EP0489930A1 - Procede de fabrication de papier et additif associe - Google Patents

Procede de fabrication de papier et additif associe Download PDF

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Publication number
EP0489930A1
EP0489930A1 EP91912068A EP91912068A EP0489930A1 EP 0489930 A1 EP0489930 A1 EP 0489930A1 EP 91912068 A EP91912068 A EP 91912068A EP 91912068 A EP91912068 A EP 91912068A EP 0489930 A1 EP0489930 A1 EP 0489930A1
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Prior art keywords
produced
cationic
acrylamide polymer
reaction
acrylamide
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EP91912068A
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German (de)
English (en)
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EP0489930A4 (en
EP0489930B1 (fr
Inventor
Toshihiko Takaki
Hideaki Takahashi
Hirotoshi Doki
Hiroshi Itoh
Haruki Tsutsumi
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Mitsui Toatsu Chemicals Inc
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Mitsui Toatsu Chemicals Inc
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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
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • 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
    • D21H17/375—Poly(meth)acrylamide
    • 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
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

Definitions

  • the present invention relates to a method for papermaking, and more particularly to, a method for papermaking comprising using both a cationic acrylamide polymer obtained by Hofmann decomposition reaction at an elevated temperature for a short time and an anionic inorganic substance or a cationic polyacrylamide produced by copolymerization, and an additive for papermaking comprising a cationic acrylamide polymer produced by Hofmann decomposition reaction and an anionic inorganic substance or a cationic polyacrylamide prepared by copolymerization.
  • a Hofmann decomposition reaction product of polyacrylamide (hereinafter referred to as "Hofmann PAM”) is a cationic resin having a primary amino group directly bonded to the polymer main chain, and has been conventionally used as a freeness improver and a paper strength improver in a step of papermaking.
  • Hofmann PAM resides in the high aggregation power, and it not only improves freeness, but also improves the strength between fibers due to the hydrogen bond of the primary amino group which is also a cationic group.
  • the present inventors have investigated various additives capable of exhibiting a desirable effect when used together with Hofmann PAM, and as a result, have found that when an anionic inorganic substance or a cationic acrylamide polymer produced by copolymerization is used together therewith, freeness can be controlled without lowering paper strength characteristics, and the present invention has been completed.
  • the present invention is concerned with a method for papermaking which comprises adding to a pulp slurry a cationic acrylamide polymer produced by reacting an acrylamide polymer with a hypohalogenite at 50 - 110°C for a short time at an alkaline region and an anionic inorganic substance or a cationic polyacrylamide produced by the copolymerization of
  • the acrylamide polymers used in the present invention include homopolymers of acrylamides (or methacrylamides), copolymers of acrylamides (or methacrylamides) and at least one unsaturated monomer capable of copolymerizing therewith, and further graft copolymers of the acrylamides (or methacrylamides) with water-soluble polymers such as starch and the like.
  • copolymerizable monomers there may be mentioned hydrophilic monomers, ionic monomers, lipophilic monomers and the like, and at least one monomer may be used.
  • the hydrophilic monomers are, for example, diacetone acrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-ethylmethacrylamide, N-ethylacrylamide, N,N-diethylacrylamide, N-propylacrylamide, N-acryloylpyrrolidine, N-acryloylpiperidine, N-acryloylmorphorine, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, various methoxypolyethylene glycol (meth) acrylates, N-vinyl-2-pyrrolidone, and the like.
  • acids such as acrylic acid, methacrylic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic aicd, styrene sulfonic acid, 2-acrylamido-2-phenylpropane sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, and the like, and salts thereof
  • amines such as N,N-dimethylaminoethyl methacrylate, N,N-diethylaminoethyl methacrylate, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminopropyl methacrylamide, N,N-dimethylaminopropyl acrylamide, and the like, and salts thereof.
  • N-alkyl (meth)acrylamide derivatives such as N,N-di-n-propyl acrylamide, N-n-butyl acrylamide, N-n-hexyl acrylamide, N-n-hexyl methacrylamide, N-n-octyl acrylamide, N-n-octyl methacrylamide, N-tert-octyl acrylamide, N-dodecyl acrylamide, N-n-dodecyl methacrylamide, and the like, N-( ⁇ -glycidoxyalkyl) (meth)acrylamide derivatives such as N,N-diglycidyl acrylamide, N,N-diglycidyl methacrylamide, N-(4-glycidoxybutyl) acrylamide, N-(4-glycidoxybutyl) methacrylamide, N-(5-glycidoxypentyl) acryl
  • the amount of the unsaturated monomer used for copolymerization varies depending on the types of unsaturated monomers and combination thereof, but is usually 0 - 50 % by weight.
