamine as a fiber conditioning agent to flocculate impregnating resins has also been disclosed. However, such proposals present problems of critical control of process steps for producing resin-filled fibrous products where the resin is added to the fibers before forming into sheets or other desired shapes whereby the resin is uniformly dispersed throughout a formed mat.
The primary object of this invention is to provide a process for incorporating and substantially uniformly dispersing resinous materials in fibrous webs, which can be done easily and economically on existing papermaking equipment and without the need for critical control of process variables.
Another object is to provide a process for incorporating resinous materials in fibrous webs in which the resinous materials .are substantially all retained and distributed substantially uniformly throughout the fibrous Web.
A further object of the invention is to produce a resinfilled paper or board which may be easily formed under heat and pressure, and may be subsequently decorated by printing, painting, or lacquering.
A still further object is to produce a resin-filled fibrous product in which the physical properties of the fibrous product may be altered as desired by proper choice of resin, polyvalent metal salt, and pulp, and by the ratio of resin to pulp.
Another object is to provide a process of incoporating resinous materials in fibrous webs in which process problems such as slow drainage on the wire, plugging of the wire and felts, and sticking to the wire, felts, and dryer drums are substantially eliminated.
Other objects and advantages of this invention will become apparent from the following description and explanation of the invention.
This invention is predicated on the unexpected discovery and concept that the interaction of a polyvalent metal ion with a water or alkali soluble resinous material capable of being precipitated by a polyvalent metal ion, in intimate association with dispersed pulp fibers and the treatment of the resulting mixture with a dilute solution of a high molecular weight polyethylene oxide alone or in "ice combination with other additives will produce a substantially uniformly dispersed resin filled moldable material. As used herein, polyvalent means having a valence greater than unity.
In general, the process for carrying out this invention comprises: the treatment of dispersed pulp fibers with a polyvalent metal ion in the form of a salt, the treatment of the resulting pulp-metal ion mixture with water or alkali resinous material in solution and the treatment of the resulting mixture with a dilute solution of a high molecular weight polyethylene oxide.
High molecular weight polyethylene oxides of the type herein referred to which have been found to be preferable for use in this invention have molecular weights ranging from at least 1,000,000 to 10,000,000 and preferably of the order of 3,650,000 and are sold by Union Carbide Chemicals Company, Division of Union Carbide Corporation, under their generally identifying trademark Polyox. And by reason 'of innovations in catalysis as well as manufacturing techniques, these high molecular weight polyethylene oxide materials are available which have molecular Weights ranging from about 50,000 to an excess of 10,000,000. Surprisingly, these high molecular weight materials are soluble in water and form relatively stable solutions at temperatures below C. Small amounts of these materials will thicken water so that it becomes a very viscous mass. As evidence of the extreme thickening properties of these particular high molecular weight polyethylene oxides, one such commercial product utilized by applicants has an average viscosity of 3,000 centipoises in a 1% aqueous solution. This particular material has a molecular weight of approximately 3,000,000. Another such commercial product has an average viscosity, as a 1% solution, of approximately 7,000 centipoises with its average molecular weight being about 6,000,000. Various techniques for producing the above type of polyethylene oxides are set forth in an article by F. N. Hill et al., entitled High Molecular Weight Polymers of Ethylene Oxide, appearing at pages 5-7 of volume 50, No. 1, January 1958 issue of Industrial and Engineering Chemistry. Particular reference is made to the paragraph entitled Polymerization on page 7 of this article.
To facilitate the practice of this invention, the following general observations are submitted for carrying out the process so as to insure incorporating and substantially uniformly dispersing resinous materials in fibrous webs. The ingredients added in each process step should be thoroughly mixed before the next ingredient is added. Other than the time taken for thorough mixing, the reaction time taken for each step is not critical, providing at least several seconds are available for complete flocculation. Reasonable care should be exercised not to excessively agitate the stock after addition of the polyethylene oxide. Alternatively, the resin solution may be added to the pulp prior to the addition of the polyvalent metal ion which should be added to the pulp fibers in the form of a soluble salt, preferably a chloride salt, although certain nitrates, acetates and sulfates have been successfully used. Excessive amounts of polyvalent metal salts (up to three times the calculated stoichiometric amount needed) have been added without adversely affecting the process. Salts of the vallkaline earth metals are preferred, although the following salts have been successfully used in the process: calcium chloride, aluminum sulfate (paper makers alum), aluminum chloride, barium chloride, zinc sulfate, magnesium sulfate, beryllium nitrate, cadmium chloride, cobaltous chloride, cupric chloride, ferrous chloride, manganous chloride, mercuric acetate, nickelous chloride, stannic chloride, and strontium chloride. The salts may be added as fine-1y divided solids, or in Water solution.
Suitable resinous materials are reaction products of an ous acid or fatty acid or combinations of same.
alkali hydroxide, such as sodium hydroxide, and a resin- These reaction products are relatively water soluble and are used as aqueous solutions so that the resinous component will be intimately mixed with the pulp fibers.
- The preferred resinous material is a mixture of the sodium salts of the acids present in tall oil and wood rosin, in a ratio of 85% tall oil and 15% rosin, hereinafter referred to as Resin A. Other materials are the sodium salts of 1 wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic, oleic, stearic, and linoleic acids,.and mixtures of j these acids used per se or after chemical modification. The ammonium salts of shellac and the sodium salts of alkali soluble polyvinyl acetate copolymers are also acceptable; The type of resinous material and polyvalent metal ion determine the melting point of the resinous component and to a considerable extent, thefinished properties of the resin filled product.
The high molecular weight polyethylene oxide has been found to be particularly effective as a means of controlling the floc size of the precipitated resin metal salts, and in improving retention of same. Flocculating agents other than polyethylene oxide have been tried, but with limited success. The function of the polyethylene oxide appears to be one of controlled flocculation of the very fine precipitate for-med by the reaction of the polyvalent metal ions with the resinous material. Furthermore, the polyethylene oxide appears to promote a high degree of uniform dispersion of the flocs in the fibrous mass. A range of from 0.002% to 0.1% of polyethylene oxide on resinfiber content has been found to be elfective in achieving this'result, depending on the consistency of the stock. 'Best results have been obtained when the polyethylene oxide is added at the rate of'3.5 pounds of polyethylene .oxide to 100,000 gallons of stock The optimum amount of polyethylene oxide necessary for desired flocculation can be determined by simple observations. A sample of pulp stock containing precipitated resin taken after incorporating the flocculating agent shows a substantially I clear Water phase on settling if suificient polyethylene oxide is present. Too much polyethylene oxide will cause the stock to appear slimy. A person skilled in the art can easily make these observations and adjust the amount of polyethylene oxide added. In general, stock which is highi 557, a product sold by Hercules Powder Company), based on the resin-fiber content. Such addition may be made f prior orfollowing the addition of the flocculating agent.
