WO2017110868A1 - Polyacrylamide-based papermaking additive, method for producing same, and method for producing paper - Google Patents

Polyacrylamide-based papermaking additive, method for producing same, and method for producing paper Download PDF

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WO2017110868A1
WO2017110868A1 PCT/JP2016/088084 JP2016088084W WO2017110868A1 WO 2017110868 A1 WO2017110868 A1 WO 2017110868A1 JP 2016088084 W JP2016088084 W JP 2016088084W WO 2017110868 A1 WO2017110868 A1 WO 2017110868A1
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Prior art keywords
polyacrylamide
paper
aldehyde
meth
additive
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PCT/JP2016/088084
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French (fr)
Japanese (ja)
Inventor
雄貴 蝦名
孝治 吉谷
英夫 茨木
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星光Pmc株式会社
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Priority to KR1020187011847A priority Critical patent/KR102063409B1/en
Priority to CN201680049404.7A priority patent/CN108026699B/en
Priority to JP2017558188A priority patent/JP6593455B2/en
Publication of WO2017110868A1 publication Critical patent/WO2017110868A1/en

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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/34Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H21/00Non-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
    • D21H21/14Non-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
    • D21H21/18Reinforcing agents

Definitions

  • the present invention relates to a polyacrylamide-based paper additive containing aldehyde-functionalized polyacrylamide having an excellent paper strength enhancing effect and good drainage, and a method for producing the same.
  • the present invention also relates to a paper production method using the polyacrylamide paper additive.
  • aldehyde-functionalized polyacrylamide-based papermaking additives are used in the papermaking process in order to improve the productivity of paper accompanying the speeding up of the paper machine or the quality of paper.
  • Aldehyde functionalized polyacrylamide is generally produced by reacting glyoxal, a dialdehyde compound, with polyacrylamide.
  • the aldehyde-functionalized polyacrylamide contains aldehyde groups having reactivity with cellulose in addition to containing amide groups having high hydrogen bonding ability in the polymer structure. For this reason, since a covalent bond can be formed with the hydroxyl group of cellulose, an excellent paper strength enhancing effect and drainage can be expected.
  • Aldehyde-functionalized polyacrylamide-based paper additive for example, introduces 15 mol% or more of aldehyde functional groups with respect to amino groups or amide groups such as polyamines and (nonionic, cationic, anionic, or amphoteric) polyamides.
  • a method for increasing the drainage of a paper machine by adding a polymer having a weight average molecular weight of 100,000 g / mol or more to a pulp slurry has been proposed (see Patent Document 1).
  • a method for producing a cellulose-reactive functionalized polyvinylamide adduct by reacting a vinylamide polymer with a cellulose-reactive agent has been proposed (see Patent Document 2).
  • dialdehyde-modified polyacrylamide excellent in paper strength enhancing effect obtained by reacting amphoteric or anionic polyacrylamide using a divinyl monomer with glyoxal has been proposed (see Patent Document 3).
  • the present invention provides a polyacrylamide-based papermaking additive containing an aldehyde-functionalized polyacrylamide having excellent paper strength enhancing effect and good drainage, a method for producing the same, and a method for producing paper using the papermaking additive. For the purpose.
  • the inventors of the present invention have studied earnestly, considering that improving the fixability of a polyacrylamide-based paper additive containing an aldehyde-functionalized polyacrylamide to a pulp leads to the solution of the above problems. Specifically, the ratio of (1) the aldehyde compound added to the aldehyde-functionalized polyacrylamide, (2) the number average molecular weight, and (3) the isoelectric point related to the ionic properties were examined. As a result, the aldehyde-functionalized polyacrylamide in which the above (1) to (3) are within a certain range is disadvantageous for the fixing efficiency to the pulp, even in the conditions where no sulfuric acid band is added and the electric conductivity is high.
  • a polyacrylamide-based papermaking additive comprising an aldehyde-functionalized polyacrylamide (A) characterized by satisfying all of the following (1) to (3): (1) In the aldehyde-functionalized polyacrylamide (A), the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the dialdehyde compound, is 3 ⁇ 20 mol% (2) Aldehyde-functionalized polyacrylamide (A) has a number average molecular weight of 500,000 to 4,000,000 (3) Aldehyde-functionalized polyacrylamide (A) has
  • the aldehyde-functionalized polyacrylamide (A ′) according to ⁇ 5> is any one of the above ⁇ 1> to ⁇ 4>.
  • a method for producing a polyacrylamide-based additive for papermaking which is an aldehyde-functionalized polyacrylamide (A), ⁇ 7>
  • the polyacrylamide papermaking additive according to any one of ⁇ 1> to ⁇ 4> is added to the pulp slurry in an amount of 0.01 to 3% by mass based on the pulp solid content. , Paper manufacturing method.
  • a polyacrylamide papermaking additive containing an aldehyde-functionalized polyacrylamide having an excellent paper strength enhancing effect and good drainage, a method for producing the same, and a method for producing paper using the papermaking additive Can be provided.
  • the polyacrylamide papermaking additive containing the aldehyde-functionalized polyacrylamide (A) of the present invention comprises (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group as a polymer constituent unit. Is a dialdehyde compound adduct of the amphoteric polyacrylamide copolymer (a).
  • the method for producing a polyacrylamide-based paper additive containing the aldehyde-functionalized polyacrylamide (A ′) of the present invention comprises (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group
  • the amphoteric polyacrylamide copolymer (a) obtained by polymerizing is reacted with the dialdehyde compound (b) so as to satisfy the following conditions (1) to (5).
  • the dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
  • the pH is 7.5 to 12.5,
  • the temperature is 1 to 60 ° C.