  • water-soluble polymers to be used for graft copolymerization with the above-mentioned monomers there may be used both natural ones and synthetic ones.
  • starches of different origin there may be used starches of different origin and modified starches such as oxidized starch, carboxyl starch, dialdehyde starch, cationmodified starch and the like, cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose and the like, alginic acid, agar, pectin, carrageenan, dextran, pururan, arum root, Arabia rubber, casein and gelatin.
  • modified starches such as oxidized starch, carboxyl starch, dialdehyde starch, cationmodified starch and the like, cellulose derivatives such as methyl cellulose, ethyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose and the like, alginic acid, agar, pectin, carrageenan, dextran, pururan, arum root, Arabia rubber, casein and gelatin.
  • polyvinyl alcohol polyvinyl ether
  • polyvinyl pyrrolidone polyethylene imine
  • polyethylene imine polyethylene imine
  • polyethylene glycol polypropylene glycol
  • polymaleic acid copolymer polyacrylic acid
  • polyacrylamides polyacrylamides and the like.
  • the amount of the monomer to be added to the above-mentioned water-soluble polymer is 0.1 - 10.0 times the weight of the water-soluble polymer.
  • the above-mentioned monomers are polymerized to prepare polyacrylamide.
  • the methods for polymerization free-radical polymerization is preferable, and as the polymerization solvent, polar solvents such as water, alcohols, dimethylformamide and the like are usable, but since Hofmann decomposition reaction is carried out in an aqueous solution. It is preferable to effect the polymerization in an aqueous solution.
  • the concentration of monomers is such a case as above is 2 - 30 % by weight, preferably 5 - 30 % by weight.
  • polymerization initiator there is not any limitation as far as it is water-soluble.
  • the polymerization initiator is usually dissolved in an aqueous solution of monomers and used.
  • peroxide initiators there may be mentioned, for example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-butyl peroxide and the like.
  • the peroxide can be used alone, but may be slso used as a redox polymerization agent by combining with a reducing agent.
  • reducing agent there may be used, for example, sulfites, hydrogen sulfites, salts of low order ionization metals such as iron, copper, cobalt and the like, organic amines such as N,N,N',N'-tetramethyl ethylenediamine and the like, and reducing sugars such as aldose, ketose and the like.
  • azo compounds there may be used 2,2'-azobis-2-amidinoprapane hydrochloride, 2,2'-azobis-2,4- dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, salts thereof and the like.
  • polymerization initiator may be used in combination.
  • transition metal ions such as ceric ion, ferric ion and the like, and further, such ions may be used in combination with the above-mentioned polymerization initiators.
  • the amount of the initiator to be added may be 0.01 - 10 % by weight based on the weight of monomers, preferably 0.02 - 8 % by weight.
  • the amount of the reducing agent to be added may be 0.1 - 100 %, preferably 0.2 - 80 % based on the initiator in terms of mole.
  • the polymerization temperature is as low as 30 to 90°C in the case of a single polymerization initiator, and much lower such as about -5 to 50°C in the case of a redox polymerization initiator.
  • the temperature may be changed accordingly as the polymerization proceeds.
  • the temperature rises due to the generated polymerization heat.
  • the atomosphere in the polymerization vessel at that time is not particularly limited, but it is desirable to replace the atmosphere with an inert gas such as nitrogen gas for the purpose of accelerating the polymerization.
  • the polymerization time is not critical, but is usually 1 - 20 hours.
  • the polyacrylamide produced by the above-mentioned method is subjected to Hofmann decomposition reaction.
  • the polyacrylamide as a starting material is prepared in an aqueous solution, it can be directly used or, if necessary, it is diluted and then used for the reaction.
  • Hofmann decomposition reaction is effected by acting a hypohalogenite on the amido group of polyacrylamide in the presence of an alkaline substance.
  • hypohalogenous acid there may be mentioned hypochlorous acid, hypobromous acid, and hypoiodous acid.
  • hypohalogenite there may be used metal or alkaline earth metal salts. Concretely, they may be sodium hypochlorite, potassium hydrochlorite, lithium hypochlorite, calcium hypochlorite, magnesium hypochlorite, barium hypochlorite and the like. Similarly, there may be mentioned alkali metal or alkaline earth metal hypobromite and hypoiodite in case of hypobromite and hypoiodite.
  • hypohalogenite by blowing a halogen gas into an alkaline solution.
