US3438808A - Polyvinyl alcohol-boric acid-containing composition,treatment of paper web therewith and the treated paper web - Google Patents

Polyvinyl alcohol-boric acid-containing composition,treatment of paper web therewith and the treated paper web Download PDF

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US3438808A
US3438808A US450137A US3438808DA US3438808A US 3438808 A US3438808 A US 3438808A US 450137 A US450137 A US 450137A US 3438808D A US3438808D A US 3438808DA US 3438808 A US3438808 A US 3438808A
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polyvinyl alcohol
web
boric acid
solution
water
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US450137A
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Raymond L Hawkins
George Davidowich
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Airco Inc
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Air Reduction Co Inc
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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
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • Cellulosic fibrous Webs are treated to apply polyvinyl alcohol to them with minimum penetration of the polyvinyl alcohol into the web by preparing an aqueous composition containing the polyvinyl alcohol in admixture with boric acid in the amount of more than 15% and at most 50% by Weight of the polyvinyl alcohol, the composition having a pH of at most 6.0, applying the composition to the web at a temperature up to about 210 F., and drying the web with the polyvinyl alcohol thereon. Most suitably there is used an aqueous composition containing 0.5% to 35% of polyvinyl alcohol with the ratio of polyvinyl alcohol to boric acid being 0.5 to 1.3 part-s by weight of boric acid per 3 parts of polyvinyl alcohol.
  • This invention relates to the treatment of fibrous webs and is more specifically concerned with the surface sizing of such webs with polyvinyl alcohol.
  • Surface sizing is primarily concerned with the creation of surface films, and consequently it is usually desirable to keep the size on the surface of the paper as much as possible, where it will do the most good. This is particularly true when using expensive sizing agents. On the other hand, it is desirable in the case of some grades of paper, to obtain some penetration of the sizing agent into the paper in order to build up the burst strength and other internal properties of the sheet.
  • borax like other alkalies
  • the application of an excess of the borax solution will react with the internal aluminum resinate size, causing a loss of the Water resistance properties of the sheet being treated.
  • the aqueous solution contairing boric acid and polyvinyl alcohol at a predetermined pH in accordance with the invention has a maximum polyvinyl alcohol content such that the polyvinyl alcohol does not materially precipitate from the solution until after it has been applied to the web to be treated.
  • the solution thus has a polyvinyl alcohol concentration at 70 F. of at mOSt 7% by Weight using a solution cdntaining highviscosity polyvinyl alcohol (4570 centipoises) and 0.8 part of boric acid per three parts of polyvinyl alcohol, as a standard.
  • boric acid When lesser amounts of boric acid are used, or when the viscosity of the polyvinyl alcohol is less, i.e.
  • FIG. 1 shows the precipitation points of solutions containing various percentages of high-viscosity polyvinyl alcohol with various concentrations of boric acid, expressed as parts by weight of boric acid per 3 parts of polyvinyl alcohol, using 0.04 part of an organic acid such as citric acid or sulfamic acid for each 3 parts of polyvinyl alcohol in the solution, and FIG.
  • a boric acid-polyvinyl alcohol solution corresponding to the criteria set forth above is directly applied to the web to be treated. It is a feature of the invention that a single application at a single point in the line of travel of the web is sufiicient, and multiple applications, as in the 2-stage borax and polyvinyl alcohol treatment procedure previously mentioned, can be eliminated. Yet, there is obtained an effective application of polyvinyl alcohol With a very low penetration into the web.
  • the effectiveness of the sizing agent i.e. polyvinyl alcohol
  • a Vanceometer which measures the penetration of oil into the web through the applied polyvinyl alcohol film or coat, and the ability of the polyvinyl alcohol film or coat to impede the penetration of the oil is referred to in the art as holdout.
  • the standard Vanceometer test procedure is that provided by Tappi Standard T454M-44.
  • the Vanceometer Absorption Tester consists of a projection lamp and condenser lenses, mounted in such a way as to cast a beam of light on a sheet surface at an angle of twenty degrees. The light is then reflected in a straight beam, through an iris diaphragm, into a photo-electric cell connected to a microammeter.
  • the size press consists of two rolls either vertically or horizontally arranged.
  • One size-press roll is usually a hard roll, whereas the other roll of the size press is generally a softer rubber-covered roll.
  • the sheet After the sheet leaves the press, it is often passed over a spread roll to remove wrinkles.
  • the angle at which the sheet passes over this roll and the distances between this roll and the press are important factors in the operation of a size press.