  • the concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass, (5)
  • the time is 20 seconds to 4 hours
  • (Meth) acrylamide in the present invention is acrylamide or methacrylamide.
  • Examples of the cationic vinyl monomer in the present invention include a vinyl monomer having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium salt. These cationic vinyl monomers may be used individually by 1 type, and may use 2 or more types together. It is preferable to use a vinyl monomer having a tertiary amino group as the cationic vinyl monomer constituting the amphoteric polyacrylamide copolymer (a) because the effect of fixing to pulp is likely to increase when used as a papermaking additive.
  • vinyl monomers having a tertiary amino group examples include dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate.
  • dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate.
  • Dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide; Hydrochloric acid salts of vinyl monomers having the tertiary amino group, and inorganic acid salts such as sulfates And organic acid salts such as formate and acetate of vinyl monomers having a tertiary amino group.
  • dialkylaminoalkyl (meth) acrylates are preferable.
  • the vinyl monomer having a quaternary ammonium salt includes a vinyl monomer obtained by the reaction of the vinyl monomer having a tertiary amino group and a quaternizing agent, and a vinyl having a quaternary ammonium salt such as diallyldimethylammonium chloride.
  • the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide; aralkyl halides such as benzyl chloride and benzyl bromide; dimethyl sulfate, diethyl sulfate, epichlorohydrin, 3-chloro-2-hydroxypropyltrimethylammonium chloride. And glycidyltrialkylammonium chloride.
  • These tertiary amino groups or vinyl monomers having quaternary ammonium salts may be used alone or in combination of two or more.
  • anionic vinyl monomer in the present invention examples include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 2- (meth) acrylamide-N-glycolic acid and N-acryloylglycine; maleic acid, fumaric acid, itaconic acid, citracone Unsaturated dicarboxylic acids such as acids; unsaturated tricarboxylic acids such as aconitic acid and 3-butene-1,2,3-tricarboxylic acid; 1-pentene-1,1,4,4-tetracarboxylic acid and 4-pentene- Unsaturated tetracarboxylic acids such as 1,2,3,4-tetracarboxylic acid and 3-hexene-1,1,6,6-tetracarboxylic acid; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl Unsaturated sulfonic acids such as propanesulfonic acid; unsaturated phosphonic acids
  • unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are suitable from the viewpoint of improving paper strength, and specifically include acrylic acid, 2-acrylamide-N-glycolic acid, itacone. Acids and their salts are particularly preferred.
  • the monomer having a (meth) allyl group in the present invention may be a monomer having a (meth) allyl group, and other functional groups such as an anionic group and a cationic group in addition to the (meth) allyl group. Even if it has, it is classified as a monomer having a (meth) allyl group. Specific examples include (meth) allylsulfonic acid or a salt thereof, (meth) allyl alcohol, (meth) allylamine, (meth) allyl ammonium salt, and the like. Of these, (meth) allylsulfonic acid or a salt thereof and dimethylhydroxyethyl methallyl ammonium chloride are preferable.
  • the monomer in the amphoteric polyacrylamide copolymer (a) of the present invention other monomers may be used as long as the effects of the present invention are not impaired.
  • the range that does not inhibit the effect of the present invention is a total of 100 mol% of (meth) acrylamide, cationic vinyl monomer, anionic vinyl monomer, and monomer having a (meth) allyl group in the amphoteric polyacrylamide copolymer (a).
  • 0 to 3.0 mol% of other monomers are more preferable.
  • Examples of other monomer components include nonionic vinyl monomers, crosslinking agents, and chain transfer agents.
  • nonionic vinyl monomers include (meth) acrylic acid esters, (meth) acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate, and methyl vinyl ether. These may be used individually by 1 type and may use 2 or more types together.
  • crosslinking agent examples include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide.
  • N-substituted (meth) acrylamides such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and other di (meth) acrylates;
  • Bis (meth) acrylamides such as N, N′-methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide; triacryl formal, triallyl isocyanurate, N, N Diallyl acrylamide, N, N-diallyl methacrylamide, triallylamine, mention may be made of polyfunctional monomers such as 3-4 functional vinyl monomers such as tetramethylolmethane tetraacrylate.
  • a water-soluble aziridinyl compound a water-soluble polyfunctional epoxy compound, a silicon compound, etc.
  • These may be used individually by 1 type and may use 2 or more types together.
  • N-substituted (meth) acrylamide is preferable.
  • chain transfer agent examples include known chain transfer agents such as alkyl mercaptans and 2,4-diphenyl-4-methyl-1-pentene. These may be used individually by 1 type and may use 2 or more types together.
  • the proportion of the monomer in the amphoteric polyacrylamide copolymer (a) is preferably 74.0 to 99.7 mol% of (meth) acrylamide, considering the ion balance and the reaction of the dialdehyde compound with respect to the amide group.
  • the range is 0.1 to 12.0 mol% of vinyl monomer, 0.1 to 10.0 mol% of anionic vinyl monomer, and 0.1 to 4.0 mol% of monomer having (meth) allyl group, more preferably (meta ) 83.0 to 99.7 mol% of acrylamide, 0.1 to 8.0 mol% of cationic vinyl monomer having tertiary amino group, 0.1 to 7.0 mol% of anionic vinyl monomer, and (meth) allyl group
  • the monomer is in the range of 0.1 to 2.0 mol%.
  • the amphoteric polyacrylamide copolymer (a) is not particularly limited with respect to its production method, and can be obtained by a known polymerization method. In order to improve the fixability to pulp as the papermaking additive of the present invention, it is preferable to polymerize the monomer component by dividing or dropping.