Defoamers may be added to control foam without materially aifecting the process. Sulfuric acidand papermarkers alum have been added to control the pH of the takes to drain each sheet.
It has been found that the temperature required to form or mold the resin-filled sheet of this invention can be adjusted by use of an acid or acid salt in combination with polyvalent metal ions. For example, addition of sulfuric acid or papermakers alum will reduce the temperature required to mold a paper board containing 20% of Resin A precipitated by calcium ion, the amount of molding temperature reduction amounting to about 20 F. Such adjustment of molding temperature greatly increases the utility of the invention by adapting the product to existing molding presses of commerce. I the resin solution by acids or acid salts in combination with polyvalent metal ions presumably. gives a mixed resin precipitate comprising free resin acid admixed with metal salts of the resin acid. I
The process of this invention was developed primarily for use on paper or board machines. However, this process is readily applied to the preparation of resin filled pulp stock for making resin-pulp preforms and the like, as by the usual pulp molding methods.
The invention will now be illustrated by the following examples which show specific embodiments thereof. However, it is to be understood that this invention in its broader aspects is not limited to these examples.
' EXAMPLE 1 400 grams of double kraft liner corrugated cuttings were dispersed in 20,000 ml. of water in a conventional type disintegrator and blended for a period of at least minutes. The pulp stock was then reduced to 1% consistency, and had a TAPPI freeness of 565 ml.
To 380 ml. portions of the 1% pulp stock were added ml. of 3.0% Resin A solution, stirring the solution in slowly. Dilu-tion water was added to give a subsequent total volume'of 790 including all the desired additives. This corresponds to a resin-pulp consistency of 0.8%. Additional ingredients were added in the following man ner. The calcium chloride was added as 35 ml. of a 0.1 molar water solution of C CI Kymene 557 was added as 6.35 ml. of a 0.1% water solution of Kymene 557. The polyethylene oxide was added as 3.15 ml. of 0.1% polyethylene oxide in water. After each addition the resin-pulp stock was thoroughly mixed, avoiding excessive agitation before the next ingredient was added.
Immediately after the desired ingredients had been thoroughly mixed, the resin-pulp stock containing the additives was poured into a British Sheet Machine filled with water up to the wire, and a handsheet was made without any further addition of water. The handsheet was then couched and dried. Several handsheets were made for each set of sheets, recording the time in seconds it Control sheets were made from the pulp stock without resin or other additives. All
sheets were dried to about 6% moisture at 220 to 245 F. The resin retention was calculated as follows:
Percent Resin Retention: 100) Oven dry sheet weightoven dry control sheet weight Calculated dry resin weight added resin filled sheet and resin properties. 60 The results for each set of sheets is given in Table I.
Table I Materials added to the pulp Drainage Percent White Handsheet stock in the order of addition pH time, sec. resin water retention 8.33 1. 3 3. 2 Dark. 7. 3. 5 76. 4 Cloudy. 8. G5 1. 8 3. 9 Dark. 8. 3 1. 4 8. 8 Do. A, CaCh, Polyethylene 8. 3 2.6 90. 6 Clear. 0x1 e. l-F Resin A, Kymene 557, Polyethyl- 8. 7 1. 7 9. 6 Dark.
ene 0x1 e. 1G Resin A, 08011, Kymene 557, 8.3 2. 9 92.8 Clear.
Polyethylene oxide. 1-H Resin A, Kymene 557, CaCl;, 8. 4 3.1 91.3 Do;
Polyethylene oxide.
Such co-precipitation of- The handsheets of Example 1, as shown in Table 1, illustrate the synergistic effect of the polyvalent metal ion, Ca++, and the polyethylene oxide on the retention of Resin A. In a comparison of Sheets 1-A containing no additives other than the resin, with Sheets 1-B, 1-C and lD, it can be seen that Kymene 557 had very little effect on resin retention, polyethylene oxide had only slightly better effect (+56%), and calcium chloride had a much greater effect (+73.2%). The combined additive effects of both calcium chloride and polyethylene oxide should be +78.8% whereas their synergistic effect demonstrated an actual increase of +87.3% resin retention as shown by Sheet 1-E. The lack of a synergistic elfect between the polyethylene oxide and the Kymene 557 is 6 indicate good drainage would be obtained on Fourdrinier or cylinder paper machines.
EXAMPLE 3 Using the pulp stock of Example 1, three sets of handsheets were made in which the 6.35 ml. of 0.1% water solution of Kymene 557 of Sheets l-G reported in Table I were replaced with similar amounts of Parez 607, Amerex 8850, or polyethyleneimine. Parez 607 is a cationic melamine formaldehyde produced by American Cyan amid Company. Amerez 8850 is a liquid polyamide resin produced by American Marietta Company. The results for each of these sets of sheets is given in Table III.
Table 111 Materials added to the stock Drainage Percent White Handsheet and the order of addition pH time, sec. resin water retention III-A Resin A, CaClz, Parez 607, Poly- 8. 1 2. 8 93. 6 Almost clear.
ethylene oxide.
HI-B Resin A, CaClg, Amerez 8850, 8. 3 3. 2 90. 7 Clear.
Polyethylene oxied.
III-C Resin A, 08012, Polyethylenei- 7.8 2.9 92.5 Do.
mine, Polyethylene oxide.
shown by Sheeet 1-F, and is confirmed by Sheets 1-G and 1-H. The drainage times shown in the table indicate satisfactory drainage would be obtained in all cases on Fourdrinier or cylinder paper machines.
EXAMPLE 2 All of the sheets showed good resin retention comparable to the results obtained with Sheets l-G reported in Table I.
EXAMPLE 4 Using a 1% consistency pulp prepared from double kraft lined corrugated cuttings in the manner illustrated in Example 1, a series of handsheets was made to illustrate the effects of various polyvalent metal salts on the retention of Resin A with and without the addition of polyethylene oxide.
To a 380 ml. portion of the 1% pulp stock, enough dilution water was added to make a total volume of 790 ml. after the resin and other ingredients were added. To this, was added 85 ml. of 3.0% Resin A solution, stirring the solution in slowly. 35 ml. of a 0.1 molar water solution of polyvalent metal salt was then added, again with Table 11 Materials added to the pulp Drainage Percent White Handsheet stock in the order of addition pH time, sec. resin water retention II-A- CaCl, Resin A, Polyethylene 8.3 3.2 92.0 Clear.
on e. II-B 0:012, Polyethylene oxide, Resin 8. 3 2. 9 84. 3 Cloudy. 1ro Cadlz, Resin a, Kymene 557, 8.3 4.1 90.1 Clear.
Polyethylene oxide. II-D CaClz, Kymene 557, Resin A, 8.2 3.3 91.2 Do.
Polyethylene oxide. II-E- Kymene 557, C3012, Resin A, 8.3 3.2 92.1 Do.
Polyethylene oxide. II-F Kymene 557, Resin A, CaOlz, 8.3 2.6 93.3 Do.
Polyethylene oxide.
The handsheets as shown in Table II illustrate the effect of the order of addition of materials to the pulp stock. It is observed that if the polyethylene oxide is added last, as in the ease of II-A and lL-C though II-F, there is substantially no difference in retention of Resin A. However, adding the polyethylene oxide before the Resin A, as in Sheet IIB, reduced the resin retention, and the white water was cloudy, indicating the presence of precipitated resin in the white water. Drainage times again mild agitation, and 3.15 ml. of 0.1% polyethylene oxide in water was added, where indicated in Table IV. In the case of handsheet IVDD (Table IV), 6.35 ml. of 0.1% Kymene 557 solution was also added following the addition of the aluminum sulfate.
The 0.1% polyethylene oxide was stirred in slowly, and a handsheet was made after mixing as described in Example 1. Several sheets were made for each variation. The results are recorded in Table IV.
