WO2009085655A1 - Compositions de papier repulpables - Google Patents

Compositions de papier repulpables Download PDF

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Publication number
WO2009085655A1
WO2009085655A1 PCT/US2008/086571 US2008086571W WO2009085655A1 WO 2009085655 A1 WO2009085655 A1 WO 2009085655A1 US 2008086571 W US2008086571 W US 2008086571W WO 2009085655 A1 WO2009085655 A1 WO 2009085655A1
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Prior art keywords
repeating units
paper
bonding agent
fibers
acid containing
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PCT/US2008/086571
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English (en)
Inventor
Ti Chou
Martin A. Cohen
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Lubrizol Advanced Materials, Inc.
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Publication of WO2009085655A1 publication Critical patent/WO2009085655A1/fr

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/18—Reinforcing agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
    • D21C5/02—Working-up waste paper
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/35—Polyalkenes, e.g. polystyrene
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/36—Polyalkenyalcohols; Polyalkenylethers; Polyalkenylesters
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/47—Condensation polymers of aldehydes or ketones
    • D21H17/49—Condensation polymers of aldehydes or ketones with compounds containing hydrogen bound to nitrogen
    • D21H17/51—Triazines, e.g. melamine
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/64—Paper recycling

Definitions

  • the present invention relates to the inclusion of a modified paper saturant/binder including elevated levels of repeat units from copolymeri/able unsaturated acid monomers for treating paper/nonwovens so that the treated paper/nonwoven is repulpable under moderate to high shear.
  • a modified paper saturant/binder including elevated levels of repeat units from copolymeri/able unsaturated acid monomers for treating paper/nonwovens so that the treated paper/nonwoven is repulpable under moderate to high shear.
  • U.S. Patent 5,133,833 relates to a process for repulping or reclaiming fibers from latex-impregnated materials such as latex impregnated papers.
  • the process involves treating the latex-impregnated material with an alkali solution for a sufficient period of time to separate the latex polymer from the fibers. This is followed by a washing step to rinse away the latex polymer thereby leaving the reclaimed fibers for subsequent use such as the formation of new paper stock.
  • Alkali sensitive acrylate, or styrene-butadiene, or styrene-acrylate, or vinyl chloride, or vinylidene chloride, or vinyl acetate copolymers are used as a component in paper or nonwoven binder/saturant to render the resulting paper and/or nonw ovens repulpable under moderate to high shear. That is, during manufacture, after manufacture and after use the papcr/nonwoven can be disseminated or dispersed into small groups or individual pulp/fibers at elevated pH whereupon the pulp/fibers of the paper/nonwoven, along with any attached polymer can be commercially recycled.
  • the alkali sensitive acrylate, or styrene-butadiene, or styrcnc- acrylate, or vinyl chloride, or vinylidene chloride, or vinyl acetate binder composition is generally a copolymer derived from at least an unsaturated acid monomer and a) one or more alkyl (alk)acrylates monomers and/or b) styrene-butadiene monomers c) styrene-acrylate monomers d) vinyl chloride monomers e) vinylidene chloride monomers f) vinyl acetate monomers optionally one or more other unsaturated monomers such as vinyl esters, vinyl ethers, acrylamides or the like,
  • Repulpable nonwoven/paper sources include abrasive paper, vacuum bags, wipes, book covers, wallcoverings, and the like,
  • saturant/binder which generally is a latex (anionic, nonionic, or cationic) reinforcing polymer and optionally containing crosslinking agents.
  • Saturant/Binder is able to enhance physical properties (such as Tensile Strength, Fold Endurance, Tear Resistance, Bursting Resistance, etc.), chemical resistance, and durability to the treated paper/nonwovens.
  • the network of fibers in generic paper generally comprises at least about 50 percent by weight of cellulosic fibers. In specialty nonwovens, the percentage of non-cellulosic fibers can be much higher than in generic paper. Thus, non-cellulosic fibers such as mineral and synthetic fibers may be included, if desired. Examples of non- cellulosic fibers include, by way of illustration only, glass wool and fibers prepared from thermosetting and thermoplastic polymers.
  • substantially all of the fibers present in the paper will be cellulosic fibers.
  • Sources of cellulosic fibers include, by way of illustration only, woods, such as softwoods and hardwoods; straws and grasses, such as rice, esparto, wheat, rye, and sabai; bamboos; jute; flax; kenaf; linen; ramie; abaca; sisal; bagasse; and cotton and cotton linters.
  • Softwoods and hardwoods are the more commonly used sources of cellulosic fibers in North America and in Europe.
  • the cellulosic fibers may be obtained by any of the commonly used pulping processes, such as mechanical, chemi- mechanical, semi-chemical, and chemical processes.
  • softwood and hardwood Kraft pulps are desirable for toughness and tear strength, but other pulps, such as recycled fibers, sulfite pulp, and the like may be used, depending upon the application.
  • a saturant/binder in the saturated paper/nonwoven is at a level of from about 5 to about 100 percent, based on the dry weight (solids/nonvolatiles) of the fibrous web (typically 100% fiber at this stage).