  • alkaline substances there may be mentioned alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal carbonate and the like.
  • alkali metal hydroxides are preferable, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are mentioned.
  • the amount of the above-mentioned substance to be added to polyacrylamides is 0.05 - 2.0 mol, preferably 0.1 - 1.5 mol per amido group in the case of hypohalogenous acid, 0.05 - 4.0 mol, preferably 0.1 - 3.0 mol per amido group in the case of alkaline substance.
  • the pH in such a case is usually 11 - 14.
  • the concentration of polyacrylamide in such a case is usually 0.1 - 17.5 % by weight, but preferably 0.1 - 10 % by weight since a high reaction concentration results in difficult agitation or causes gelation.
  • the reaction concentration when the reaction concentration is less than 1 %, the reaction speed becomes so slow that it is more preperable that the reaction concentration is 1 - 10 % by weight.
  • the reaction temperature may be 50 - 110°C, preferably 60 - 100°C.
  • the Hofmann decomposition reaction is carried out at the above-mentioned temperature range within a short time.
  • the reaction time varies depending on reaction temperature and polymer concentration in the reaction solution, and therefore, the reaction time can not be definitely mentioned, but, for example, when the polymer concentration is 1 % by weight, it is within ten and several minutes at 50°C and within several minutes at 65°C and sufficiently within several tens sec. at 80°C. Further, when the polymer concentration is high, the reaction time can be shorter.
  • reaction time and the reaction temperature may be generally within the range defined by the following two formulas, and when the reaction is carried out within such range, a good result can be obtained,
  • Cationic polyacrylamides produced under the above-mentioned conditions have a cation eqivalent determined by colloid titration at pH 2 of about 0 - 10.0 meq/g, and said cation equivalent can be controlled by the amount of hypohalogenite added.
  • the amount of the by- production is about 0 - 10.0 meq/g in terms of anion equivalent measured by colloid titration at pH 10.
  • the amount of by-production can be controlled by adjusting the amount of the alkaline substance added.
  • the procedure of stopping the reaction may be (1) adding a reducing agent, (2) cooling, (3) lowering the pH of the solution by adding an acid, or the like. These procedures may be used alone or in combination.
  • (1) is a method for deactivating the remaining hypohalogenite and the like by the reaction with a reducing agent.
  • hypohalogenite when a hypohalogenite is reacted in an amount of equivalent mol. or less based on mol. of acrylamide unit of the polymer and at a high temperature, after completion of the reaction, unreacted hypohalogenite hardly remains.
  • the product can be used as a paper strength agent without deactivating active chlorine by using a reducing agent.
  • (2) is concerned with a method for suppressing the proceeding of reaction.
  • a procedure thereof there may be cooling with heat exchanger, diluting with cold water and the like.
  • the temperature is usually 50°C or less, preferably 45°C or less more preferably 40°C or less.
  • Hofmann decomposition reaction is stopped by lowering the pH of the solution after completion of the reaction which is usually alkaline such as pH 12 - 13 by using an acid and the progress of hydrolysis reaction is simultaneously suppressed.
  • the pH is neutral or less, preferably 4 - 6.
  • a reaction stopping method may be appropriately selected from (1) - (3) depending on the reaction conditions, and the methods may be used in combination.
  • Anionic inorganic substances which can be used together with Hofmann decomposition PAM produced by the above-mentioned method may be sodium silicate, anionic particule-like inorganic substances and mixtures thereof.
  • Sodium silicate can be produced by melting silicon dioxide with sodium carbonate or sodium hydroxide at an elevated temperature, and commercially available water glass also may be used.
  • the structure is shown by the following general formula: NaO ⁇ nSiO2 ⁇ xH2O where n is 1 - 4.
  • the examples are sodium metasilicate, sodium orthosilicate, No. 1, No. 2 and No. 3 water glasses and the like.
  • the form to be used may be such that flake or powder thereof or the like is dissolved in water, or commercially available aqueous solution products also may be used.
  • an anionic particle-like inorganic substance it is necessary only that it is not soluble in water and is anionically charged in water, and various materials can be used.
  • the examples may be silicon dioxide, aluminum oxide, antimony oxide, titanium oxide, and oxides such as clay minerals, for example, alminosilicates such as montmorillonite, bentonite, kaolin, activated clay, silica sand, diatomaceous earth and the like, magnesiasilicates such as talc, and further carbonates such as calcium carbonate and the like.
  • alminosilicates such as montmorillonite, bentonite, kaolin, activated clay, silica sand, diatomaceous earth and the like
  • magnesiasilicates such as talc
  • further carbonates such as calcium carbonate and the like.