Table IV 1 Materials added to the stock Drainage Percent Floccu- Handsheet and the order of addition pH time, sec. resin lation retention Resin A, BaClz 7- 6 5 82. Fair. Resin1 A, 13301:, Polyethylene 7. 9 2. 96. 4 Excellent.
on e. Resin A, ZnSOr 6. 3 3. 3 45. 1 Fair. Resin1 A, ZnS O4, Polyethylene 6- 3 3. 1 62 9 E cell nt,
0x1 e. Resin A, MgSOr 0 4. 0 73. 2 Fair. Resi :l A, MgSO4, Polyethylene 8.0 3. 3 89.0 Excellent.
on e. Resin A, CaClzn 6- 5 2- 2 79.1 Fair. Resin1 A, CaClz, Polyethylene 7. 8 2. 7 91. 6 Excellent.
on e. Resin A, Be(N0a)2 5. 4 6. 6 91. 3 Fair. Resin A, Be (N092, Polyethy- 5.4 3. 9 94. 5 Excellent.
lene oxide. Resin A, CdClg 6- 2. 7 93. 0 Fair. Resini A, CdOl Polyethylene 6. 4 2.3 98. 6 Excellent.
on e. Resin A, C0011 6. 9 4. 0 87. 0 Fair. Resin1 A, 00011, Polyethylene 7. 2 3. 4 94. 2 Excellent.
on e. Resin A, CuC12 5. 4 7. 5 93. 4 Good. Resini A, 01101:, Polyethylene 5. 4 4. 9 100. 5 Do.
on e. Resin A, FeClz 6. 4 6. 2 85. 3 Fair. Resini A, FeClz, Polyethylene 6.4 6.4 89. 7 Good,
0x1 e. Resin A, MnClr 7- 1 3. 6 78. 3 Fair. Resin1 A, MnCl Polyethylene 7. 2 3.0 91. 8 Good.
oxi e. Resin A, Hg (Ac): 9 8. 4 84. 7 Fair. Resini A, Hg (Ach, Polyethylene 4. 6 4 0 98. 6 Excelle t.
on e. Resin A, NiOli 7 1 5 6 86. 1 Good. Resin1 A, NiCl Polyethylene 7. l 8. 8 94. 1 Excellent.
0x1 e. Resin A, S11C14 1. 9 3. 7 75. 9 Fair. Resin1 A, SnOh, Polyethylene 1. 6 3. 7 96. 5 Excellent.
OX1 e. IV-AA Resin A, SrOl 7- 9 2. 9 71.1 Fair.
B Resin; A, SlCh, Polyethylene 7.9 2. 7 85. 6 Excellent.
oxi e. Resin A, Al (S093 -8 6. 4 82. 9 Fair.
Resin A, All (SO93, Kymene 3. 8 4. 4 91. 7 Excell nt.
557, Polyethylene Oxide.
In this series of handsheets the degree of flocculations EXAMPLE 9 was determined by observations of the flocs and clarity of the Water phase. In each case, the polyethylene oxide substantially increased the retention of the Resin A, and in most cases the drainage time was decreased by the addition of the polyethylene oxide.
EXAMPLE 5 of 790 ml. after addition of the resin and other ingredients.
To this was added 71.5 ml. of 3.56% sodium oleate, 34.5 ml. of 0.1 molar calcium chloride, and 3.15 ml. of a 0.1% solution of polyethylene oxide in water. Between each addition, the resin pulp stock was thoroughly mixed before the addition of the next ingredient. A handsheet was made in the manner described in Example 1 and the data obtained are reported in Table V.
EXAMPLE 6 The procedure of Example 5 was repeated using 100 grams of abietic acid and grams of sodium hydroxide.
EXAMPLE 7 The procedure of Example 5 was repeated using 50 grams of abietic acid, 50 grams of oleic acid and 20 grams of sodium hydroxide.
EXAMPLE 8 The procedure of Example 5 was repeated using 100 grams of linoleic acid and 20 grams of sodium hydroxide.
A paste of sodium palmitate was prepared in the laboratory by heating grams of palmitic acid with 17.1 grams of sodium hydroxide in enough water to make a total batch weight of 500 grams. The reacted paste was then dissolved in water and diluted to 3.90% solids. A portion of this solution was reacted with calcium chloride and this mixture was dried and the Parr Bar stick point was determined on the dried resin.
To a 380 ml. portion of the pulp stock of Example 4, enough dilution water was added to make a total volume of 790 ml. after addition of the resin and other ingredients. To this was added 65 ml. of 3.90% sodium palmitate, 50 ml. of 0.1 molar calcium chloride and 3.15 n11. of a 0.1% solution of polyethylene oxide in water. Between additions, the stock was thoroughly mixed before the addition of the next ingredient. A handsheet was made in the manner described in Example 1 and the data, obtained are reported in Table V. a
EXAMPLE 10 The procedure of Example 9 was repeated using 100 grams of K wood rosin and 14.63 grams of sodium hydroxide.
EXAMPLE 11 The procedure of Example 9 was repeated using 100, grams of WW wood rosin and 14.63 grams of sodium hydroxide.
EXAMPLE 12 The procedure of Example 9 was repeated using 100 grams of a distilled tall oil fatty acid containing 5% rosin acids, and 15.14 gramsof sodium hydroxide.
EXAMPLE 13 The procedure of Example 9 was repeated using 100 grams of stearic acid and 14.06 grams of. sodium hydroxide.
9 EXAMPLE 14 100 grams of a commercial grade of alkali soluble vinylacetate copolymer were added to a solution of 5.5 grams of sodium hydroxide in 900 grams of water. The
10 EXAMPLE 17 To prepare a 40% resin-60% fiber board, 3400 grams of double kraft lined corrugated cuttings were furnished to a beater and beaten to a TAPPI freeness of 575 ml.
mixture was stirred until the vinylacetate copolymer was The pulp stock was then dropped to a chest, and 1338 dissolved, diluted with water to approximately 3% solids, grams of dry Resin A and 935 grams of dry sodium salt and the diluted solution was used in preparing and making of B wood rosin were added to the stock as dilute water handsheets. solutions. Additional water was added to the resin-fiber To a 380 ml. portion of the pulp stock of Example 4, stock in the chest to give a resin-pulp consistency of 0.8%. enough dilution water was added to make a total volume 400 grams of calcium chloride (dry basis) were disof 790 ml. after the addition of resin and the other solved in a minimum of water and added to the resiningredients. To this was added 86 ml. of 3% solution fiber stock. This was added slowly while agitating the of polyvinyl acetate copolymer prepared above, 50 ml. of stock to insure complete and uniform resin precipitation. 0.1 molar aluminum chloride, and 3.15 ml. of a 0.1% To this was added 700 ml. of 10% sulfuric acid and solution of polyethylene oxide in water. Between addi- 94.5 ml. of 6% Water solution of Parez 607, and thoroughtions, the stock was thoroughly mixed before the addition ly mixed. 284 ml. of a 1% Water solution of polyethylene of the next ingredient. A handsheet was made in the oxide was added, and the stock was mixed using a manner described in Example 1 and the data obtained minimum of agitation. The pH of the stock was 5.4. are reported in Table V. 20 Using this stock, a resin-fiber board having a basis weight of 68 pounds per thousand square feet was pro- EXAMPLE 15 duced on a Fourdrinier machine at a speed of 1.95 feet 50 81331113 Of an Orange Shellac Were addefi to 450 grams per minute. Due to agitation of the resin-pulp stock in Of Water, and 5 grams of ammoelllm'hydroxlde the chest, a small amount of 1% polyethylene oxide was were then added to the mlx ur T1115 mlXtIlTe added as the trial progressed to insure good flocculation. heat d to 140 f r 10 minutes, and the reacted fesln, Formation and drainage of the sheet on the Wire were hereinafter referred to as Resin B, was cooled and diluted good, Th Percent resin retention was l l d as with water to approximately 3% solids. f 1l To a 380 ml. portion of the pulp stock of Example 4, enough dilution water was added to make a total volume Percent Resm retentlon" of 790 ml. after the addition of the resin and the other Fll'fiemble y Sollds 111 Whlte Wat X100 ingredients. To this was added 86 ml. of 2.96% solution Filterable dry solids in treated stock of Resin B prepared as above, 100 ml. of 0.1 molar cal- The calculated resin retention was cium chloride, and 3.15 ml. of a 0.1% solution of polyethylene oxide in water. Between additions, the stock EXAMPLE 18 was thoroughly mixed before the addition of the next To r e a r i .6()% fibe b d 3400 grams ingredient. A handsheet was made in the mann r of double kraft lined cuttings were furnished to a beater scribed in Example 1. and beaten to a TAPPI freeness of slightly over 500 ml. EXAMPLE 16 The pulp stock was dropped to a chest, and 1265 grams 40 of dry Resin A and 885 grams of dry sodium salt of B 150 g of pulverized extracted P e W PItch were wood rosin were added to the stock as dilute water soludispersed in 375 grams of Wa confaltllflg 20 grams tions. Additional water was added to the resin-fiber stock sodium hydroxide. This mixture was stirred for 30 minto give a resimpulp consistency f g utes, and the reacted resin, hereinafter referred to as 323 grams of calcium chloride (dry basis) dissolved Re1I1 C, was dllllted Wlth Water to apprexlmately 3% in a minimum