  • the saturant may be present in the saturated paper at a level of from about 10 to about 70 weight percent.
  • the saturant may be present in the saturated paper at a level of from about 15 to about 60 weight percent.
  • saturants/binders known to the art and to the literature can be the starting point for an improved saturant for repulpable paper.
  • Such saturants often include from about 70 to about 98 or 100 percent, on a dry weight basis, of an addition synthetic polymer (e.g., latex or dispersion) having a glass transition temperature of from about -4O 0 C to about 7O 0 C.
  • the solids content of the saturant/binder when applied may be from about 4 to about 80 percent of the applied saturant.
  • the addition polymer dispersion reinforcing polymer may have glass transition temperature of from about -15 0 C to about 15 0 C.
  • the saturant/binder can be combined with the fibers or fibrous web by any conventional method such as beater addition, saturation, impregnation, spray, coating, etc.
  • substantially all of the fibers of the paper can be cellulosic fibers.
  • the latex reinforcing polymer may be anionic, nonionic. cat ⁇ onic and/or mixtures.
  • the improved saturant of this disclosure can be prepared by any process. Two preferred processes will be referred to as either the one-component saturant or the two-component saturant.
  • the two-component saturant is a blend of two separate polymers wherein the blend has the requisite properties (including alkali sensitivity) due to a lesser amount on a weight basis of a second high acid content polymer.
  • the high acid content polymer contributes alkali sensitivity to the blend in the two-component saturant.
  • the other polymer in the two-component blend is any of the conventional latexes used as paper saturants.
  • the one-component saturant uses higher amounts of acid monomers in a recipe to make a conventional latex paper saturant.
  • the acid monomers when used in appropriate amounts, make the one-component saturant as sensitive to alkali as the two-component saturant.
  • the one-component and two-component systems can be used interchangeably in making saturant for repulpable paper. Either method of imparting alkali sensitivity gives similar properties, i.e., it produces a repulpable paper.
  • the high acid content polymer used in the two-component saturant can be a solution in aqueous phase, a latex, or a dispersion.
  • these high acid polymers comprise about 4 to about 20 wt% of repeating units from an ethylenically unsaturated monomer(s) having one or more acid groups (preferably carboxylic acid, but including sufonic acid, phosphoric or phosphonic acid, etc.), These repeating units can be in the acid form or in the form of a neutralized salt of the acid.
  • Carboset® resins made by Lubrizol Advanced Materials, Inc., Brecksville, Ohio, their headquarters.
  • the Carboset 500 series can be utilized and include Carboset 51 1 , Carboset 514H, Carboset 514A, Carboset 515, Carboset 519, Carboset 527, Carboset 537, and Carboset 552 with Carboset 511, 527, 537, 514H, 514W, 515, and 552 being preferred.
  • a hydrosol with similar monomer composition may be utilized.
  • these Carboset type polymer dispersions are blended as the 5 to 40 weight % substitution level on a dry basis with the polymer of a conventional saturant/binder (i.e., 5 to 40 weight percent of the polymer of the saturant would be replaced with 5-40 weight percent of a high acid content polymer).
  • a conventional saturant/binder i.e., 5 to 40 weight percent of the polymer of the saturant would be replaced with 5-40 weight percent of a high acid content polymer.
  • any type of polyacid polymers such as Carbosperse K-700 from The Lubrizol Corporation, can be used to replace 5 to 40 percent weight of saturant/binder and to impart alkali sensitivity of the blend.
  • the acid monomers associated with the pH sensitivity could be included in the polymerization recipe of a commercial or conventional saturant or binder to make a one-component saturant/binder with alkali sensitivity.
  • polymer with a composition of 91 ,5 ethyl acrylate / 3.0 acrylonitrile ⁇ 1.0 N-methylol aerylamide / 4.5 acrylic acid, or 92.0 ethyl acrylate / 0.7 aerylamide / 4.5 acrylic acid / 1.9 itaconic acid are alkali sensitive saturant/binder,
  • Latex saturants for use in papermaking. These latexes may be used as described as the major component in a two- component repulpable latex saturant with alkali sensitivity according to the invention. If a single component latex saturant is desired, these latexes below could be polymerized with the appropriate amount of ethylenically unsaturated acid containing monomers substituted for a portion of the conventional monomers to these recipes.
  • Suitable latex reinforcing polymers include acrylate polymers or copolymers, styrene-butadienc copolymers, vinyl-acetate polymers or copolymers, styrene-acrylate copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, or a vinyl acetate- ethylene copolymer. These polymers may be anionicaily, nonionicaJly, and/or cationically stabilized colloidal dispersions or blends thereof.
  • Suitable polyacrylates include alkyl (alk)acrylate polymer wherein the alkyl has from 1 to about 15 carbon atoms (such that the (alk)acrylic acid ester has from 4 to 18 carbon atoms) such as ethyl acrylate, butyl acrylate, etc., along with blends of various other polymers such as acrylonitrile polymers, styrene-butadiene copolymers, styrene-acrylate copolymers, vinyl chloride copolymers, vinylidene chloride copolymers, vinyl acetate copolymers, ethylene-vinyl chloride copolymers and the like.