  • the particle size is usually 100 ⁇ m or less, preferably 50 ⁇ m or less, more preferably 10 ⁇ m or less.
  • the ratio of anionic inorganic substance to Hofmann decomposition PAM when both are added may be such that the amount of anionic inorganic substance is 1 - 500 % by weight, preferably 2 - 400 % by weight, more preferably 3 - 300 % by weight based on Hofmann decomposition PAM.
  • the ratio is too small, the effect due to the combined use is not obtained while when it is too large, the function of Hofmann decomposition PAM is deteriorated.
  • the Hofmann decomposition rate is not particularly critical, but usually 5 - 60 mol %, preferably 10 - 50 mol %.
  • Hofmann decomposition PAM used in the present invention is produced by the reaction at a high temperature for a short time and the product can be directly used, and since the resulting reaction fluid is strongly alkaline, the combined addition may be effected by any procedure.
  • the amount of Hofmann decomposition PAM and anionic inorganic substance added to pulp is usually 0.005 - 5.0 %, preferably 0.01 - 2.0 % based on the dry weight of pulp.
  • the ratio of Hofmann decomposition PAM to anionic inorganic substance varies depending on papermaking conditions. Concretely, for example, when it is intended to increase freeness so as to accelerate the papermaking speed, the ratio of anionic inorganic substance is rendered small while when it is intended to control the formation and make uniform paper, the ratio of anionic inorganic substance is increased.
  • the water-soluble anionic resins used here may be water-soluble resins having an anionic substituent such as carboxyl group, sulfonic acid group, phosphoric aicd group and the like, or salts thereof.
  • resins examples include : anionic acrylamide resins, anionic polyvinyl alcohol resins, carboxymethylcellulose, carboxymethylated starch, sodium alginate, and the like.
  • the addition may be effected before or after Hofmann decomposition PAM and sodium silicate are added to a pulp slurry, or simultaneously. Further, the addition may be effected to each of Hofmann decomposition PAM and sodium silicate or to a mixture solution thereof.
  • the place where the addition is effected may be anywhere as far as it is before forming a wet sheet.
  • a papermaking machine there may be used either Fourdrinier paper machine or cylinder paper machine.
  • the present additive for papermaking is added to a pulp slurry having a concentration of 0.5 - 5.0 %, a pH 4.0 - 9.0 at a temperature of 20 - 70°C, a wet sheet is formed at a wire part and then water is squeezed at a press part.
  • the nip pressure at the press part ranges from 20 to 400 kg/cm. After passing the press part, the wet sheet is transferred to a dry part and dried with steam.
  • the steam pressure is 2 - 15 kg/cm2 and the drying is carried out in a drum at 80 - 200°C.
  • chemical treatments may be effected at a size press or calender so as to improve printing property, surface strength, water resistance, and water repellency.
  • the additive for papermaking in the present invention comprising a Hofmann decomposition PAM and an anionic inorganic substance as effective components.
  • concentration of the effective components may be 0.001 - 50 %.
  • the amount ratio of anionic inorganic substance to Hofmann decomposition PAM may be 1 - 500 % by weight, preferably 2 - 400 %, more preferably 3 - 300 %.
  • the Hofmann decomposition rate here is not particularly critical, but usually 5 - 60 mol %, preferably 10 - 50 mol %.
  • Hofmann decomposition PAM As a procedure for mixing a Hofmann decomposition PAM and an anionic inorganic substance, (i) upon carrying out Hofmann decomposition reaction, they may be added to or dissolved in sodium hydroxide, sodium hypochlorite or a mixture solution thereof in advance and the resulting mixture is used for the Hofmann decomposition reaction. (ii) After Hofmann decomposition reaction, they may be mixed with the resulting reaction fluid.
  • the solution after the Hofmann decomposition reaction is usually of pH 12 - 13, but the pH may be lowered wtih an inorganic or organic acid before it is mixed with an anionic inorganic substance, and further, it is possible to lower the pH after mixing with an anionic inorganic substance.
  • the additive for papermaking of the present invention may have pH 2 - 14.
  • the cationic monomers of the general formula (I) as above are, for example, (meth)acrylic acid ester derivatives represented by dimethylaminoethyl (meth)acrylate and diethylaminoethyl (meth)acrylate, and (meth)acrylamide derivatives represented by dimethylaminopropyl (meth)acrylamide and diethylaminopropyl (meth)acrylamide.