amount of Water were added to the diluted solids. resin-pulp stock. The stock was thoroughly mixed, and To a 400 l- P0111011 of a eonslstency SIUTTY of 278 ml. of 1% polyethylene oxide in water were added. u le klaft llned Corrugated eumngs havlng TAPPI The stock was then mixed using a minimum of agitation. freeness of 565 ml. was added 84 ml. of 3% solution of The PH f the treated Stock was 7.1. Using this Stock Resllt C fOHOWlIlg W1th4O mPlar calclum a resin fiber board having a basis weight of 83 pounds ChlOIldeh P 0f i mixture l per thousand square feet was produced on a Fourdrinier by adding dilute sulfuric acid. Successive additions of machine at a speed 1 f 237 fe t minute' AS in of 01% Perez 9 e Of a 01% ample 18, flocculation was controlled in the chest by addi- 8011111011 0f P y y oxlde Water Were made, and tion of small amounts of 1% polyethylene oxide during enough Water e added to bung the @1331 Volume to the trial. Formation and drainage of the sheet on the 790 ml. The resin-fiber stock was then mixed thoroughly 59 wi e were good, and there was no evidence of plugging and a handsheet Was made in the mann r d s i in the wire or felts or sticking to the press or felts. The Example 1. calculated resin retention was 98.9%.
Table V Example Drainage Percent Parr Bar No. Resin pH time, sec. resin stick point retention F.
Sodium Oleate 9. 5 4. 0 84.1 188 Sodium Abietate 9.6 5. 0 72.6 50-50 Sodium Abietate-Sodium 9.8 5. 5 89.6 277 Oleate Mixture. Sodium Linoleate 9.6 6.0 89. 5 198 Sodium Palmitate 8. 1 4. 6 86. 6 310 Sodium Salt of K Wood R0sin s. 5 5. 7 s1. 4 463 Sodium Salt of WW Wood Rosn-.- 8.6 5. 4 85.5 434 SodiumSaltofTallOilFattyAcid. 7.2 5.0 82.0 201 Sodium Stearate 8.1 4. 4 92. 7 316 Alkali soluble vinylacetate 4. 3 3. 7 93.0 450+ copolymer. Resin B 8. 2 45. 7 88.3 Resin 0 5. 0 8. 0 84.1
*Not determined.
1 1 EXAMPLE 19 To prepare a 25.8% resin-74.2% fiber board, 3400 grams of double kraft lined cuttings were furnished to a heater and beaten to a TAPPI freeness of slightly over 500 ml. The pulp stock was dropped to a chest, and 695 grams of dry Resin A and 485 grams of dry sodium salt of B wood rosin were added to the stock as dilute water solutions. Additional water was added to the resin pulp stock to give a resin-pulp consistency of 0.8%.
332 grams of dry barium chloride were dissolved in a minimum amount of water and added to the resin-pulp stock. The stock was thoroughly mixed, and 229 ml. of 1% polyethylene oxide in water were added. The stock was mixed using a minimum of agitation. The pH of the stock was 7.05.
Using this stock, a resin fiber board having a basis weight of 83 pounds per thousand square feet was produced on a Fourdrinier paper machine without difiiculty at a speed of 2.37 feet per minute. As in Example 18, flocculation was controlled in the chest by the addition of small amounts of 1% polyethylene oxide during the trial. Formation and drainage of the sheet on the wire were good, and there was no evidence of plugging the wire or felts or sticking to the press or felts. The calculated resin retention was 99.9%.
EXAMPLE 20 To prepare a 46.8%-53.2% fiber board, 3240 grams of double kraft lined cuttings were furnished to a beater and beaten to a TAPPI freeness of 562. The pulp stock was then dropped to a chest, and 2812 grams of dry Resin A were added as a dilute water solution. Additional water was added to the resin-fiber stock in the chest to give a resin-pulp consistency of 0.8%.
To this stock was added successively, 422 grams of calcium chloride (dry basis) dissolved in a minimum of water, and 6.052 grams of Kymene 557 dissolved in 1212 ml. of water, mixing thoroughly between the addition of each ingredient. 606 ml. 0.5% polyethylene oxide in water was added, and the stock was mixed using a minimum of agitation. The pH of the stock was 5.5.
EXAMPLE 21 3550 pounds of double kraft lined corrugated cuttings V were beaten in a hydrapulper, at a stock consistency of about 4%, to remove large lumps of fibers. The TAPPI freeness of the resultant pulp was 430 ml. 200 pounds of a 76% commercial grade of calcium chloride were added to the hydrapulper near the end of the beating cycle.
After dewatering and dropping the stock to the beater,
chest, it was refined through the jordans, at a consistency of 4.45% to a TAPPI freeness of 265 ml. 1195 pounds of Resin A in the form of a 20.4% water solution were added to the refined pulp fiber and thoroughly mixed with it. At this point, 200 gallons of a 0.6% solution of a defoamer, and 30 pounds of aluminum sulfate which had been dissolved in a minimum amount of water were added. After these additions, the stock had a pH of 6.5 and a TAPPI freeness of 285 ml.
The stock was continuously pumped to the headbox of a cylinder papennachine, and a 2.5% water solution of Kyrnene 557 was metered into headbox at the rate of 1750 ml. per minute. After this point, recirculation of white water from the cylinder vats resulted in a dilution of the stock to a consistency of between 0.42 and 0.49%. Immediately preceding the flow of the stock into. the bottom of the cylinder vats, a 0.077% water solution of polyethylene oxide was metered into the stock at approximately 7500 ml. per minute. The stock was then dewatered on the cylinder mold, dried and machine calendered. A 25 point board having a basis weight of 93 pounds per thousand square feet was produced at a speed of 160 feet per minute. The composition of the board was 25.2% Resin A and 74.8% pulp fibers.
The board product was laminated to a 3 ply thickness with a heat setting adhesive. The laminated board when presteamed for 60 seconds was easily formed in a press heated to a temperature of 160 F.
EXAMPLE 22 400 grams of double kraft lined corrugated cuttings Were dispersed in 20,000 ml. of Water in a laboratory disintegrator and blended for a period of at least 60 minutes. The pulp stock was then reduced to 0.76% consistency and had a TAPPI freeness of .500 to 550 ml. To 95 ml. portions of the 0.76% pulp stock were added 286 ml. of a 3.0% Resin A solution, stirring the solution in slowly. Dilution water was added to give a subsequent total volume of 1188 ml, including all the desired additives. This corresponds to a resin-pulp consistency of approximately 0.8%. Additional ingredients were added in the following manner. The calcium chloride was added as ml. of a 0.1 molar water solution of calcium chloride. Parez 607 was added as 9.5 ml. of a 0.1% water solution. The polyethylene oxide was added as 4.75 ml. of 0.1% polyethylene oxide in water. After each addition, the resin pulp stock was thoroughly mixed, avoiding excessive agitation, before the next ingredient was added.
After the polyethylene oxide was thoroughly mixed in, a handsheet containing approximately 90% resin was made in the manner described in Example 1. tention was 98.6%.
The resin-filled board of the examples of this invention may be formed under heat and pressure into a Widevariety of useful products. Luggage, automobile panels,
trays, mannequins, containers and the like may be prethose skilled in the art that the procedures described and the resultant products are adaptable to the use of any of a wide range of fibers. Chemical wood pulps and cellulosic fibers from other sources, inorganic fibers, both natural and manufactured, such as fibers from glass, as bestos fibers, synthetic organic fibers and the like may be used Without departing from the scope of the invention. p 7
Likewise, the product of the invention may be adapted toa wide range of uses by choice of resin, precipitating ion, amount of resin, density of the resin-fiberboard, and other obvious variations evident. to those skilled inthe art. Similarly, the surface of the resinfiberboard of this invention may be treated with sizings and/ or coatings to serve as a base for further decorative treatments. Finally, fibrous, relatively resin-free surface layers may be provided by employment of the process 1 of the invention on the middle cylinders of a multicylinder machine while the liner cylinders operate on resin-free pulp stocks. For some uses, multiple layers of the resin-filled board can be assembled, as by pasting, to provide thicker sections as may be desired.