  • amphoteric polyacrylamide copolymer (a) there are no particular restrictions on the number average molecular weight and molecular weight distribution of the amphoteric polyacrylamide copolymer (a), but the molecular weight increases upon reaction with the dialdehyde compound and exceeds the appropriate number average molecular weight and molecular weight distribution range.
  • a number average molecular weight of 50,000 to 3,000,000 and a molecular weight distribution of 2.0 to 7.0 are preferred.
  • the aldehyde functionalized polyacrylamide (A) of the present invention is not limited with respect to its production method.
  • the dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
  • the pH is 7.5 to 12.5,
  • the temperature is 1 to 60 ° C.
  • the concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass, (5)
  • the time is 20 seconds to 4 hours
  • the dialdehyde compound (b) to be reacted with the amphoteric polyacrylamide copolymer (a) is a group consisting of glyoxal, glutaraldehyde, 2,5-diformylfuran, 2-hydroxyadipaldehyde, succinaldehyde, and combinations thereof Selected from.
  • Glyoxal is most preferable from the viewpoint of reactivity and drainage effect.
  • the amount of the dialdehyde compound (b) to be reacted with the amphoteric polyacrylamide copolymer (a) is the amide of the amphoteric polyacrylamide copolymer (a) from the viewpoint of reaction efficiency and effect. It is preferable to react by mixing 10 to 60% in molar ratio with respect to the group (production condition 1). By performing such a reaction, it is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the aldehyde compound in the aldehyde-functionalized polyacrylamide (A). The amide reaction rate tends to be 3 to 20 mol%.
  • the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) if the base is added as necessary to adjust the pH of the reaction solution to 7.5 to 12.5, the amphoteric polyacrylamide copolymer is reacted. This is preferable because the reaction between the polymer (a) and the dialdehyde compound (b) is promoted (production condition 2).
  • the concentration of the amphoteric polyacrylamide copolymer (a) is within the range of 0.5 to 11.0% by mass, the predetermined molecular weight, intrinsic viscosity, aldehyde is suppressed while suppressing the thickening of the reaction solution. This is preferable because it is easy to adjust the amount of functionalized amide. (Production condition 4).
  • the reaction time of the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) is preferably in the range of 20 seconds to 4 hours, since the reaction between the polyacrylamide and the dialdehyde compound is promoted. (Production conditions 5).
  • the polyacrylamide papermaking additive containing the aldehyde-functionalized polyacrylamide (A) of the present invention satisfies all of the following (1) to (3).
  • the amide reaction rate which is the ratio of the amide group added by the dialdehyde compound to the amide group of the (meth) acrylamide structural unit before the dialdehyde addition, 3 to 20 mol%
  • the amide reaction rate which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the aldehyde compound, is 3 to 20 mol%.
  • (Polyacrylamide (A) condition 1) more preferably 3 to 15 mol%.
  • the amide reaction rate referred to in the present invention is calculated from an integration ratio of 179 to 181 ppm (aldehyde functionalized amide peak) and 182 ppm to 185 ppm (amide group peak) by 13 C-NMR measurement.
  • the amide reaction rate is less than 3%, the amount of aldehyde groups in the polymer is insufficient, and when it is higher than 20%, the polymers cause a cross-linking reaction with the dialdehyde compound due to excessive progress of the reaction. Insufficient amount of aldehyde groups. For this reason, the covalent bond between the cellulose by an aldehyde group cannot be formed, but it is disadvantageous for the paper strength improvement effect or drainage.
  • the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) needs to be 500,000 to 4,000,000 (polyacrylamide (A) condition 2), more preferably 500,000 to 3,000,000.
  • the number average molecular weight is less than 500,000, the proportion of the low molecular weight polymer component that has a small contribution to fixing to the pulp is increased, resulting in poor fixing effect.
  • it exceeds 4 million the pulp is agglomerated to cause deterioration of the paper texture, which is disadvantageous for the paper strength enhancing effect.
  • the number average molecular weight in the present invention refers to that obtained by GPC-MALS method in which a multi-angle light scattering detector is connected to GPC.
  • Aldehyde functionalized polyacrylamide (A) needs to exhibit an isoelectric point where the ionization degree is 0 meq / g between pH 3.5 and 8.5 (polyacrylamide (A) condition 3).
  • the isoelectric point is between pH 3.5 and 8.5, the polymer forms a complex by the ionic interaction of the cation and anion in the papermaking system, and the fixing effect to the pulp is enhanced. It is advantageous for drainage.
  • the isoelectric point as used in the present invention is measured by a PCD electrometer, but is not limited to the above apparatus as long as the same principle can be measured.
  • the molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) is preferably 2.0 to 8.0, more preferably 2.0 to 7.0.
  • the molecular weight distribution is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and if it exceeds 8.0, it tends to cause excessive pulp aggregation.
  • the aldehyde-functionalized polyacrylamide (A) having an appropriate molecular weight distribution is less likely to cause deterioration of the paper texture due to excessive pulp agglomeration, and is advantageous for the paper strength enhancing effect.
  • the weight average molecular weight in the present invention required for obtaining the molecular weight distribution refers to that obtained by GPC-MALLS method in which a multi-angle light scattering detector is connected to GPC.
  • the aldehyde-functionalized polyacrylamide (A) is a main component, and the proportion of the polyacrylamide based paper is preferably 60% by mass or more, more preferably 80% by mass based on the total solid content. It is preferable that Further, the polyacrylamide papermaking additive of the present invention may contain an unreacted dialdehyde compound. In that case, it is preferable to add an acid to adjust the pH to 2.5 to 4.5 to stop the reaction with the dialdehyde compound to make an additive for papermaking. The reaction solution can be added to the pulp slurry as it is without lowering.