  • the organic or inorganic acid salts may be salts of inorganic acids such as sulfuric acid, hydrochloric acid, phosphoric acid and the like, or salts of organic acids such as acetic acid, formic acid and the like.
  • quaternary ammonium salts obtained by the reaction of the compound of the general formula (I) above with a quaternizing agent there may be mentioned, for example, vinyl monomers having a quaternary ammonium salt produced by the reaction of a vinyl monomer having a tertiary amino group with a quaternizing agent such as methyl chloride, methyl bromide, methyl iodide, dimethyl sulfuric acid, epichlorohydrin, benzyl chloride and the like.
  • a vinyl monomer having a tertiary amino group, or organic or inorganic salts thereof may be used in combination with a quaternary ammonium salts obtained by the reaction with a quaternizing agent.
  • the mixing ratio of these components is not critical.
  • the amount of the cationic monomer is usually 0.5 - 70 mol %, preferably 2 - 50 mol %.
  • the ⁇ , ⁇ -unsaturated carboxylic acids or salts thereof for example, alkali metal salts or ammonium salt thereof are vinyl monomers having anionicity, for example, unsaturated carboxylic acids such as maleic acid, fumaric acid, itaconic acid, (meth)acrylic acid, crotonic acid, citraconic acid, and the like, and alkali metal salts thereof such as sodium salts, potassium salts and the like, and ammonium salts thereof.
  • the amount of the monomer may be 0.5 - 20 mol %, preferably 2 - 20 mol %.
  • the monomer represented by the general formula (II) of the present invention may be acrylamide and methacrylamide, and commercially available such monomers in the form of powder or an aqueous solution may be sufficiently used.
  • the amount of the monomer used may be 10 - 90 mol %.
  • a crosslinking monomer (d) As a fourth component other than (a) - (c), there may be used a crosslinking monomer (d).
  • the crosslinking monomer may be a monomer having at least two double bonds in the molecule and an N-alkoxymethyl (meth)acrylamide derivative.
  • examples of the former include methylene bisacrylamide, diallyl acrylamide, triacrylformal, diacryloylimide, ethylene glycol acrylate, ethylene glycol dimethacrylate, propylene glycol diacrylate 1,3-butylene glycol dimethacrylate, 1,4-butylene glycol methacrylate, glycerol dimethacrylate, neopentyl glycol dimethacrylate, trimethylol propane triacrylate, divinylbenzene, diallyl phthalate, and the like.
  • the N-alkoxymethyl (meth)acrylamide derivatives include N-hydroxymethyl (meth)acrylamide, for example, N-methylol (meth)acrylamide, N-methoxymethyl (meth)acrylamide, N-ethoxymethyl (meth)acrylamide, N-n-butoxymethyl (metha)acrylamide, N-tert-butoxymethyl (meth)acrylamide, and the like.
  • the amount of the crosslinking agent varies depending on the type of crosslinking monomer, but is usually 0.0001 - 20 mol %, preferably 0.001 - 10 mol %.
  • the amount is less than 0.0001 mol %, the paper strength effect can not be sufficiently exhibited. On the contrary, when the amount exceeds 20 mol %, gelation is liable to occur.
  • cationic polyacrylamide (B) of the present invention there may be used conventional methods for polymerizing such type of water-soluble vinyl monomers.
  • free-radical polymerization is preferable.
  • the concentration of the monomer may be 2 - 30 % by weight, preferably 5 - 30 % by weight.
  • the polymerization initiator is not particularly critical as far as it is water-soluble, and is usually used by dissolving it in an aqueous solution of the monomer.
  • polymerization initiators are peroxides such as hydrogen peroxide, benzoyl peroxide and the like; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate and the like, bromates such as sodium bromate, potassium bromate and the like, perborates such as sodium perborate, potassium perborate, ammonium perborate, and the like; percarbonates such as sodium percarbonate, potassium percarbonate, ammonium percarbonate and the like; perphosphates such as sodium perphosphate, potassium perphosphate, ammonium perphosphate, and the like; tert-butyl peroxide and the like.
  • peroxides such as hydrogen peroxide, benzoyl peroxide and the like
  • persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate and the like, bromates such as sodium bromate, potassium bromate and the like
  • perborates such as sodium perborate, potassium per
  • the above-mentioned initiators may be used alone or in combination with a reducing agent as a redox type polymerization agent.
  • reducing agent there may be mentioned, for example, sulfites, hydrogensulfites, salts of iron, copper, cobalt and the like of a low order ionization, organic amines such as N,N,N',N'-tetramethyl ethylenediamine and the like, and reducing sugars such as aldose and ketose.