  • the saturant/binder is an acrylate polymer dispersion desirably from about 50 to about 98 weight % of the repeating units of said polymer are C 4 -Ci 8 (alk)acrylate monomers and in another embodiment from about 70 to about 98 wt.% of said repeating units are said (alk)acrylate monomers.
  • the alkyl portion of said monomers is a Cl to Cl 5 alkyl group without heteroatoms such as oxygen or nitrogen.
  • the alkyl (alk)acrylate have from 4 to 1 1 carbon atoms, more desirably from 4 to 7 carbon atoms.
  • the residual monomers forming repeating units can be selected from the unsaturated monomers listed later in this document,
  • the saturant/binder is a styrene-butadiene polymer dispersion (meaning it is formed from a styrenic type monomer as listed Anlagenow and a conjugated diene monomer) desirably from about 30 to about 70 weight % of said polymer is repeating units derived from a styrenic monomer and from about 29 to about 70 weight % repeating units derived from polymerizing a conjugated diene monomer of 4 to 6 carbon atoms.
  • from about 35 to about 65 weight % of the repeating units are derived from a styrenic monomer and from about 34 to about 65 weight percent of repeating units are derived from polymerizing a conjugated diene of 4 to 6 carbon atoms.
  • the styrenic monomer is styrene.
  • the diene monomer comprises butadiene and/or is substantially butadiene.
  • Other ethylenically unsaturated monomers can be copolymerized with the styrenic monomer and diene monomer as is well known to the art.
  • the saturant binder is a vinyl acetate polymer, desirably from about 20, 30 or 50 to about 98 or 99 weight percent of the repeating units of the polymer are derived from polymerizing vinyl ester monomers of 4 to 20 carbon atoms such as vinyl acetate and other monomers where the acetate is replaced by other carboxylic acids.
  • the vinyl acetate polymer desirably has less than 50 weight percent of the repeating units of alkyl acrylates as previously described. If more than 50 weight percent of the repeating units are from alkyl acrylates, the polymer will be called an acrylate polymer.
  • the other repeating units of the vinyl acetate polymer are any of the other ethylenically unsaturated monomers listed in this disclosure.
  • the acetate polymer will be appropriately modified to be a one-component or two-component material with alkali sensitivity.
  • the saturant is a vinyl chloride polymer, desirably from about 20, 50, 60, 70 or 80 to about 98 or 99 weight percent of the repeating units are derived from polymerizing vinyl chloride monomer.
  • the residual monomers can be any of the ethylenically unsaturated monomers listed in this disclosure that readily co-polymerizc with the vinyl chloride monomer.
  • the saturant is a vinylidene chloride polymer
  • desirably from about 35, 50, 60, 70 or 80 to about 98 or 99 weight percent of the repeating units are derived from polymerizing vinylidene chloride monomer. Since vinylidene chloride homopolymer can be highly crystalline, it is often desirable to use relatively large amounts of co- monomers to disrupt crystal Unity.
  • the residual repeating units can be derived from polymerizing any of the other ethylenically unsaturated monomers listed in this disclosure that readily copolymerize with vinylidene chloride. Examples of copolymerizable monomers with vinylidene chloride include acrylates, methacrylates, acrylonitrile.
  • the saturated paper of the present invention may be made in accordance with any known procedures. Briefly, and by way of illustration only, the web may be made by preparing an aqueous suspension of fibers, optionally with at least about 50 percent, by dry weight, of the fibers being cellulosic fibers; distributing the suspension on a forming wire; removing water from the distributed suspension to form a paper; and treating the paper with the saturant.
  • the aqueous suspension is prepared by methods well known to those having ordinary skill in the art.
  • the web can also be made by a well known airlaid nonwoven process.
  • the drylaid or airlaid web is treated with binder using spray process.
  • the expressions "by dry weight” and “based on the dry weight of the cellulosic fibers” refer to weights of fibers, e.g., cellulosic fibers, or other materials which are essentially free of water in accordance with standard practice in the papermaking art (dried to constant weight at 105 0 C). When used, such expressions mean that weights were calculated as though no water were present.
  • the paper formed by removing water from the suspension of fibers may be dried prior to the treatment of the paper with the saturant. Drying of the paper may be accomplished by any known means. Examples of known drying means include, by way of illustration only, convection ovens, radiant heat, infrared radiation, forced air ovens, and heated rolls or cans. Drying also includes air drying without the addition of heat energy, other than that present in the ambient environment.
  • the aqueous suspension may contain other materials or additives as is well known in the papermaking art.
  • the suspension may contain acids and bases to control pH, such as hydrochloric acid, sulfuric acid, acetic acid, oxalic acid, phosphoric acid, phosphorous acid, sodium hydroxide, potassium hydroxide, ammonium hydroxide or ammonia, sodium carbonate, sodium bicarbonate, sodium dihydrogcn phosphate, disodium hydrogen phosphate, and trisodium phosphate: alum; sizing agents, including cationic starches, alkyl ketene dimers, rosin and rosin acids, various styrene-acrylate emulsions, copolymers of styrene and maleic anhydride, and the like: dry strength adhesives, such as natural and chemically modified starches and gums; cellulose derivatives such as carb ox ym ethyl
  • Processing agents are also generally utilized in fairly large amounts and the same includes various defoamers, retention aids which enhance flocculation of fiber slurry so that very fine fibers are agglomerated and thus form a flock which is more easily processed.