  • Examples of the base used for pH adjustment include sodium hydroxide, potassium hydroxide, ammonia and the like, and examples of the acid include sulfuric acid, hydrochloric acid, acetic acid and the like.
  • antiseptic preservative, an antifoamer, etc. may be contained.
  • the polyacrylamide papermaking additive of the present invention is preferably added to the pulp slurry (hereinafter sometimes abbreviated as “internal addition”).
  • Pulp slurry is a slurry of pulp diluted with water.
  • pulp bleached or unbleached chemical pulp such as kraft pulp and sulfite pulp; bleached or unbleached pulp such as groundwood pulp, mechanical pulp, thermomechanical pulp, etc .; waste newspaper, magazine waste paper, corrugated paper Examples include waste paper pulp such as deinked waste paper.
  • the polyacrylamide paper additive of the present invention is usually 0.01 to 3.0% by mass, preferably 0.05 to 2.5% by mass, more preferably 0.1 to 2.0% by mass per pulp solid content. % Is used.
  • an aluminum compound such as a sulfuric acid band or polyaninium chloride (PAC) is added, it is preferable to add 0.1 to 1.0% by mass per pulp solid content.
  • a method of adding a polyacrylamide paper additive to a pulp slurry a method of adding a polyacrylamide paper additive without using any aluminum compound, a polyacrylamide paper additive after adding an aluminum compound
  • a method of adding an agent, a method of adding an aluminum compound after adding a polyacrylamide-based papermaking additive, a method of simultaneously adding an aluminum compound and a polyacrylamide-based papermaking additive, and the like are also good.
  • an acidic system using aluminum sulfate or a neutral system using no or a small amount of aluminum sulfate may be used.
  • an acidic rosin sizing agent, a neutral rosin sizing agent, an alkyl ketene dimer sizing agent, an alkenyl or alkyl succinic anhydride sizing agent, and the like may be added to the pulp slurry.
  • a method for adding these sizing agents after adding a sizing agent to a pulp slurry, a method of adding a polyacrylamide papermaking additive, a method of adding a sizing agent after adding a polyacrylamide papermaking additive, examples include a method of adding a polyacrylamide paper additive to a sizing agent after diluting and premixing.
  • fillers such as clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc.
  • the paper to be produced usually has a basis weight of about 10 to 400 g / m 2 .
  • surface paper strength enhancer such as starch, polyvinyl alcohol, acrylamide polymer, surface sizing agent, dye, coating color, anti-slip agent, etc. as required It may be applied.
  • the papermaking pH of the pulp slurry obtained by adding the polyacrylamide papermaking additive of the present invention to the pulp slurry and adding other additives as necessary is 3.5 to 8.5. From the viewpoint of the paper strength enhancing effect, it is preferably 6.5 to 8.5.
  • the papermaking pH in the present invention is the pH of the pulp slurry immediately before dewatering with the papermaking machine, and the pH of the pulp slurry immediately before dewatering with the papermaking machine generally corresponds to the pH at the inlet in the actual machine. .
  • the paper produced using the polyacrylamide papermaking additive of the present invention includes information paper such as PPC paper, photosensitive paper base paper, and thermal paper base paper, art base paper, cast coated paper, coated base paper such as high-quality coated paper, etc.
  • Sanitary paper such as tissue paper, towel paper, napkin base paper, fruit bag base paper, cleaning tag base paper, decorative board base paper / wall paper base, photographic paper base, processed base paper such as base paper for food containers, heavy paper Examples include wrapping paper such as bifuran kraft paper and single gloss kraft paper, electrical insulation paper, liner, core, paper tube base paper, gypsum board base paper, newsprint paper, paperboard board, etc. Therefore, it is possible to give a useful paper strength enhancing effect to the paper made. Among these, it is particularly preferable to use paper that requires paper strength or paper that restricts the use of sulfuric acid bands (information paper, coated base paper, paperboard board).
  • the paper referred to in the present invention includes paperboard.
  • the number average molecular weight, weight average molecular weight, and molecular weight distribution were obtained by GPC-MALLS method in which a multi-angle light scattering detector was connected to GPC under the following measurement conditions.
  • HPLC Agilent 1100 series column: SHODEX SB806MHQ manufactured by Showa Denko K.K.
  • Eluent phosphate buffer containing sodium nitrate (pH 3)
  • Flow rate 1.0 ml / min
  • Detector 1 Multi-angle light scattering detector DAWN manufactured by Wyatt Technology
  • Detector 2 Suggested refractive index detector RI-101 manufactured by Showa Denko KK
  • amphoteric polyacrylamide copolymer (a-1) having a solid content of 15.0%.
  • Table 1 shows the results of measuring the ratio (mol%) of the monomer units constituting the amphoteric polyacrylamide copolymer (a-1), the number average molecular weight, the weight average molecular weight, and the molecular weight distribution.
  • amphoteric polyacrylamide copolymer (a-) having a solid content of 15.0% was prepared in the same manner as in Production Example 1 except that the compositions of the monomers (1) and monomers (2) were changed as shown in Table 1. 2) to (a-14) and (ra-1) to (ra-6) were obtained.
  • the degree of ionization of the polyacrylamide paper additive (A-1) was adjusted by adjusting the polymer concentration to 0.1% by weight using a PCD electrometer PCD02 (manufactured by MUTEC) and adjusting the pH with an acid-base component. The aqueous solution was measured. As a result, the isoelectric point at which 0 meq / g was reached was pH 4.4, and it was confirmed that an isoelectric point was present in the pH range of 3.5 to 8.5. The results are shown in Table 3.
  • Examples 2 to 16 and Comparative Examples 1 to 10 Except that the amphoteric polyacrylamide copolymer (a) type, reaction temperature, pH, concentration, time, glyoxal amount (mol% vs. amide group of copolymer (a)) were changed as shown in Table 2.