  • Another method of surface-sizing utilizes a tub for holding the size into which the sheet is dipped.
  • the time of contact of the paper with the size depends upon the speed of the machine, the dimensions of the tub, and the area of the sheet submerged in the size at one time.
  • the size tub is located within the drier section so that the sheet is partially dried before reaching the tub. Drying of the sized paper is completed by passing the paper over six to eight driers.
  • the size tub results in longer contact of the paper with the size, and results in about 25% more size being picked up by the paper.
  • the process of this invention is no way limited to the apparatus used for applying the polyvinyl alcohol-boric acid solution to the web and any convenient apparatus can be used.
  • the solution can be applied by means of a Champion coater and in general the solution performs well on roll coaters, air knife coaters and on blade coaters, and in the latter cases speeds in excess of 2000 f.p.m. may be involved.
  • the solution can be applied to the web, in accordance with the process of the invention, at any point after formation of the web.
  • Polyvinyl alcohol is a water-soluble member of the class of vinyl resins which are generally made from vinyl acetate by hydrolysis.
  • the hydrolysis can be carried to any degree of completion, resulting in polyvinyl alcohol of several different degrees of hydrolysis or grades.
  • the percentage hydrolysis indicates the percentage of the original acetate groups that have been replaced by OH groups.
  • any polyvinyl acetate which is more than 50% hydrolyzed is termed polyvinyl alcohol.
  • the number of acetate groups which are converted to hydroxyl groups is referred to as the degree of hydrolysis. This is frequently expressed as percent hydrolysis, that is, a polyvinyl alcohol which is 85% hydrolyzed is one in which 85% of the acetate groups have been converted to hydroxyl groups.
  • Polyvinyl alcohol having a degree of hydrolysis of from about 80-89% is generally referred to as partially-hydrolyzed polyvinyl alcohol.
  • Polyvinyl alcohol having a minimum degree of hydrolysis of about 96% is generally referred to as fully-hydrolyzed polyvinyl alcohol, and polyvinyl alcohol having a minimum degree of hydrolysis of 99.7+% is commonly referred to as super-fully-hydrolyzed polyvinyl alcohol.
  • the molecular chain length of the polyvinyl alcohol also affects properties. The most outstanding effect is that as molecular weight increases the viscosity of solutions of polyvinyl alcohol increases. Water resistance also is notably greater in the higher viscosity types. The degree of polymerization of the higher viscosity types is in the range 1500-3000, and of the lower viescosity types, 200-1000.
  • the percent hydrolysis of the polyvinyl alcohol suitable for use in accordance with this invention can vary from about 55 percent to 100 percent. Naturally, for a specific application it may be desirable to employ a polyvinyl alcohol having a particular percent hydrolysis. Polyvinyl alcohol having a particular percent hydrolysis also varies in viscosity. Thus, it is possible to obtain a low, medium or high viscosity partially-hydrolyzed polyvinyl alcohol.
  • the viscosity of the polyvinyl alcohol is determined by the degree of polymerization of the polyvinyl acetate, i.e., if the degree of polymerization of the polyvinyl acetate is high, a high viscosity polyvinyl alcohol will generally result.
  • any polyvinyl alcohol having a viscosity of 2 to 150 centipoises in a 4% aqueous solution at 20 C. is generally acceptable.
  • the polyvinyl alcohol should be highly hydrolyzed and should. be of the medium or high viscosity type, viz having a viscosity of 20-40 centipoises (medium viscosity) or a viscosity of to centipoises (high viscosity).
  • the medium viscosity type of polyvinyl alcohol provides pick strength that is greater than that achievable with the low-viscosity types but essentially equivalent to that of the high-viscosity types.
  • the medium viscosity type is preferred.
  • polyvinyl alcohol which has an extremely high degree of hydrolysis.
  • materials are known in the art as super-hydrolyzed polyvinyl alcohol resin or fully-hydrolyzed polyvinyl alcohol resin.
  • the super-hydrolyzed grade may, as mentioned, have a degree of hydrolysis of 99.7+% and the fully-hydrolyzed grade may, as mentioned, have a percent hydrolysis of 96% or higher.
  • Such material is sold under a variety of trade names.
  • the commercially available super-hydrolyzed grades may be mentioned Vinol and Vinol 165 produced by Air Reduction Company, Incorporated.
  • polyvinyl alcohol having a percent hydrolysis of 99% may be mentioned Vinol 260, Vinol 230 and Vinol 205.