  • Various dyes and pigments can also be utilized.
  • optional cationic polymers include, by way of illustration only, polyamides, amide-epichlorohydrin resins, polyethylcneimines, polyacrylamides, and urea- formaldehyde resins.
  • this can be accomplished by substituting from about 5 to about 40 weight percent, in one embodiment from 5 to about 30 weight percent, in still another embodiment from about 5 to about 25 percent by weight of a convention acrylate, or styrene-butadiene, or styrene-acrylate, or vinyl chloride, or vinylidene chloride, or vinyl acetate latex copolymers with polymers high in repeating units derived from ethylenically unsaturated acid monomers.
  • An important aspect of the present invention is utilization of alkali sensitive repeating units/polymers for saturating paper, cellulose, and the like using either the one- component or two-component saturant.
  • the alkali sensitive polymers are copolymers derived from at least two or optionally three or more different monomers with at least one of the monomers being an unsaturated acid.
  • the paper, cellulose, etc. is generally made repulpable by the substitution of alkali sensitive addition polymer dispersion, desirably having the specified percentages of repeating units derived from unsaturated carboxylic acid monomers.
  • Preferred copolymers are derived from unsaturated acid monomers, one or more alkyl (alk)acrylates, styrene-butadiene, styrene-acrylate, vinyl chloride, vinylidene chloride, or vinyl acetate or derivatives thereof.
  • Desirable copolymers include any of the above one or more monomers with at least one unsaturated acid.
  • Dispersion is a broader term than latex in this description and is used to indicate one or more polymers in a media, wherein at least one of the polymers is in a dispersed phase. An additional polymer(s) may be present as a dispersed and/or dissolved phase.
  • alkyl (alk)acrylate will refer to alkyl acrylates and/or alkyl alkacrylates where alkyl refers to the alcohol based moiety reacted with the carboxylic acid and the (alk) refers to an optional alkyl group on the beta carbon of the unsaturated monomer. While these can be made in various ways, they are often referred to as esters of the reaction between acrylic acid or (alk)acrylic acid and various alcohois.
  • a preferred embodiment of the saturant/binder latex is aikyl (alk)acrylate polymers with high percentages e.g., above 51 or 70 weight % of repeating units from alkyl (alk)acrylates with 4-18 carbon atoms.
  • alkyl (aJk)aerylates in the latex we will be referring to such monomers without heteroatoms such as nitrogen in the R 1 group as shown below.
  • alkyl (alk)acrylates that may be present in smaller amounts within any of the polymers, we will be using the broader definition of alkyl (alk)acrylates which include things like cyanoalkyl, hydroxyalkyl, epoxyalkyl, etc. in the R 1 group.
  • R 1 is an alkyl group containing 1 to about 15 carbon atoms, an alkoxyalkyl group containing a total of 1 to about 10 carbon atoms, a cyanoalkyl group containing 1 to about 10 carbon atoms, or a hydroxy alkyl group containing from 1 to about 18 carbon atoms.
  • the alkyl structure can contain primary, secondary, or tertiary carbon configurations and normally contains 1 to about 10 carbon atoms with 2 to 8 carbon atoms being preferred.
  • acrylic esters examples include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, n-pentyl acryiate, isoamyl acrylate, n-hexyl acrylate, 2-methylpentyl acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, n-decyl acrylate, n-dodecyl acrylate, n-octadecyl acrylate, and the like.
  • Preferred examples include ethyl acrylate, butyl acrylate, 2-ethyl hexyl acrylaie, and the like.
  • the various alkyl alkacrylates (or esters of alkacrylic acid) have the formula
  • R 1 is as set forth above with respect to Formula 1 and R 2 is an alkyl having from 1 to about 4 carbon atoms, desirably 1 or 2 carbon atoms with methyl being especially preferred.
  • alkyl (aik)acrylates include methyl methacrylate, ethyl methacrylate, methoxymethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, butoxy ethyl acrylate, ethoxypropyl acrylate, and the like.
  • Derivatives include hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, and the like. Mixtures of two or more of the above monomers can also be utilized.
  • An important aspect of the present invention is a utilization of ethylenically unsaturated acids in the formation of a) a one-component saturant such as an alkali sensitive acrylate, styrene-butadiene, styrene- acrylate, vinyl chloride, vinylidene chloride, or vinyl acetate latex polymers or b) a high acid content polymer blended with a conventional paper saturant polymer.
  • Such acids are unsaturated acids and include acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, 2-carboethyl acrylate and the like. Acrylic acid is preferred.
  • Half esters of the above earboxylic acids can also be used as monomers wherein the ester portion is desirably an alkyl having from 1 to about 10 carbon atoms and specific examples include mono methyl maleate, mono methyl fumerate, mono methyl itaconate, and the like.