  • Example 1 was carried out in the same manner as in Example 1 to obtain polyacrylamide-based papermaking additives containing aldehyde-functionalized polyacrylamides (A-2) to (A-16) and (RA-1) to (RA-10) .
  • Table 3 shows the results of measuring the number average molecular weight, molecular weight distribution, amide reaction rate, and isoelectric point of the obtained aldehyde-functionalized polyacrylamide in the same manner as in Example 1.
  • Example 1 0.5% by mass of a sulfuric acid band was added to a pulp slurry of corrugated waste paper having a concentration of 2.4%, a beating degree (Canadian Standard Freeness) of 350, and an electric conductivity of 200 mS / m based on the pulp solid content. Next, 0.3% by mass of the polyacrylamide-based papermaking additive obtained in Example 1 was added to the pulp solid content in terms of solid content. After stirring this pulp slurry, the pulp concentration was diluted to 0.8% with water of pH 7.0, and then paper was made with a sheet machine made by The Noble & Wood, and after pressing, 100 ° C.
  • DDT Tappi, Vol. 56, No. 10 (1973), page 46 of “Dynamic Drainage Jar”. 0.8%)
  • Application Examples 2-32 and Application Comparison Examples 1-24 In Application Example 1, the same operation as in Application Example 1 was carried out except that the type of polyacrylamide paper additive and the mass% were changed as shown in Table 4, and a paper having a basis weight of 80 g / m 2 was obtained. Obtained. The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 4. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 4.
  • Application Examples 34 to 64, Application Comparison Examples 25 to 48 In Application Example 33, the same operation as in Application Example 33 was performed except that the type and mass% of the polyacrylamide papermaking additive were changed as shown in Table 5, and a paper having a basis weight of 80 g / m 2 was obtained. Obtained. The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 5. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 5.
  • Paper was made with a sheet machine made by Wood (TheNoble & Wood), and after pressing, dried with a drum dryer at 100 ° C. for 100 seconds to obtain paper with a basis weight of 60 g / m 2 .
  • the obtained paper was evaluated in the same manner as in Application Example 1. The results are shown in Table 7.
  • the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 7.
  • Application Examples 82 to 112, Application Comparative Examples 61 to 84 In Application Example 81, except that the mass% of the sulfuric acid band and the type of polyacrylamide internal paper strength agent were changed as shown in Table 7, the same operation as in Application Example 81 was performed, and the basis weight was 60 g / m 2. I got the paper. The obtained paper was evaluated in the same manner as in Application Example 81. The results are shown in Table 7. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 81. The results are shown in Table 7.
  • the polyacrylamide papermaking additive of the present invention described in the examples is more pulpy than the polyacrylamide papermaking additive of the comparative example that does not satisfy even one of the configurations and conditions of the present invention. Regardless of the electrical conductivity and the presence or absence of a sulfuric acid band, it has excellent fixability to pulp, and is excellent at a level that satisfies paper strength and drainage.
  • the cationic vinyl monomer unit constituting the amphoteric polyacrylamide copolymer is more preferable. It can be seen that the tertiary amine is more excellent in paper strength enhancing effect and drainage.
  • the polyacrylamide papermaking additive of the present invention introduces an aldehyde group into the polymer structure.
  • the moisture content of the wet paper is low, and in addition to the paper strength enhancing effect and drainage, the water squeezing improving effect is also excellent.

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Abstract

The present invention pertains to: a polyacrylamide-based papermaking additive including an aldehyde-functionalized polyacrylamide which has excellent paper-strengthening effects and provides satisfactory water-filterability; and a method for producing paper by using the polyacrylamide-based papermaking additive. The polyacrylamide-based papermaking additive includes an aldehyde-functionalized polyacrylamide (A) which is a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) including, as polymer structural units, (meth)acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a (meth)allyl-group-including monomer, and which is characterized by satisfying various conditions.

Description

ポリアクリルアミド系製紙用添加剤及びその製造方法、並びに紙の製造方法Polyacrylamide paper additive, method for producing the same, and method for producing paper
 本発明は、紙力増強効果が優れ、濾水性が良好なアルデヒド官能化ポリアクリルアミドを含むポリアクリルアミド系製紙用添加剤及びその製造方法に関する。また、該ポリアクリルアミド系製紙用添加剤を用いた紙の製造方法に関する。 The present invention relates to a polyacrylamide-based paper additive containing aldehyde-functionalized polyacrylamide having an excellent paper strength enhancing effect and good drainage, and a method for producing the same. The present invention also relates to a paper production method using the polyacrylamide paper additive.
 抄紙機の高速化に伴う紙の生産性の向上、あるいは紙質の品質向上を図る為に、製紙工程では種々のアルデヒド官能化ポリアクリルアミド系製紙用添加剤が用いられている。アルデヒド官能化ポリアクリルアミドは一般的に、ジアルデヒド化合物であるグリオキサールとポリアクリルアミドを反応させる工程により製造される。アルデヒド官能化ポリアクリルアミドは、ポリマー構造中に高い水素結合能を有するアミド基を含有していることに加え、セルロースとの反応性を有するアルデヒド基を含有する。このため、セルロースの水酸基と共有結合を形成することができるので、優れた紙力増強効果および濾水性が期待できる。 Various aldehyde-functionalized polyacrylamide-based papermaking additives are used in the papermaking process in order to improve the productivity of paper accompanying the speeding up of the paper machine or the quality of paper. Aldehyde functionalized polyacrylamide is generally produced by reacting glyoxal, a dialdehyde compound, with polyacrylamide. The aldehyde-functionalized polyacrylamide contains aldehyde groups having reactivity with cellulose in addition to containing amide groups having high hydrogen bonding ability in the polymer structure. For this reason, since a covalent bond can be formed with the hydroxyl group of cellulose, an excellent paper strength enhancing effect and drainage can be expected.