  • Other polyvinyl alcohols having a percent hydrolysis between about 98% and 99% and sold under the trade names Vinol 325and Vinol 350 by the same company are also especially suitable.
  • the super-hydrolyzed and fully-hydrolyzed grades of polyvinyl alcohol have the advantage that films produced therefrom are extremely resistant to attack by cold water.
  • the resistance of films produced from polyvinyl alcohol to cold water attack apparently reaches a maximum when the degree of hydrolysis of the polyvinyl alcohol is at a maximum.
  • a premix is formed by dissolving the boric acid in acidified water and heating the solution to a temperature of from to 210 F. The premix is then added with agitation to a solution of polyvinyl alcohol in acidified water which has also been heated to from about 160 to 210 F. After combining the premix with the polyvinyl alcohol solution, the mass is cooked with agitation for a short period of time such as about 30 minutes. The mass is then cooled to room temperature and the pH of the mass is determined. If the pH is above 6.0, it is adjusted to 6.0 or below, preferably 5.0 or below.
  • all of the ingredients are added to cold water, that is, the polyvinyl alcohol, the boric acid and a pH-adjusting acid are added to cold water, and the mass is then heated with agitation to a temperature sufiicient to dissolve the polyvinyl alcohol, and the mass is cooked at a temperature of from about 160 to 210 F. for a short period of time, such as about 30 minutes.
  • a further method for the preparation of polyvinyl alcohol solutions for use in the method of the present invention consists of forming a dry blend which is comprised of polyvinyl alcohol, boric acid, and a dry acid.
  • the dry blend may also contain a biocide such as Dowicide A,
  • This dry blend may be stored for extended periods and shipped to the user.
  • the dry blend is added to the appropriate quantity of water with agitation to form a uniform mixture, the mixture is heated to a temperature of from about 160 to about 210 F. and cooked for about 30 minutes, the amount of pH-adjusting acid being sufiicient to provide a pH of at most 6.0.
  • the solution as applied possess a pH of at most 6.0.
  • the viscosity decreases slightly.
  • a particularly suitable solution for use according to the present invention can be made if the pH is maintained within the range of 6.0 to 2.0, preferably 5.0 to 2.0.
  • the viscosity also decreases slightly; however, even at a pH of 2.0 the solution possesses an acceptable viscosity.
  • the pH of the solutions of the present invention may be controlled by the use of any water-soluble acid or acid salt, such as alum.
  • suitable water-soluble acids are hydrochloric acid, acetic acid, formic acid and phosphoric acid, although other acids, either organic or inorganic, may be employed.
  • a dry blend is to be formed, it is desirable to employ a dry acid such as citric acid, oxalic acid or sulfamic acid.
  • an acid anhydride such as maleic anhydride may be employed for controlling the pH.
  • the term acid as employed herein refers to any acidic material which is capable as controlling the pH of the solutions within the limits set forth.
  • the pigments and other additives normally used in polyvinyl alcohol coating compositions can be employed as long as they are acid stable, i.e. capable of being made acidic without decomposition or deterioration.
  • a pigment such as clay or the light
  • other materials such as, for example, a soluble pyrophosphate which may act as a dispersing and stabilizing agent, e.g. tetrasodium pyrophosphate.
  • This mixture commonly termed a pigment slip or, since it usually contains clay, a clay slip, is then compounded with the binder material to produce a composition known in the art as a coating color, which is useful for coating a cellulose web, e.g. a paper or paperboard web.
  • the clay employed can be conventional coating clay and is used in conventional manner in the form of a slip, i.e. dispersed in water to a solids content, for example, of 66%.
  • the present invention permits the use of any of the clays customarily used for coating paper, including the hydrous aluminum silicates or kaolin group clays, hydrated silica clays, and the specific types of clays recommended in Kaolin Clays and Their Industrial Uses, copyright 1949 by J. M. Huber Corp., New York, N.Y., particularly in chapters 10-16.
  • the slip may also contain a small amount, e.g. 0.1 to 0.50, of a dispersing or stabilizing agent such as tetrasodium pyrophosphate, The modification of the coating color using these materials or other conventional additives, will be within the knowledge of those skilled in the art.
  • a dispersing or stabilizing agent such as tetrasodium pyrophosphate
  • Typical defoaming agents include tributyl phosphate, pine oil, and symmetrical ditertiary acetylenic glycols sold under the trade name Surfynol 104A and Surfynol PC.