  • the amount of repeating units from the one or more unsaturated acids is very important in forming the one-component alkali sensitive latex polymers.
  • the amount of add monomer varies somewhat depending on how oleophilic the other monomers in the addition polymer dispersion/latex (saturant/binder) are.
  • For acrylate polymers and vinyl acetate polymers generally about 2 to about 4,5 or 6 weight %.
  • the alkali sensitive addition polymer dispersion in another embodiment from about 2.4 or 2.6 to about 5 or 6 weight % of the total dry weight of the alkali sensitive addition polymer dispersion is said repeating units from unsaturated acid monomers.
  • unsaturated acid monomers For styrene-butadiene polymers, vinyl chloride polymers, and vinylidene chloride polymers generally about 1 to about 7 weight %, in another embodiment from about 1.4 or 1.6 to about 3, 4, 5 or 6 weight % of the total dry weigh to the alkali sensitive addition polymer dispersion is said repeating units from acid monomers.
  • the preferred unsaturated acid monomer is unsaturated mono or dicarboxylic acid monomers.
  • the unsaturated acid monomers include unsaturated sulfonic acid monomers and/or unsaturated phosphonic or phosphoric acid monomers.
  • the amount of acid may need to be adjusted slightly with the particular type of acid and the particular type of copolymer formed for optimal performance. Care should be taken not to use excessive amounts of acid inasmuch as the paper will become water sensitive.
  • the polymer from at least one alkyl (alk)acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, styrene-butadiene, or styrene-acrylate monomers along with the one or more unsaturated acid monomers form a preferred alkali sensitive latex copolymer for the addition polymer dispersion.
  • the amount of dry weight of the repeating units from acrylate, alkyl (alk)acrylate, vinyl chloride, vinylidene chloride, vinyl acetate, styrene, butadiene, vinyl acetate and unsaturated acid repeat groups along with any/all the alkali sensitive latex polymers (utilized in a two-component system) is generally a majority and desirably at least about 70 or at least about 75 percent by weight of the total polymers in the saturant/binder on a dry weight basis.
  • co-polymerizable (ethyl enical Iy unsaturated) monomers in lesser amounts may be utilized to make the one or more alkali sensitive latex copolymers including styrenic monomers ⁇ as a co-monomer in the acrylate latex), vinyl chloride type monomers, acrylonitrile type monomers, various vinyl ester monomers, various acryl amides monomers, various alkynol acrylamides and the like.
  • styrenic monomers as both a primary monomer in styrene-b ⁇ tadiene polymers or a co- monomer in acrylate polymers
  • they are often referred to as vinyl substituted aromatic compounds (styrenic monomers) and include styrene, alkyl substituted styrene 1- vinylnapl ⁇ thalene, 2-vinyInaphthalene, and the alkyl, cycloalkyl, aryl, alkaryl and aralkyl derivatives thereof in which the total number of carbon atoms in the combined substituents is generally from 8 to about 12.
  • Examples of such compounds include 3- methyl styrene vinyltoluene; alpha-methylstyrene; 4-n-propyl styrene. 4-t-butylstyrene, 4- dodecyl- styrene.
  • the vinyl chloride type monomers include vinyl chloride, vinylidene chloride, and the like.
  • the vinyl esters can generally be represented by the following formula
  • R 3 is an alkyl generally having from 1 to about 10 or 12 carbon atoms with from about 1 to about 6 carbon atoms being preferred.
  • suitable vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl valerate, and the like.
  • Vinyl esters with larger R groups include the vinyl versatate monomers, such as Veo VA-P, Veo Va-IO, and Veo Va-1 1.
  • 00361 The various vinyl ethers can be represented by the formula
  • H H 2 C CO-R 4 Fo ⁇ mjla 4
  • R 4 is desirably an alkyl having from 1 to about 10 carbon atoms.
  • R 4 is desirably an alkyl having from 1 to about 10 carbon atoms.
  • Specific examples include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and the like with methyl vinyl ether being preferred.
  • the acrylonitrile type monomers include acrylonitrile, or methacrylonitrile, or ethacrylonitrile, and the like can be utilized, Acrylamide monomers which can be polymerized to form an alkali sensitive latex copolymer generally have the following formula
  • R 5 is H or methyl and R 6 is generally hydrogen or an alkyl, straight chain or branched, having from 1 to about 18 carbon atoms.
  • R 6 is generally hydrogen or an alkyl, straight chain or branched, having from 1 to about 18 carbon atoms.
  • Specific examples include acrylamide, ethyl acrylamide, butyl acrylamide, tert-octyl acrylamide, and the like.
  • the one or more acrylamides can be utilized in large amounts such as up to about 20 percent by weight of the alkali sensitive latex copolymer and desirably from about 0.5 to about 10 percent by weight.
  • the alkenol acrylamides can generally have the formula
  • R 7 is H or methyl
  • R 8 can be hydrogen and preferably is an alkyl, straight chain or branched, having from 1 to about 18 carbon atoms and desirably from 1 to 10 carbon atoms.