 アルデヒド官能化ポリアクリルアミド系製紙用添加剤は、例えば、ポリアミンや(ノニオン性、カチオン性、アニオン性、または両性)ポリアミド等のアミノ基又はアミド基に対して、アルデヒド官能基が15モル%以上導入された重量平均分子量100,000g/モル以上のポリマーをパルプスラリーに添加することで、抄紙機の濾水性を高める方法が提案されている(特許文献1参照) 。また、ビニルアミドポリマーに対してセルロース反応性剤を反応させることにより、セルロース反応性官能化ポリビニルアミド付加物を製造するための方法が提案されている(特許文献2参照)。さらに、ジビニルモノマーを使用した両性あるいはアニオン性ポリアクリルアミドをグリオキサールと反応させた、紙力増強効果に優れたジアルデヒド変性ポリアクリルアミドが提案されている(特許文献3参照) 。 Aldehyde-functionalized polyacrylamide-based paper additive, for example, introduces 15 mol% or more of aldehyde functional groups with respect to amino groups or amide groups such as polyamines and (nonionic, cationic, anionic, or amphoteric) polyamides. A method for increasing the drainage of a paper machine by adding a polymer having a weight average molecular weight of 100,000 g / mol or more to a pulp slurry has been proposed (see Patent Document 1). In addition, a method for producing a cellulose-reactive functionalized polyvinylamide adduct by reacting a vinylamide polymer with a cellulose-reactive agent has been proposed (see Patent Document 2). Furthermore, dialdehyde-modified polyacrylamide excellent in paper strength enhancing effect obtained by reacting amphoteric or anionic polyacrylamide using a divinyl monomer with glyoxal has been proposed (see Patent Document 3).
 しかしながら、これらは、紙力増強効果及び濾水性において十分に満足できるものではなかった。 However, these were not fully satisfactory in terms of paper strength enhancing effect and drainage.
特表2007-518896号公報Special table 2007-518896 特表2010-502800号公報Special table 2010-502800 WO2000/011046号公報WO2000 / 011046
 本発明は、紙力増強効果が優れ、濾水性が良好なアルデヒド官能化ポリアクリルアミドを含むポリアクリルアミド系製紙用添加剤及びその製造方法並びにその製紙用添加剤を用いた紙の製造方法を提供することを目的とする。 The present invention provides a polyacrylamide-based papermaking additive containing an aldehyde-functionalized polyacrylamide having excellent paper strength enhancing effect and good drainage, a method for producing the same, and a method for producing paper using the papermaking additive. For the purpose.
 本発明者らは、アルデヒド官能化ポリアクリルアミドを含むポリアクリルアミド系製紙用添加剤のパルプへの定着性を向上させることが、前記課題の解決に繋がると考え、鋭意検討した。具体的には、アルデヒド官能化ポリアクリルアミドの、(1)アルデヒド化合物が付加している割合や、(2)数平均分子量、及び(3)イオン特性に関わる等電点について検討した。その結果、前記(1)~(3)が一定の範囲内にあるアルデヒド官能化ポリアクリルアミドが、パルプへの定着効率に不利な、硫酸バンド無添加条件や電気伝導度の高い条件においても、従来のアルデヒド官能化ポリアクリルアミドよりも紙力増強効果が優れ、濾水性が良好なことを見出し、本発明を完成した。また、本発明のアルデヒド官能化ポリアクリルアミドを含むポリアクリルアミド系製紙用添加剤を使用することで、パルプシート乾燥前の湿紙水分率が低くなり、搾水性向上効果があることも見出した。 The inventors of the present invention have studied earnestly, considering that improving the fixability of a polyacrylamide-based paper additive containing an aldehyde-functionalized polyacrylamide to a pulp leads to the solution of the above problems. Specifically, the ratio of (1) the aldehyde compound added to the aldehyde-functionalized polyacrylamide, (2) the number average molecular weight, and (3) the isoelectric point related to the ionic properties were examined. As a result, the aldehyde-functionalized polyacrylamide in which the above (1) to (3) are within a certain range is disadvantageous for the fixing efficiency to the pulp, even in the conditions where no sulfuric acid band is added and the electric conductivity is high. It was found that the paper strength enhancing effect was superior to that of aldehyde-functionalized polyacrylamide and the drainage was good, and the present invention was completed. It has also been found that by using the polyacrylamide papermaking additive containing the aldehyde-functionalized polyacrylamide of the present invention, the moisture content of the wet paper before drying the pulp sheet is lowered, and the water squeezing effect is improved.