  • aqueous polyvinyl alcohol-boric acid solutions of this invention can be applied to the fibrous sheet or web at temperatures up to about 210 F. although about 205 F. is usually a practical maximum. Ordinarily the temperature of application is not below room temperature (ambient temperature) e.g. F., but lower temperatures, e.g. 35 F. can be employed if desired by preliminary refrigeration.
  • the amount of the solution applied per unit area or" the web can vary, but ordinarily it is applied at a rate to provide a polyvinyl alcohol deposition of 0.05 to 2 pounds per 1000 square feet, preferably 0.1 to 0.5 pound per 1000 square feet.
  • boric acid is specifically referred to above and is used in the numbered examples of actual operation which follow, it will be understood that the term boric acid includes other water-soluble boron compounds, e.g. boron compounds such as sodium borate which form boric acid in aqueous solutions at pH values of 6 or less.
  • boron compounds such as sodium borate which form boric acid in aqueous solutions at pH values of 6 or less.
  • EXAMPLE I This example illustrates the preparation of a sizing composition and the treatment of a web of paper in accordance with the process of this invention.
  • Example II 92 86 78 58 0.05 lb. per 1,000 square feet polyvinyl alcohol control- 84 57 43 25 EXAMPLE III This example also illustrates the preparation of a sizing composition and the treatment of a web of paperboard in accordance with the process of this invention.
  • Avg. Vanceometer value, percent gloss- This example also illustrates the preparation of a sizing composition and the treatment of a web of paperboard in accordance with the process of this invention.
  • EXAMPLE VI 1 Following the procedures of the foregoing examples, 0.5 part of boric acid and 3.0 parts of Vinol 165 were added slowly to 50.4 parts of water at a temperature of 105 F. and thoroughly mixed. The resultant slurry was adjusted to a pH of approximately 3.0 by the addition of !85% phosphoric acid. The slurry was then cooked with agitation for 25 min. at 200 F. Water was then added to the solution thus produced to adjust the solids concentration to 4.5% and additional 85 phosphoric acid was added to give the solution a final pH of about 3. 8.
  • EXAMPLE VIII This example illustrates the application of the invention to the coating of a web of paper by means of a coating color.
  • the invention is used as the binder in the formulation.
  • the color employed was prepared in the following manner.
  • a pigment slip was made by adding to water 0.10 part dispersant (TSPP), 10 parts TiO and 90 parts clay to a 66% solids content, and dispersed in a colloid mill.
  • a second mixture was made consisting of 90 parts water, 10 parts of a mixture of 0.5 part boric acid, and 3.0 parts polyvinyl alcohol, 0.10 part defoamer and sufficient phosphoric acid to give a pH less than 5.8.
  • the mixture had a 10% solids content.
  • the combined mixture was applied to the paper web in the manner descirbed in the foregoing examples using a Champion coater, with fully satisfactory coating properties being obtained.
  • EXAMPLE IX This example illustrates the application of the invention to the coating or upgrading of a web of paper by means of a coating color while still maintaining holdout properties.
  • a coating color was made by mixing 91 parts water, 0.1 part dispersant and 5.0 parts TiO This mixture was dispersed and there were added to it 4.0 parts of a mix- Avg. Vanceometer value, Polyvinyl percent gloss (NOS-12 oil) Size solution alcohol coat wt., 5 sees. sees. secs. 1b./1,000 square feet 0.6 part boric acid and 3. 4 0.07 93 93 92 parts VINOL 165. 0. 08 95 95 94 0.6 parts boric acid, 3.4 parts VINOL 165 and 5.0 parts TiOz (RA46) 1 0.09 92 92 90 1 +0.13 lb. per 1,000 sq. ft. of 'liO EXAMPLE X This example illustrates the preparation of a sizing composition and the treatment of a web of 42 lb. un
  • bleached kraft (beer liner stock) in accordance with the process of this invention.
  • This solution was then applied to a web of 42 lb. unbleached kraft having a moisture content of 5 .0 at the rate of 200 ft./min. by means of an air knife to provide 0.3 lb. of coating per 1000 square feet of web.
  • the solution was at a temperature of F. when applied and the web was then dried at a temperature of F. to a final moisture content of 5.0%.
  • the surface of the thus-treated web was then tested with the Vanceometer Absorption Tester, and the following results were obtained:
  • Vanceometer gloss (mieroamperes NC il) Treatment S-12 o 5 sees. 20 sees. 60 secs.