  • alkenol acrylamides include methanol acrylamide, ethanol acrylamide, propanol acrylamide, methylol methacrylamide, and the like.
  • Functionalized acrylamides can also be utilized to increase latex colloidal stability, to enhance latex hydrophilicity, and to improve the durability of the treated paper.
  • acrylamides examples include AMPSO?), i.e., acrylamidotnethylpropane sulfonic acid, DMAPMA, i.e., dimethylaminopropyl methacry amide, and the like.
  • AMPSO? i.e., acrylamidotnethylpropane sulfonic acid
  • DMAPMA i.e., dimethylaminopropyl methacry amide
  • (alk)acrylate monomers, styrenc-butadiene monomers, styrene-acrylate monomers, vinyl chloride monomers, vinylidene chloride monomers, and/or vinyl acetate monomers along with at least one unsaturated acid monomer and optionally one or more of any of the less desired above noted monomers can be polymerized by one or more free radical initiators to form one or more different alkali sensitive copolymers of the present invention.
  • free radical initiators known to the art and to the literature can be utilized to initiate polymerization of the various above-noted monomers or comonomers to form a polymer or copolymer.
  • Such free radical initiators generally include the persulfates, the peroxides, and azo compounds, as well as redox combinations and radiation sources.
  • Examples of preferred persulfate initiators include potassium persulfate, sodium p ⁇ rsulfate, or ammonium persulfate, and the like.
  • the free radical polymerization can be an emulsion, bulk, solution, dispersion, etc., polymerization.
  • any type of peroxide, azo, redox system, or related initiator system can be utilized.
  • Peroxide systems inlude dicumyl peroxide, cumene hydroperoxide, t- butyl perbenzoate, bis(t-butylperoxy) diisopropyl benzene, diisopropyi benzene hydroperoxide and n-butyl 4,4-bis(t-butylperoxy) valerate, as well as benzoyl peroxide, and t-butyl hydroperoxide, and the like. Cumene hydroperoxide, t-butyl hydroperoxide and diisopropyl benzene hydroperoxide are preferred.
  • Azo initiators include 2,2'- azobis(isobutyronitrile)(AlBN) and related azo initiators.
  • Alkali sensitive acrylate polymers or copolymers, styrene-butadiene copolymers, vinyl-acetate polymers or copolymers, styrene-acrylate copolymers, vinyl chloride copolymers, vinyiidene chloride copolymers, or vinyl acetate-ethyl ene copolymers can be made by utilizing chain-transfer agents/polymer physical property modifiers.
  • chain-transfer agents can be utilized such as various mercaptans, for example, thiocthanoi mercaptan, hydroxyl ethyl mercaptan, various reaction products of alkyl esters of mercaptan with acidic acid or with thiogylcolic acid, and the like wherein the alkyl group has from about 2 to about 20 carbon atoms.
  • Another suitable chain transfer agent is beta mercapto propanionic acid and its esters such as butyl-3-mercaptopro ⁇ rinate.
  • crosslinkable monomers include methylene bisacrylamide and the like.
  • suitable crosslinking agents is the various diacrylates and polyacrylates such as trimethylol propane triacrylate, pentaerythritol triacrylate, polyallyl compounds such as pentaerythritol tri-allyl ether, and the like.
  • the alkali sensitive copolymers of the present invention made from the above noted monomers in order to be suitable for use in the present invention desirably are sensitive to strong alkali solutions, have high, amounts of acid repeat units therein.
  • the alkali sensitive copolymers (irrespective of whether they are a one-component or two- component saturant) are generally sensitive in solutions having a pH of from about 7,0 to about 12, desirably from about 8.0 to about 1 1 and preferably from about 8.5 to about 10.
  • the polymer Tg is desirably less than about 70 0 C, and preferably from about -20 0 C to about 55°C. High Tg values are avoided inasmuch as the polymer is too stiff.
  • alkali sensitive copolymer e.g., a one-component system
  • blends of two or more such copolymers can be utilized so long as they are compatible with one another (e.g., a two or high component system).
  • Recovery of fibers can occur in several different manners.
  • One method is to collect unused nonwoven or paper, such as scrap, off spec paper, trims, cut-outs, etc., and/or used paper which has been treated with effective amounts of the alkali sensitive acrylate.
  • styrene-acrylate, styrene-butadiene, vinyl chloride, vinylidene chloride, or vinyl acetate latex copolymer dispersions and place them in a large vat or tank with added water and base.
  • the nonwoven or paper can be pre-shredded to a lesser or greater extent to facilitate addition of the fibers to the tank, stirring, or other handling.
  • the tank can contain any volume but volumes in the amounts of about 4,000 to 5,000 gallons arc common in the industry. Treatment can occur for longer times at ambient temperature or the contents may be heated to a warm temperature such as from about 80 0 F to about 15O 0 F, in another embodiment from about 9O 0 F to about 14O 0 F, and in a third embodiment from about 100 0 F to about 130 0 F. Higher temperatures are avoided.