  • azo compounds there may be used 2,2'-azobis-4-amidinopropane hydrochloride, 2,2'-azobis-2,4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid, salts thereof and the like.
  • polymerization initiator may be used in combination.
  • the polymerization temperature is as low as 30 to 90°C in the case of a single polymerization initiator, and much lower such as about 5 to 50°C in the case of a redox polymerization initiator.
  • the temperature may be changed accordingly as the polymerization proceeds.
  • the temperature rises due to the generated polymerization heat.
  • the atmosphere in the polymerization vessel at that time is not particularly limited, but it is desirable to replace the atmosphere with an inert gas such as nitrogen gas for the purpose of accelerating the polymerization.
  • the polymerization time is not critical, but is usually 1 - 20 hours.
  • the method of the present invention is used for making paper from pulp, and is effective to improve remarkably freeness for draining water upon papermaking and improve paper strength serving to enhance the mechanical strength of paper.
  • the amount ratio of Hofmann decomposition PAM and cationic polyacrylamide (B) is optional depending on pulp raw material and white water. However, from the standpoint of mixing effect, it may range from 95 : 5 to 5 : 95, preferably from 80 :20 to 20 :80.
  • the cationic polyacrylamide may be added to pulp in such a monner that Hofmann decomposition PAM and cationic polyacrylamide (B) are separately added to pulp slurry, or Hofmann decomposition PAM and cationic polyacrylamide (B) are firstly mixed and then added to pulp slurry. Either may be used.
  • the water-soluble anionic resins used here may be water-soluble resins having an anionic substituent such as carboxyl group, sulfonic acid group, phosphoric acid group and the like, or salts thereof.
  • resins examples include: anionic acrylamide resins, anionic polyvinyl alcohol resins, carboxymethylcellulose, carboxymethylated starch, sodium alginate, and the like.
  • the point where the agents are to be added is not particularly critical.
  • the agents may be added before or after or simultaneously with adding Hofmann decomposition PAM and cationic polyacrylamide (B) to pulp slurry. Further, the agents may be mixed separately with each of Hofmann decomposition PAM and cationic polyacrylamide (B), or may be mixed with a mixture solution of Hofmann decomposition PAM and cationic polyacrylamide (B).
  • the place where the addition is effected may be anywhere as far as it is before forming a wet sheet.
  • a papermaking machine there may be used either Fourdrinier paper machine or cylinder paper machine.
  • the present additive for papermaking is added to a pulp slurry having a concentration of 0.5 - 5.0 %, pH 4.0 - 9.0 at a temperature of 20 - 70°C, a wet sheet is formed at a wire part and then water is squeezed at a press part.
  • the nip pressure at the press part ranges from 20 to 400 kg/cm. After passing the press part, the wet sheet is transferred to a dry part and dried with steam.
  • the steam pressure is 2 - 15 kg/cm2 and the drying is carried out in a drum at 80 - 200°C.
  • chemical treatments may be effected at a size press or calender so as to improve printing property, surface strength, water resistance, and water repellency.
  • the additives for papermaking according to the present invention may be in the form of a water-soluble liquid mixture comprising Hofmann decomposition PAM and cationic polyacrylamide (B) as active components.
  • the concentration of the active components may range from 0.001 to 50 %.
  • the amount ratio of Hofmann decomposition PAM to cationic polyacrylamide (B) may range, in terms of weight, from 95 : 5 to 5 : 95, preferably from 80 : 20 to 20 : 80.
  • the decomposition rate of Hofmann decomposition is not particularly critical, but is usually 5 - 60 mol %, preferably 10 - 50 mol %.
  • a method for mixing Hofmann decomposition PAM and cationic polyacrylamide (B) may be as shown below.
  • the solution after Hofmann decomposition reaction is usually of pH 12 - 13, but the pH may be lowered with an inorganic or organic acid before or after mixing with cationic polyacrylamide (B).
  • the additives for papermaking according to the present invention may range from 2 to 14.
  • reaction product A part of the reaction product was added to an aqueous solution of pH 2 and a colloid titration by means of a 1/400 N aqueous solution of potassium polyvinyl sulfonate using toluidine blue as indicator.
  • the resulting cationicity was 4.4 meq./g.
  • reaction product A part of the reaction product was added to an aqueous solution of pH 2 and a colloid titration was carried out using a 1/400 N aqueous solution of potassium polyvinyl sulfonate with toluidine blue as indicator and the cationcity was 4.4 meq./g.