While the foregoing presents preferred embodiments of the present invention, it is obvious that other modification and/or equivalents may be employed without departing from the scope of the invention, which is defined in the appended claims.
Resin re- What is claimed is:
1. A new article of manufacture consisting essentially of a fibrous product having resinous material incorporated and substantially uniformly distributed therethrough, said product containing from about 15% to about 90% resinous material and from about to about 85% fiber, said resinou material being present in the form of a polyvalent metal salt derived by the precipitation of the soluble alkali salt of the resinous material with a polyvalent metal ion, said fibrous product including a fiocculant for said resinous material of about 0.002% to 0.1% high molecular weight polyethylene oxide based on the resin-fiber content.
2. A new article of manufacture consisting essentially of a fibrous product having resinou material incorporated and substantially uniformly distributed therethrough, said product containing from about to about 90% resinous material and from about 10% to about 85% fiber, said resinous material being present in the form of a polyvalent metal salt derived by the precipitation of the soluble alkali salt of the resinous material with a polyvalent metal ion, said fibrous product including a fiocculant for said resinous material of about 0.002% to 0.1% high molecular weight polyethylene oxide based on the resin-fiber content, said polyvalent metal ion being in the form of a Water-soluble salt selected from the group consisting of calcium, barium, magnesium, stron: tium and aluminum and present in an amount up to three times the stoichiometric amount required.
3. A new article of manufacture consisting essentially of a fibrous product having resinou material incorporated and substantially uniformly distributed therethrough, said product containing from about 15% to about 90% resinous material and from about 10% to about 85 fiber, said resinous material being present in the form of a polyvalent metal salt derived by the precipitation of the soluble alkali salt of the resinous material with a polyvalent metal ion, said fibrous product including a fiocculant for said resinous material of about 0.002% to 0.1% high molecular weight polyethylene oxide based on the resin-fiber content, said soluble alkali salt of the resinous material being selected from the group consisting of sodium salts of the acids present in tall oil and wood rosin; sodium salts of wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic, oleic, stearic, linoleic acids; the ammonium salt of shellac and the sodium salt of alkali soluble polyvinyl acetate copolymers.
4. The fibrous product of claim 1 wherein the polyvalent metal ion is derived from calcium chloride.
5. The fibrous product of claim 1 wherein the polyvalent metal salt of the resinous material is derived from sodium salts of wood rosin.
6. The fibrous product of claim 1 wherein the polyvalent metal salt of the resinous material is derived from sodium salts of fatty acids.
7. The fibrous product of claim 1 wherein the resinous material consists essentially of an alkali soluble shellac.
8. The fibrous product of claim 1 wherein the resinous material consists essentially of alkali soluble polyvinyl acetate copolymers.
9. The fibrous product of claim 1 wherein the resinous material is a mixture of sodium salts of the acids present in tall oil and wood rosin in the ratio of 85% tall oil and 15 rosin.
10. A process for preparing a fibrous product containing from about 15% to about 90% resinous material and from about 10% to about 85% fiber which comprises the steps of preparing an aqueous dispersion of fibrous material with a polyvalent metal ion, said metal ion being in the form of a water-soluble salt selected from the group consisting of calcium, barium, magnesium, strontium and aluminum and present in an amount up to three times the stoichiometric amount required, treating the resulting fiber-metal ion solution with an alkali soluble salt of a resinous material to precipitate said material in the form of a polyvalent metal salt, said alkali soluble salt of the resinous material being selected from the group consisting of sodium salts of the acids present in tall oil and wood rosin; sodium salts of wood rosin, tall oil fatty acids, extracted pine wood pitch, abietic acid, stearic, linoleic acids; the ammonium salt of shellac and the sodium salt of alakali soluble polyvinyl acetate copolyrners, thereafter treating the resulting mixture with a solution of high molecular weight polyethylene oxide, the concentration of said polyethylene oxide being in the range of from 0.002% to 0.1% based on the resin-fiber content whereby said polyethylene oxide is capable of effecting the flocculation of said precipitated water soluble resinous material.
11. A process for preparing a fibrous product containing from about 15% to about resinous material and from about 10% to about 85% fiber which comprises the steps of preparing an aqueous dispersion of fibrous material with a polyvalent metal ion, said metal ion being in the form of a water-soluble salt selected from the group consisting of calcium, barium, magnesium, strontium and aluminum and present in an amount up to three times the stoichiometric amount required, treating the resulting fiber-metal ion solution with a resinous material consisting essentially of a mixture of the sodium salts present in tall oil and Wood rosin, in the ratio of 85 tall oil and 15% rosin, thereafter treating the resulting mixture With a solution of high molecular weight polyethylene oxide, the concentration of said polyethylene oxide being in the range of from 0.002% to 0.1% based on the resin-fiber content whereby said polyethylene oxide is capable of effecting the flocculation of said precipitated water soluble resinous material.
12. A process for preparing a fibrous product having a range of about 72.6% to substantially resin retention, which comprises preparing an aqueous dispersion of fibrous material, interacting a polyvalent metal ion with a water soluble resinous material capable of being precipitated by a polyvalent metal ion, in intimate association with said dispersion of fibrous material, said polyvalent metal ion being in the form of a water-soluble salt selected from the group consisting of calcium, barium, magnesium, strontium and aluminum and present in an amount up to three times the stoichiometric amount required, thereafter treating the resulting mixture with a a solution of high molecular weight polyethylene oxide whereby said polyethylene oxide is capable of effecting the flocculation of said precipitated water soluble resinous material.
13. A process for substantially uniformly dispersing resinous materials in a fibrous product comprising preparing a slurry of dispersed fibers, incorporating into said slurry with mild agitation a resinous material in the form of a polyvalent metal salt derived by the precipitation of the soluble alkali salt of the resinous material with a polyvalent metal ion, controlling the resulting floc size of said resinous material in the fibrous product by the introduction of a high molecular weight polyethylene oxide of a concentration of the order of 0.002% to 0.1% based in the resin-fiber content whereby said polyethylene oxide is capable of effecting the flocculation of said precipitated water soluble resinous material.
References Cited by the Examiner UNITED STATES PATENTS 1,840,399 1/1932 Lane 162l79 2,447,064 8/1948 Gebhart 162-179 2,712,994 7/1955 Niles 162179 2,987,489 6/1961 Bailey et al. 2602 3,008,868 11/1961 Feigley et a1 l62-179 3,024,160 3/1962 Kapral 162179 3,112,242 1l/1963 Jones 162180 3,141,815 7/1964 Manley 162l64 (Other references on following page) 15 16 FOREIGN PATENTS Development News, Can You Profit by the Unique 498,054 12/1953 Canada. Properties of Pluronicsi', vol. 30, N0. 22, June 2, 1962, 610,357 12/1960 Canada. P- 2283-2285- OTHER REFERENCES 5 DONALL H. SYLVESTER, Primary Examiner.
Bailey et 211.: High Molecular Weight Polymers of BASHORE, Examiner Ethylene Oxide, Industrial and Engineering Chemistry,
' vol. 50, No. 1, January 1-958, pp. 8-11.