  • Example X 89 89 89 EXAMPLE XI This example illustrates the preparation of a sizing composition and the treatment of a Web of 42 lb. unbleached kraft in accordance with the process of this invention.
  • This solution was then applied to a web of 42 lb. kraft having a moisture content of about 5.0% at the rate of 725 ft./min. by means of a water box on the calender stack.
  • the solution was at a temperature of 145 F. when applied and the web was then dried at a temperature of about F. to a final moisture content of 5.0%.
  • the surface of the thus-treated web was then tested with the Vanceometer Absorption Tester, and the following results were obtained:
  • Vanceometer gloss microamperes, NOS-12 oil
  • Vanceometer gloss (microamperes, N os-12 oil) 60 sees.
  • a process for treating a paper web to apply polyvinyl alcohol thereto with minimum penetration of the polyvinyl alcohol into the web which comprises preparing an aqueous composition containing said polyvinyl alcohol in admixture with boric acid in the amount of more than 15% and up to 50% by weight of the polyvinyl alcohol, said composition having a pH of at most 6.0, applying said composition to said web at a temperature up to about 210 F., and drying said web with the polyvinyl alcohol thereon.
  • a process for treating a paper web to apply polyvinyl alcohol thereto with minimum penetration of the polyvinyl alcohol into the web which comprises preparing an aqueous composition containing said polyvinyl alcohol in admixture with boric acid in the amount of more than 15% and up to 50% by weight of the polyvinyl alcohol, said composition having a pH of at most 6.0 and containing at least about 0.5% of polyvinyl alcohol, applying said composition to said web at a temperature up to about 210 F., and drying said web with the polyvinyl alcohol thereon.
  • a process for treating a paper web to apply polyvinyl alcohol thereto with minimum penetration of the polyvinyl alcohol into the web which comprises applying to said web an aqueous composition containing at least about 0.5% of polyvinyl alcohol in admixture with boric acid in the amount of more than 15% and up to 50% by weight of the polyvinyl alcohol, said composition having a pH of at most 6.0, said composition being applied to said web at a temperature up to about 210 F., and drying said web with the polyvinyl alcohol thereon.
  • a process for treating a paper web to apply polyvinyl alcohol thereto with minimum penetration of the polyvinyl alcohol into the web which comprises applying to said web an aqueous composition containing 0.5% to 35% of polyvinyl alcohol in admixture with boric acid in the ratio of 0.5 to 1.3 parts by weight of boric acid per 3 parts of polyvinyl alcohol, said composition having a pH of at most 6.0, said coating being applied to said Web at a temperature up to about 210 F., and drying said web with the polyvinyl alcohol thereon.
  • An aqueous polyvinyl alcohol composition for application to a cellulosic fibrous web and effective to deposit polyvinyl alcohol on said web with minimum penetration of polyvinyl alcohol into the web comprising water, polyvinyl alcohol, and boric acid, said boric acid being present in the amount of more than 15 and up to 50% by weight based on the polyvinyl alcohol and said composition having a pH of at most 6.0.
  • An aqueous polyvinyl alcohol composition for application to a cellulosic fibrous web and effective to deposit polyvinyl alcohol on said web with minimum penetration of polyvinyl alcohol into the web comprising water, polyvinyl alcohol, and boric acid, said polyvinyl alcohol being present in the amount of 0.5% to 35% and said boric acid being present in the amount of more than 15 and up to 50% by weight based on the polyvinyl alcohol, and said composition having a pH of at most 60.
  • An aqueous polyvinyl alcohol composition for application to a cellulosic fibrous web and effective to deposit polyvinyl alcohol on said web with minimum penetration of polyvinyl alcohol into the web comprising water, polyvinyl alcohol, and boric acid, said polyvinyl alcohol being present in the amount of 0.5% to 35% and said boric acid being present in the ratio of 0.5 to 1.3 parts by weight of boric acid per 3 parts of polyvinyl alcohol, and said composition having a pH of at most 6.0.
  • a paper web having a dried film of polyvinyl alcohol thereon deposited from a composition comprising water, 0.5% to 35% of polyvinyl alcohol, and boric acid, said boric acid being present in the ratio of 0.5 to 1.3 p arts by weight of boric acid per 3 parts of polyvinyl alcohol, and said composition having a pH of at most 6.0.
  • a paper web having a dried film of polyvinyl alcohol thereon deposited from a composition comprising water, 0.5% to 35% of polyvinyl alcohol, and boric acid, said boric acid being present in the amount of more than 15% but at most 50% by weight based on the polyvinyl alcohol, and said solution having a pH of at most 6.0.