  • CSF Canadian Standard Freeness
  • Part of the resulting pulp slurry was taken to measure CSF according to JIS-P-8121, and the remainder was used to make paper in a TAPPI square sheet machine, and then the resulting paper was dried for two hours at 110°C by a hot air blowing dryer to obtain a hand-made paper with a basis weight of 150 ⁇ 3 g/m2.
  • Example 1 The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.60 % based on the dry weight. Table 1 shows the result.
  • Example 1 The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.90 % based on the dry weight. Table 1 shows the result.
  • Example 1 The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 1.50 % based on the dry weight. Table 1 shows the result.
  • Example 1 The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 0.003 % based on the dry weight. Table 1 shows the result.
  • Example 1 The procedure of Example 1 was repeated to effect the hand-making paper test except that No. 3 water glass was added in an amount of 5.00 % based on the dry weight. Table 1 shows the result.
  • CSF Canadian Standard Freeness
  • colloidal silica (Snowtex 40, particle size 10 - 20 nm, manufactured by Nissan Kagaku K.K.) was added thereto in an amount of 0.25 % based on the dry weight of pulp followed by stirring for 30 sec, and Hofmann PAM (A) obtained in Preparation Example 1 was added thereto in an amount of 1.50 % based on the dry weight of pulp. The stirring was continued for further 30 sec.
  • Example 5 The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 0.50 % based on the dry weight. Table 2 shows the result.
  • Example 5 The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 1.00 % based on the dry weight. Table 2 shows the result.
  • Example 5 The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 0.001 % based on the dry weight. Table 2 shows the result.
  • Example 5 The procedure of Example 5 was repeated to effect the hand-making paper test except that colloidal silica was added in an amount of 10.0 % based on the dry weight. Table 2 shows the result.
  • reaction mixture was kept at 85°C, and three hours after the beginning of the polymerization, water was added to stop the polymerization reaction and there was obtained a stable aqueous solution of acrylamide polymer having 15.3 % of non-volatile matter, Brookfield viscosity of 6,800 cps at 25°C and pH 4.3.
  • reaction product was added to an aqueous solution of pH 2 and a colloid titration was then carried out using a 1/400 N aqueous solution of potassium polyvinyl sulfonate with toluidine blue as indicator and the cationicity was 3.8 meq./g.
  • CSF Canadian Standard Freeness
  • acrylamide polymer obtained in Preparation Example 3 was added to the resulting mixture as above in an amount of 0.30 % based on the dry weight of pulp.
  • Stirring was effected for one minute and then Hofmann PAM (C) obtained in Preparation Example 4 was added thereto in an amount of 0.10 % based on the dry weight of pulp.
  • the stirring was continued for a further one minute and then a part of the resulting pulp slurry was taken to measure CSF according to JIS-P-8121, and the remainder was used to make paper in a TAPPI square sheet machine.
  • the resulting product was dried by a hot air blowing dryer at 110°C for 2 hours to obtain a hand-make paper with a basis weight of 125 ⁇ 3 g/m2.
  • Example 8 The procedure of Example 8 was repeated to effect the hand-making paper test except that the polyacrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.20 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.20 % based on the dry weight. Table 3 shows the result.
  • Example 8 The procedure of Example 8 was repeated to effect the hand-making paper test except that the polyacrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.10 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.30 % based on the dry weight. Table 3 shows the result.
  • Example 8 The procedure of Example 8 was repeated to effect the test except that the acrylamide polymer obtained in Preparation Example 3 was added in an amount of 0.40 % based on the dry weight and Hofmann PAM (C) obtained in Preparation Example 4 was not added. Table 3 shows the result.
  • Example 8 The procedure of Example 8 was repeated to effect the test except that Hofmann PAM (C) obtained in Preparation Example 4 was added in an amount of 0.40 % based on the dry weight and the acrylamide polymer obtained in Preparation Example 3 was not added. Table 3 shows the result.
  • papers manufactured according to the conditions of the present invention exhibit rather a tendency of improved paper strength by the addition of anionic inorganic substances though addition of anionic inorganic substances usually changes the freeness.
  • the present invention exhibits a great effect.
  • papers made under the conditions within the scope of the present invention can exhibit excellent characteristics such as specific rupture strength, specific compression strength, internal bond strength and the like as compared with the case where an acrylamide polymer obtained in Preparation Example 3 or 4 is used alone while the papers made according to the present invention retains the same level of freeness as that in the case where the acrylamide polymer obtained in Preparation Example 4 is used alone.
  • the paper produced by the method of the present invention exhibits excellent specific rupture strength, specific compression strength, internal bond strength and the like.