Claims (1)

12. A PROCESS FOR PREPARING A FIBROUS PRODUCT HAVING A RANGE OOF ABOUT 72.6% TO SUBSTANTIALLY 100% RESIN RETENTION, WHICH COMPRISES PREPARING AN AQUEOUS DISPERSION OF FIBROUS MATERIAL, INTERACTING A POLYVALENT METAL ION WITH A WATER SOLUBLE RESINOUS MATERIAL CAPABLE OF BEING PRECIPITATED BY A POLYVALENT METAL ION, IN INTIMATE ASSOCIATION WITH SID DISPERSION OF FIBROUS MATERIAL, SAID POLYVALENT METAL ION BEING IN THE FORM OF A WATER-SOLUBLE SALT SELECTED FROM THE GROUP CONSISTING OF CALCIUM, BARIUM, MAGNESIUM, STRONTIUM AND ALUMINUM AND PRESENT IN AN AMOUNT UP TO THREE TIMES THE STIOCHIOMETRIC AMOUNT REQUIRED, THEREAFTER TREATING THE RESULTING MIXTURE WITH A A SOLUTION OF HIGH MOLECULAR WIEGHT POLYETHYLENE OXIDEE WHEREBY SAID POLYETHYLENE OXIDE IS CAPABLE OF EFFECTING THE FLOCCULATION OF SAID PRECIPITATED WATER SOLUBLE RESINOUS. MATERIAL.
US39759964 1961-07-05 1964-09-18 Fibrous product containing resinous material and polyethylene oxide and process thereof Expired - Lifetime US3281312A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US39759964 US3281312A (en) 1961-07-05 1964-09-18 Fibrous product containing resinous material and polyethylene oxide and process thereof