 すなわち、前記課題を解決するための手段である本発明は、
<1>(メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、および(メタ)アリル基を有するモノマーをポリマー構成単位として有する両性ポリアクリルアミド共重合体(a)のジアルデヒド化合物付加物であり、下記(1)~(3)全てを満足することを特徴とするアルデヒド官能化ポリアクリルアミド(A)を含む、ポリアクリルアミド系製紙用添加剤、
(1)アルデヒド官能化ポリアクリルアミド(A)中の、アミド基及びジアルデヒド化合物が付加しているアミド基に対して、ジアルデヒド化合物が付加しているアミド基の割合であるアミド反応率が3~20モル%
(2)アルデヒド官能化ポリアクリルアミド(A)の数平均分子量が50万~400万
(3)アルデヒド官能化ポリアクリルアミド(A)がpH3.5~8.5の間でイオン化度が0meq/gになる等電点が存在する
<2>アルデヒド官能化ポリアクリルアミド(A)の分子量分布が2.0~8.0であることを特徴とする、前記<1>に記載のポリアクリルアミド系製紙用添加剤、
<3>ポリマー構成単位の割合が、(メタ)アクリルアミド :74.0~99.7mol%、カチオン性ビニルモノマー :0.1~12.0mol%、アニオン性ビニルモノマー :0.1~10.0mol%、(メタ)アリル基を有するモノマー :0.1~4.0mol%であることを特徴とする、前記<1>又は<2>に記載のポリアクリルアミド系製紙用添加剤、
<4>ポリマー構成単位のカチオン性ビニルモノマーが、3級アミノ基を有することを特徴とする、前記<1>~<3>いずれか一項に記載のポリアクリルアミド系製紙用添加剤、
<5>(メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、及び(メタ)アリル基を有するモノマーを重合することによって得られる両性ポリアクリルアミド共重合体(a)に下記(1)~(5)の条件となるようにジアルデヒド化合物(b)を反応させることを特徴とする、アルデヒド官能化したポリアクリルアミド(A’)を含むポリアクリルアミド系製紙用添加剤の製造方法、
(1)両性ポリアクリルアミド共重合体(a)のアミド基に対してジアルデヒド化合物(b)がモル比率で10~60%であること、
(2)pHが7.5~12.5であること、
(3)温度が1~60℃であること、
(4)両性ポリアクリルアミド共重合体(a)の反応前の濃度が0.5~11.0質量%であること、
(5)時間が20秒~4時間であること
<6>前記<5>に記載のアルデヒド官能化ポリアクリルアミド(A’)が、前記<1>~<4>のいずれか一項に記載のアルデヒド官能化ポリアクリルアミド(A)であること特徴とする、ポリアクリルアミド系製紙用添加剤の製造方法、
<7>ジアルデヒド化合物(b)が、グリオキサールであることを特徴とする、前記<5>に記載のポリアクリルアミド系製紙用添加剤の製造方法、
<8>パルプスラリーに、前記<1>~<4>いずれか一項に記載のポリアクリルアミド系製紙用添加剤をパルプ固形分に対して0.01~3質量%添加することを特徴とする、紙の製造方法。
That is, the present invention, which is a means for solving the above problems,
<1> A dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having, as a polymer constituent unit, a (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group A polyacrylamide-based papermaking additive comprising an aldehyde-functionalized polyacrylamide (A) characterized by satisfying all of the following (1) to (3):
(1) In the aldehyde-functionalized polyacrylamide (A), the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the dialdehyde compound, is 3 ~ 20 mol%
(2) Aldehyde-functionalized polyacrylamide (A) has a number average molecular weight of 500,000 to 4,000,000 (3) Aldehyde-functionalized polyacrylamide (A) has a pH of 3.5 to 8.5 and an ionization degree of 0 meq / g <2> The addition for polyacrylamide papermaking as described in <1> above, wherein the molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) having an isoelectric point is 2.0 to 8.0 Agent,
<3> The proportion of polymer structural units is (meth) acrylamide: 74.0 to 99.7 mol%, cationic vinyl monomer: 0.1 to 12.0 mol%, anionic vinyl monomer: 0.1 to 10.0 mol %, A monomer having a (meth) allyl group: 0.1 to 4.0 mol%, an additive for polyacrylamide papermaking according to the above <1> or <2>,
<4> The additive for polyacrylamide papermaking according to any one of <1> to <3>, wherein the cationic vinyl monomer of the polymer structural unit has a tertiary amino group,
<5> Amphoteric polyacrylamide copolymer (a) obtained by polymerizing (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group includes the following (1) to ( 5) a method for producing a polyacrylamide-based papermaking additive comprising aldehyde-functionalized polyacrylamide (A ′), wherein the dialdehyde compound (b) is reacted so as to satisfy the conditions of 5)
(1) The dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
(2) the pH is 7.5 to 12.5,
(3) The temperature is 1 to 60 ° C.
(4) The concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass,
(5) The time is 20 seconds to 4 hours. <6> The aldehyde-functionalized polyacrylamide (A ′) according to <5> is any one of the above <1> to <4>. A method for producing a polyacrylamide-based additive for papermaking, which is an aldehyde-functionalized polyacrylamide (A),
<7> The method for producing a polyacrylamide-based paper additive according to <5>, wherein the dialdehyde compound (b) is glyoxal,
<8> The polyacrylamide papermaking additive according to any one of <1> to <4> is added to the pulp slurry in an amount of 0.01 to 3% by mass based on the pulp solid content. , Paper manufacturing method.
 本発明によれば、紙力増強効果が優れ、濾水性が良好なアルデヒド官能化ポリアクリルアミドを含むポリアクリルアミド系製紙用添加剤とその製造方法、およびその製紙用添加剤を用いた紙の製造方法を提供することができる。 According to the present invention, a polyacrylamide papermaking additive containing an aldehyde-functionalized polyacrylamide having an excellent paper strength enhancing effect and good drainage, a method for producing the same, and a method for producing paper using the papermaking additive Can be provided.
 本発明のアルデヒド官能化ポリアクリルアミド(A)を含むポリアクリルアミド系製紙用添加剤は、(メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、および(メタ)アリル基を有するモノマーをポリマー構成単位として有する両性ポリアクリルアミド共重合体(a)のジアルデヒド化合物付加物である。
 本発明のアルデヒド官能化ポリアクリルアミド(A’)を含むポリアクリルアミド系製紙用添加剤の製造方法は、(メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、及び(メタ)アリル基を有するモノマーを重合することによって得られる両性ポリアクリルアミド共重合体(a)に下記(1)~(5)の条件となるようにジアルデヒド化合物(b)を反応させることを特徴とするものである。
(1)両性ポリアクリルアミド共重合体(a)のアミド基に対してジアルデヒド化合物(b)がモル比率で10~60%であること、
(2)pHが7.5~12.5であること、
(3)温度が1~60℃であること、
(4)両性ポリアクリルアミド共重合体(a)の反応前の濃度が0.5~11.0質量%であること、
(5)時間が20秒~4時間であること
The polyacrylamide papermaking additive containing the aldehyde-functionalized polyacrylamide (A) of the present invention comprises (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group as a polymer constituent unit. Is a dialdehyde compound adduct of the amphoteric polyacrylamide copolymer (a).