  • the aqueous solution is adjusted to a higher pH by the addition of high pH compounds thereto, such as ammonium hydroxide, sodium hydroxide and the like. Target pH values are at least 7.0 or from 8,0 to about 1 1 , and in another embodiment from about 8.5 to about 10.
  • the saturant binder quickly becomes weakened by the alkali solution and is ready to be subjected to mechanical shear.
  • the paper to be recycled was blended in a Waring Blender for one to three minutes. It is desired that the tank contain a blender or impeller so that the nonwoven/paper is mixed, agitated, and subjected to shear.
  • the paper and fibers may be allowed to remain in the tank before or after shearing the paper into fibers.
  • the material in the tank is used as is as a source/supplement of pulp for papermaking. It contains at various levels of dispersion, e.g., individual fibers with or without saturant/binder thereon along with various other forms of fibers such as small bundles of 2, 3, or 4 fibers connected by saturant/binder. Generally, no attempt need be made to separate any free saturant/binder from the recycled fibers (i.e., any saturant/binder attached to the recycled fibers goes back into the next nonwoven/paper). In one embodiment, it is desirable to blend the recycled nonwoven/paper fibers with virgin fibers.
  • the fibers going into the paper/no ⁇ woven production process can be from 1 to about 50 weight % recycled fibers (by this process) on a dry fiber basis of the total fibers going into the nonwoven/paper.
  • the recycled fibers can be from about 5 or 10 to about 30 or 40 weight % of the total fibers in the new nonwoven/paper.
  • the recycled fibers are from about 15 to about 30 weight % of the total fibers.
  • the recyclable or repulpable nonw ovens/papers suitable for use in the present invention generally include industrial type paper, such as filtration media; vacuum bags; industrial wipes; book covers; abrasive paper substrates; paper substrates for adhesives, paper wallcoverings; durable paper; tapes; protective masking; decorative paper; crepe tape; label paper; stationary, nonwovens for personal care items, and the like.
  • industrial type paper such as filtration media; vacuum bags; industrial wipes; book covers; abrasive paper substrates; paper substrates for adhesives, paper wallcoverings; durable paper; tapes; protective masking; decorative paper; crepe tape; label paper; stationary, nonwovens for personal care items, and the like.
  • the following examples serve to illustrate the invention but not to limit the same. It was desired to develop a family of paper/nonwoven saturants/binders that would exhibit good physical properties but that could be converted to paper/nonwovens that could be recycled.
  • Saturated paper was made from the additized paper saturants.
  • the virgin pulp source was typically a non-saturated cellulose fiber mass called base paper.
  • Three base papers have been used for lab saturation studies. They are characterized by 13.9 lb/1300 ft 2 (53 g/m 2 ), nominally 5 rails thick, 0.42 g/cm 3 density; 13.3 lb/1300 ft 2 (50 g/m 2 ), nominally 4 mils thick, 0,49 g/cin 3 density; or 13.4 lb/1300 ft 2 , nominally 3.5 mil thick. If base paper was to test saturants, the paper could be saturated as received.
  • base paper was to be blended with recycled paper, both the base paper and the recycled paper were dispersed in water and formed into a hand sheet of similar dimensions and weight to base paper in the laboratory. Generally, it was the intent to add about 25 parts by weight of polymeric saturant for every 100 parts by weight of fibers.
  • repulped saturated paper was blended with base paper on a 25:75 or 10:90 weight basis based on the weight of the dry fibers.
  • the repulping procedure was to cut the paper to be recycled into small squares and dilute to 2 wt.% solids with water.
  • the pH was adjusted to about 9 with ammonium hydroxide and heated to 130-140 0 F, Then, it was agitated for 1, 2, or 3 minutes in a Waring Blender.
  • Handsheets were formed in the laboratory from the repulped material and evaluated for appearance, and then some of these were dried and tested for physical properties.
  • the physical properties of virgin sheets with and without pH sensitive additives were analyzed to determine if the additives were affecting paper physical properties.
  • the physical properties from handsheets from recycled saturated paper were tested.
  • the saturated paper was just dried to dryness while others were post cured at 300 0 F ( 149°C) to fully activate self-crosslinking moieties in the paper saturant (If present).
  • the monomers of the high acid content polymers were substituted into the polymerization recipe of conventional paper saturants in comparable amounts to the presence of those monomers in the blends of conventional saturants and the high acid content polymers. These were evaluated for physical properties of the resulting paper and in paper made from repulped saturated paper.
  • Level 1 means substituting 5 wt.% of Carboset 5 ⁇ 4H for the Hycar 2671
  • Level 2 means substituting 10 wt.% of Carboset 514H for the Hycar 2671
  • Level 3 means substituting 15 wt.% of Carboset 5 J4H for the Hycar 2671
  • Level 4 means substituting 20 wt.% of Carboset 514H for the Hycar 2671 Table A2 HYCAR ® 2671 Commercial Carboxylated Setf-Crosslinking Acrylate Emulsion
  • Hycar 2671 as a paper saturant illustrate that additions of 10, 15, and 20 wt.% of highly pH sensitive polymer increases the speed and ability to repulp saturated paper into individual fibers and doesn't significantly adversely affect physical properties of the paper.