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US12182161A 1961-07-05 1961-07-05
US39759964 US3281312A (en) 1961-07-05 1964-09-18 Fibrous product containing resinous material and polyethylene oxide and process thereof

Publications (1)

Publication Number Publication Date
US3281312A true US3281312A (en) 1966-10-25

Family

ID=26819840

Family Applications (1)

Application Number Title Priority Date Filing Date
US39759964 Expired - Lifetime US3281312A (en) 1961-07-05 1964-09-18 Fibrous product containing resinous material and polyethylene oxide and process thereof

Country Status (1)

Country Link
US (1) US3281312A (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070236A (en) * 1974-11-15 1978-01-24 Sandoz Ltd. Paper manufacture with improved retention agents
US4313790A (en) * 1980-03-31 1982-02-02 Pulp And Paper Research Institute Of Canada Additives for increased retention and pitch control in paper manufacture
US5578168A (en) * 1993-04-30 1996-11-26 Hercules Incorporated Aqueous suspensions of poly(ethylene oxide) useful as retention aids in paper manufacture
US6372088B1 (en) * 1999-03-31 2002-04-16 Pulp And Paper Reserch Institute Of Canada Enhancer performance for PEO
EP1950345A1 (en) * 2005-10-25 2008-07-30 Sumitomo Seika Chemicals Co., Ltd. Papermaking method and papermaking system
WO2013116027A1 (en) 2012-01-30 2013-08-08 Dow Global Technologies Llc Process for preparing high molecular weight polymers by polymerizing epoxide monomers
WO2013116026A1 (en) 2012-01-30 2013-08-08 Dow Global Technologies Llc Process for preparing olefin oxide polymerization catalysts
EP2927011A4 (en) * 2012-11-27 2015-11-11 Kj Speciality Paper Co Ltd Base paper for decorative laminate and decorative laminate