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US450137A 1965-04-22 1965-04-22 Polyvinyl alcohol-boric acid-containing composition,treatment of paper web therewith and the treated paper web Expired - Lifetime US3438808A (en)

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Cited By (20)

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DE2132017A1 (de) * 1970-06-29 1972-02-10 Xerox Corp Elektrofotografisches Kopierpapier
US3650805A (en) * 1967-06-30 1972-03-21 Saburo Imoto Method of manufacturing coated paper
US3654928A (en) * 1970-02-24 1972-04-11 Kimberly Clark Co Flushable wrapper for absorbent pads
US4297153A (en) * 1979-02-09 1981-10-27 Marvin Glass & Associates Method and apparatus for making doll clothing and doll house accessories
US4343134A (en) * 1978-01-18 1982-08-10 Air Products And Chemicals, Inc. Flushable towelette
US4343133A (en) * 1978-01-18 1982-08-10 Air Products And Chemicals, Inc. Polyvinyl acetate latex impregnated towelette
US4386183A (en) * 1981-04-16 1983-05-31 Air Products And Chemicals, Inc. Release coatings based on polyvinyl alcohol
US4409352A (en) * 1980-12-09 1983-10-11 International Standard Electric Corporation Method of making a dispersion lacquer for luminescent screens
US4440830A (en) * 1981-04-16 1984-04-03 Wempe Lawrence K Substrates coated with release composition based on polyvinyl alcohol and composites with pressure sensitive adhesives
US4537807A (en) * 1983-11-18 1985-08-27 The Borden Company, Limited Binder for pre-moistened paper products
US4877686A (en) * 1986-05-20 1989-10-31 Societe Anonyme: Aussedat-Rey Recording sheet for ink-jet printing and process for its preparation
US5234968A (en) * 1990-05-25 1993-08-10 Hoechst Aktiengesellschaft Thickening system for water-based building material mixes
US5684068A (en) * 1995-07-31 1997-11-04 International Cellulose Corp. Spray-on insulation
US6251476B1 (en) 2000-03-27 2001-06-26 International Cellulose Corp. Methods for spray-on insulation for walls and floor
US6319863B1 (en) * 1997-09-26 2001-11-20 Uni-Charm Corporation Water-disintegratable fibrous sheet containing modified polyvinyl alcohol
US6511561B1 (en) * 1998-06-19 2003-01-28 Wacker-Chemie Gmbh Fiber binding powder composition for consolidating fiber materials
US20050056391A1 (en) * 2003-09-17 2005-03-17 Huang Yan C. Papers having borate-based complexing and method of making same
WO2006011948A1 (en) 2004-06-24 2006-02-02 Celanese International Corporation Substrate coating compositions and their use
US20080050176A1 (en) * 2006-08-23 2008-02-28 Ets Technologies Inc. Elastomeric Binding Compositions
US8287962B2 (en) 2007-05-30 2012-10-16 Omnova Solutions Inc. Paper surface treatment compositions

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US2251296A (en) * 1938-06-01 1941-08-05 Du Pont Paper product
US2439108A (en) * 1943-09-11 1948-04-06 Eastman Kodak Co Coating with polyvinyl alcohol
US3135648A (en) * 1961-07-13 1964-06-02 Air Reduction Polyvinyl alcohol adhesive containing a boron compound and cellulosic articles laminated therewith

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2251296A (en) * 1938-06-01 1941-08-05 Du Pont Paper product
US2439108A (en) * 1943-09-11 1948-04-06 Eastman Kodak Co Coating with polyvinyl alcohol
US3135648A (en) * 1961-07-13 1964-06-02 Air Reduction Polyvinyl alcohol adhesive containing a boron compound and cellulosic articles laminated therewith

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3650805A (en) * 1967-06-30 1972-03-21 Saburo Imoto Method of manufacturing coated paper
US3654928A (en) * 1970-02-24 1972-04-11 Kimberly Clark Co Flushable wrapper for absorbent pads
DE2132017A1 (de) * 1970-06-29 1972-02-10 Xerox Corp Elektrofotografisches Kopierpapier
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SE340401B (enrdf_load_stackoverflow) 1971-11-15
GB1131039A (en) 1968-10-16
DE1696172A1 (de) 1971-11-18
DE1696172B2 (de) 1975-07-24

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