  • Level I means substituting 5 wt.°/o of Carboset 5 I4H for the Hycar 26469
  • Level 2 means substituting 10 wt,% of Carboset 514H for the Hycar 26469
  • Level 3 means substituting 15 wt.% of Carboset 514H for the Hycar 26469
  • Level 4 means substituting 20 wt.% of Carboset 514H for the Hycar 26469 Tabie B2 HYCAR ® 26469
  • Level 2 means substituting 10 wt.% of Carboset 552 for the ⁇ Hycar 26469 + 1 Part of Melamine Formaldehyde Resin)
  • Level 4 means substituting 20 wt.% of Carboset 552 for the (Hycar 26469 + 1 Part of Melamine Formaldehyde Resin)
  • Level 2 means substituting 10 wt.% of Carboset 552 far the (Hycar 26469 + 5 Part of Melamine Formaldehyde Resin)
  • Level 4 means substituting 20 wl.% of Carboset 552 for the (Hycar 26469 + 5 Part of Melamine Formaldehyde Resin)
  • Results indicate that the saturant/binder can be more easily fractured so that recycling of the fibers is more efficient at higher loadings of the very pH sensitive polymer.
  • Level 2 means substituting 10 wt.% of Hydrosol 515 for the 913-620- 123
  • Level 4 means substituting 20 wt.% of Hydrosol 515 for the 913-620- 123
  • Level 2 means substituting 10 wt.% of Hydrosol 515 for the 913-620-123
  • Level 4 means substituting 20 wt.% of Hydrosol 515 for the 913-620-123
  • Hycar 2671, 913-620-104, 913-620-123, and 913-793-105 Quality of Handsheet from Recycled Fiber Dispersion
  • Level 1 means substituting 5 wt.% of Carboset 514H for the Sfycar 1 168
  • Level 2 means substituting 10 vvt.% of Carboset 5 I4H for the Sty car 1 168
  • Level 3 means substituting 15 wt.% of Carboset 514H for the Stycar 1 168
  • Level 4 means substituting 20 wt.% of Carboset 514H for the Stycar 1 168
  • Level 2 means substituting 10 wt.% of Carboset 552 for the Vycar 460x45
  • Level 4 means substituting 20 wt.% of Carboset 552 for the Vycar 460x45
  • Level 2 means substituting 10 wt.% of Carhoset 552 for the Vycar 578 Lovei 4 means substituting 20 wt.% of Carbosei 552 for the Vycar 578 Tabie N2 Vycar® 578 Latex Commercial Non-Car boxylated Non S elf- C ros slinking Vinyl Chloride Emulsion
  • the non-crosslinked Vycar vinyl chloride polymer seems to result in papers/nonwovcns that recycle very well.
  • the crosslinked Vycar vinyl chloride and vinyl-acetate polymers result in papers/nonwovens that recycle better with the addition of polymers sensitive to pH.

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Abstract

La présente invention concerne des latex traditionnels pour des saturants de papier, modifiés afin d'améliorer la capacité à repulper. Ils peuvent être modifiés avec des polymères à haute teneur en acide ou être polymérisés avec des quantités supérieures de monomères à insaturation éthylénique comportant des groupes acides. Le papier qui résulte de l'utilisation de tels saturants/liants possède des propriétés physiques suffisantes mais il est plus facilement recyclé à l'aide de mélangeurs à cisaillement élevé, à des valeurs de pH élevées. Ces saturants, lorsqu'ils sont formés en films, sont caractérisés par une tension réduite à la cassure après le trempage dans un pH 10.
PCT/US2008/086571 2007-12-20 2008-12-12 Compositions de papier repulpables WO2009085655A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2363527A1 (fr) * 2010-01-29 2011-09-07 Taicang Kingfu Plastic Manufacture Co., Ltd, Latte de store composite et son procédé de fabrication

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225383A (en) * 1978-02-02 1980-09-30 The Dow Chemical Company Highly filled sheets and method of preparation thereof
EP0470689A1 (fr) * 1990-08-06 1992-02-12 Gencorp Inc. Liant copolymère
US5266163A (en) * 1990-05-12 1993-11-30 Rohm Gmbh Process for the treatment of a pigment suspended in water and method of manufacturing paper
EP0576128A1 (fr) * 1992-06-23 1993-12-29 Rohm And Haas Company Mélange de polymères contenant un polymère riche en acide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225383A (en) * 1978-02-02 1980-09-30 The Dow Chemical Company Highly filled sheets and method of preparation thereof
US5266163A (en) * 1990-05-12 1993-11-30 Rohm Gmbh Process for the treatment of a pigment suspended in water and method of manufacturing paper
EP0470689A1 (fr) * 1990-08-06 1992-02-12 Gencorp Inc. Liant copolymère
EP0576128A1 (fr) * 1992-06-23 1993-12-29 Rohm And Haas Company Mélange de polymères contenant un polymère riche en acide

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2363527A1 (fr) * 2010-01-29 2011-09-07 Taicang Kingfu Plastic Manufacture Co., Ltd, Latte de store composite et son procédé de fabrication

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