  • Addition of the anionic inorganic substance is suitable for controlling the formation and producing a paper of high strength even if the freeness is somewhat adversely affected.
  • the cationic polyacrylamide is added, the level of freeness attained by using an acrylamide polymer alone can be retained, the formation is not lowered despite of good freeness which usually indicates lowering thereof, and the paper strength characteristic is excellent as compared with that when the acrylamide polymer is used alone.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

Additif destiné à la fabrication du papier et comportant (A) un polymère acrylamide cationique obtenu par la réaction d'un polymère acrylamide avec un hypohalite sous des conditions alcalines, à une température comprise entre 50 et 110 °C, et pendant une courte durée; et (B) soit une substance inorganique anionique soit un polyacrylamide cationique obtenu par la copolymérisation d'un monomère cationique tel qu'un ester acrylique ou un dérivé d'acrylamide, un acide carboxylique insaturé-alpha,beta ou un sel, et l'acrylamide.
EP91912068A 1990-06-28 1991-06-27 Procede de fabrication de papier et additif associe Expired - Lifetime EP0489930B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP16837990 1990-06-28
JP16837690 1990-06-28
JP168379/90 1990-06-28
JP168376/90 1990-06-28
PCT/JP1991/000869 WO1992000417A1 (fr) 1990-06-28 1991-06-27 Procede de fabrication de papier et additif associe

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EP0489930A1 true EP0489930A1 (fr) 1992-06-17
EP0489930A4 EP0489930A4 (en) 1992-12-09
EP0489930B1 EP0489930B1 (fr) 1995-05-10

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EP (1) EP0489930B1 (fr)
KR (2) KR950011186B1 (fr)
CA (1) CA2065282C (fr)
DE (1) DE69109639T2 (fr)
FI (1) FI920866A0 (fr)
WO (1) WO1992000417A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697400A3 (fr) * 1994-08-19 1996-06-19 Nippon Paint Co Ltd Monomère à base d'amide et polymère préparé à partir de ces derniers
EP0735186A3 (fr) * 1995-03-30 1998-02-18 Japan Pmc Corporation Adjuvant pour la papeterie et procédé papetier
WO2006061456A1 (fr) * 2004-12-10 2006-06-15 Metso Paper, Inc. Procédé de fabrication de nervurage ou de revêtement d’essai

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101395270B1 (ko) * 2012-08-03 2014-05-15 (주)기륭산업 친환경적 제지용 지력증강제의 제조방법
CN114481692B (zh) * 2022-03-01 2023-07-18 山东博汇纸业股份有限公司 一种复合纸力增强剂及其制备方法

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Publication number Priority date Publication date Assignee Title
JPS58108206A (ja) * 1981-12-21 1983-06-28 Konan Kagaku Kogyo Kk 安定なポリアクリルアミドカチオン変性物水溶液の製造方法
JPS6065195A (ja) * 1983-09-19 1985-04-13 星光化学工業株式会社 製紙工程に於ける填料歩留向上方法
JP2515495B2 (ja) * 1985-07-12 1996-07-10 星光化学工業 株式会社 中性紙の製方
JPH086008B2 (ja) * 1985-11-18 1996-01-24 星光化学工業株式会社 置換コハク酸無水物の水性分散液
US5039757A (en) * 1988-12-28 1991-08-13 Mitsui Toatsu Chemicals, Inc. Method of manufacturing cationic acrylamide polymers, cationic acrylamide polymers, and the applications of these polymers

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0697400A3 (fr) * 1994-08-19 1996-06-19 Nippon Paint Co Ltd Monomère à base d'amide et polymère préparé à partir de ces derniers
EP0735186A3 (fr) * 1995-03-30 1998-02-18 Japan Pmc Corporation Adjuvant pour la papeterie et procédé papetier
WO2006061456A1 (fr) * 2004-12-10 2006-06-15 Metso Paper, Inc. Procédé de fabrication de nervurage ou de revêtement d’essai

Also Published As

Publication number Publication date
EP0489930A4 (en) 1992-12-09
FI920866A7 (fi) 1992-02-27
DE69109639D1 (de) 1995-06-14
WO1992000417A1 (fr) 1992-01-09
CA2065282C (fr) 1996-10-22
KR950011186B1 (ko) 1995-09-29
CA2065282A1 (fr) 1991-12-29
KR950009738B1 (ko) 1995-08-26
DE69109639T2 (de) 1995-09-07
KR920702453A (ko) 1992-09-04
FI920866A0 (fi) 1992-02-27
EP0489930B1 (fr) 1995-05-10

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