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1840399A (en) * 1929-03-01 1932-01-12 Eastman Kodak Co Sized paper and method of making same
US2447064A (en) * 1943-08-14 1948-08-17 Colgate Palmolive Peet Co Preparation of aluminum salts
CA498054A (en) * 1953-12-01 Canadian International Paper Company Manufacture of cellulose
US2712994A (en) * 1949-01-27 1955-07-12 Monsanto Chemicals Process for improving paper and product
CA610357A (en) * 1960-12-13 Rayonier Inc. Cellulose containing polypropylene oxide-polyethylene oxide polymers
US2987489A (en) * 1958-11-19 1961-06-06 Union Carbide Corp Polymerization of epoxides
US3008868A (en) * 1957-12-23 1961-11-14 Armstrong Cork Co Drainage rate of cellulosic papermaking slurries
US3024160A (en) * 1956-08-31 1962-03-06 Process Methods Corp Paper, particularly printing paper, and method of making same
US3112242A (en) * 1960-05-10 1963-11-26 Int Paper Co Treating a wood pulp slurry with a water-soluble acid prior to addition of sizing materials thereto
US3141815A (en) * 1960-07-27 1964-07-21 Nalco Chemical Co Process of improving inorganic filler retention in paper by addition of ethylene oxide homopolymer

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA498054A (en) * 1953-12-01 Canadian International Paper Company Manufacture of cellulose
CA610357A (en) * 1960-12-13 Rayonier Inc. Cellulose containing polypropylene oxide-polyethylene oxide polymers
US1840399A (en) * 1929-03-01 1932-01-12 Eastman Kodak Co Sized paper and method of making same
US2447064A (en) * 1943-08-14 1948-08-17 Colgate Palmolive Peet Co Preparation of aluminum salts
US2712994A (en) * 1949-01-27 1955-07-12 Monsanto Chemicals Process for improving paper and product
US3024160A (en) * 1956-08-31 1962-03-06 Process Methods Corp Paper, particularly printing paper, and method of making same
US3008868A (en) * 1957-12-23 1961-11-14 Armstrong Cork Co Drainage rate of cellulosic papermaking slurries
US2987489A (en) * 1958-11-19 1961-06-06 Union Carbide Corp Polymerization of epoxides
US3112242A (en) * 1960-05-10 1963-11-26 Int Paper Co Treating a wood pulp slurry with a water-soluble acid prior to addition of sizing materials thereto
US3141815A (en) * 1960-07-27 1964-07-21 Nalco Chemical Co Process of improving inorganic filler retention in paper by addition of ethylene oxide homopolymer

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070236A (en) * 1974-11-15 1978-01-24 Sandoz Ltd. Paper manufacture with improved retention agents
US4313790A (en) * 1980-03-31 1982-02-02 Pulp And Paper Research Institute Of Canada Additives for increased retention and pitch control in paper manufacture
US5578168A (en) * 1993-04-30 1996-11-26 Hercules Incorporated Aqueous suspensions of poly(ethylene oxide) useful as retention aids in paper manufacture
US6372088B1 (en) * 1999-03-31 2002-04-16 Pulp And Paper Reserch Institute Of Canada Enhancer performance for PEO
EP1950345A1 (en) * 2005-10-25 2008-07-30 Sumitomo Seika Chemicals Co., Ltd. Papermaking method and papermaking system
US20090250182A1 (en) * 2005-10-25 2009-10-08 Sumitomo Seika Chemicals Co., Ltd. Papermaking Method and Papermaking System
EP1950345A4 (en) * 2005-10-25 2012-03-07 Sumitomo Seika Chemicals Papermaking method and papermaking system
WO2013116027A1 (en) 2012-01-30 2013-08-08 Dow Global Technologies Llc Process for preparing high molecular weight polymers by polymerizing epoxide monomers
WO2013116026A1 (en) 2012-01-30 2013-08-08 Dow Global Technologies Llc Process for preparing olefin oxide polymerization catalysts
US9598536B2 (en) 2012-01-30 2017-03-21 Dow Global Technologies Llc Process for preparing high molecular weight polymers by polymerizing epoxide monomers
EP2927011A4 (en) * 2012-11-27 2015-11-11 Kj Speciality Paper Co Ltd Base paper for decorative laminate and decorative laminate

Similar Documents

Publication Publication Date Title
US2601597A (en) Application of dispersed coating materials to cellulosic fibers
DE1546369C3 (en) Process for making paper, paperboard and the like with improved wet strength. Eliminated from: 1177824
US4388150A (en) Papermaking and products made thereby
CA1097467A (en) Mineral fillers
CA1174015A (en) Material in sheet form, convertible into a finished product by moulding-stamping or heat-shaping, comprising reinforcing fibres and a thermoplastics resin in powder form, and process for preparing said material
US2721140A (en) Paper of high wet strength and process therefor
US4946557A (en) Process for the production of paper
AU608577B2 (en) Manufacturing process for paper
DE3706525A1 (en) METHOD FOR PRODUCING PAPER, CARDBOARD AND CARDBOARD WITH HIGH DRY RESISTANCE
US5972100A (en) Pretreatment of filler with cationic ketene dimer
US3409500A (en) Method of sizing paper with cationic polyamine and carboxylic anhydride
US3281312A (en) Fibrous product containing resinous material and polyethylene oxide and process thereof
US3036950A (en) Process for incorporating resins into paper
US3252852A (en) Process of adding a polyethylene iminecalcium carbonate filler to cellulosic fibers and paper thereof
NZ285321A (en) Inorganic filler material (calcium carbonate) treated with an anionic treatment agent followed by a cationic polymer and use thereof as a sizing agent in paper making
US2068926A (en) Method of making artificial lumber
CH640026A5 (en) METHOD FOR PRODUCING A HIGH FILLING LEAF.
US4022634A (en) Ammonia-containing sizing compositions
US3445330A (en) Method of sizing paper with carboxylic acid anhydride particles and polyamines
CA1203052A (en) Sizing compositions containing a formic acid salt, processes, and paper sized with the compositions
US2972560A (en) Method of manufacturing paper
US5482595A (en) Method for improving retention and drainage characteristics in alkaline papermaking
US4025354A (en) Urea containing sizing compositions
US3109769A (en) Process for incorporating resins into paper
US3441472A (en) Method of forming glass-asbestos water-laid sheet