The method for producing a polyacrylamide-based paper additive containing the aldehyde-functionalized polyacrylamide (A ′) of the present invention comprises (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group The amphoteric polyacrylamide copolymer (a) obtained by polymerizing is reacted with the dialdehyde compound (b) so as to satisfy the following conditions (1) to (5).
(1) The dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
(2) the pH is 7.5 to 12.5,
(3) The temperature is 1 to 60 ° C.
(4) The concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass,
(5) The time is 20 seconds to 4 hours
 本発明における(メタ)アクリルアミドは、アクリルアミド又はメタクリルアミドである。 (Meth) acrylamide in the present invention is acrylamide or methacrylamide.
 本発明におけるカチオン性ビニルモノマーとしては、1級アミノ基、2級アミノ基、3級アミノ基、又は4級アンモニウム塩類を有するビニルモノマーを挙げることができる。これらのカチオン性ビニルモノマーは1種単独で用いられていても良いし、2種以上を併用されていても良い。両性ポリアクリルアミド共重合体(a)を構成するカチオン性ビニルモノマーに、3級アミノ基を有するビニルモノマーを用いると、製紙用添加剤としたときにパルプへの定着効果が高まりやすいため好ましい。 Examples of the cationic vinyl monomer in the present invention include a vinyl monomer having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium salt. These cationic vinyl monomers may be used individually by 1 type, and may use 2 or more types together. It is preferable to use a vinyl monomer having a tertiary amino group as the cationic vinyl monomer constituting the amphoteric polyacrylamide copolymer (a) because the effect of fixing to pulp is likely to increase when used as a papermaking additive.
 3級アミノ基を有するビニルモノマーとしては、例えばジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ジメチルアミノプロピル(メタ)アクリレート、及びジエチルアミノプロピル(メタ)アクリレート等のジアルキルアミノアルキル(メタ)アクリレート類;ジメチルアミノプロピル(メタ)アクリルアミド、及びジエチルアミノプロピル(メタ)アクリルアミド等のジアルキルアミノアルキル(メタ)アクリルアミド類;前記3級アミノ基を有するビニルモノマーの塩酸塩、及び硫酸塩等の無機酸塩類、並びに前記3級アミノ基を有するビニルモノマーのギ酸塩、及び酢酸塩等の有機酸塩類が挙げられる。これらの中でも、ジアルキルアミノアルキル(メタ)アクリレート類が好ましい。 Examples of vinyl monomers having a tertiary amino group include dialkylaminoalkyl (meth) such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate. Acrylates; Dialkylaminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide; Hydrochloric acid salts of vinyl monomers having the tertiary amino group, and inorganic acid salts such as sulfates And organic acid salts such as formate and acetate of vinyl monomers having a tertiary amino group. Among these, dialkylaminoalkyl (meth) acrylates are preferable.
 また、4級アンモニウム塩類を有するビニルモノマーとしては、前記3級アミノ基を有するビニルモノマーと4級化剤との反応によって得られるビニルモノマー、およびジアリルジメチルアンモニウムクロライド等の4級アンモニウム塩類を有するビニルモノマーが挙げられる。前記4級化剤としては、メチルクロライド、メチルブロマイド等のアルキルハライド;ベンジルクロライド、ベンジルブロマイド等のアラルキルハライド;ジメチル硫酸、ジエチル硫酸、エピクロロヒドリン、3-クロロ-2-ヒドロキシプロピルトリメチルアンモニウムクロライド、及びグリシジルトリアルキルアンモニウムクロライド等が挙げられる。これらの3級アミノ基、又は4級アンモニウム塩類を有するビニルモノマーは1種単独で用いられていても良いし、2種以上を併用されていても良い。 The vinyl monomer having a quaternary ammonium salt includes a vinyl monomer obtained by the reaction of the vinyl monomer having a tertiary amino group and a quaternizing agent, and a vinyl having a quaternary ammonium salt such as diallyldimethylammonium chloride. Monomer. Examples of the quaternizing agent include alkyl halides such as methyl chloride and methyl bromide; aralkyl halides such as benzyl chloride and benzyl bromide; dimethyl sulfate, diethyl sulfate, epichlorohydrin, 3-chloro-2-hydroxypropyltrimethylammonium chloride. And glycidyltrialkylammonium chloride. These tertiary amino groups or vinyl monomers having quaternary ammonium salts may be used alone or in combination of two or more.
 本発明におけるアニオン性ビニルモノマーとしては、アクリル酸、メタクリル酸、2-(メタ)アクリルアミド-N-グリコール酸、N-アクリロイルグリシン等の不飽和モノカルボン酸;マレイン酸、フマル酸、イタコン酸、シトラコン酸等の不飽和ジカルボン酸;アコニット酸、3-ブテン-1,2,3-トリカルボン酸等の不飽和トリカルボン酸;1-ペンテン-1,1,4,4-テトラカルボン酸、4-ペンテン-1,2,3,4-テトラカルボン酸、3-ヘキセン-1,1,6,6-テトラカルボン酸等の不飽和テトラカルボン酸;ビニルスルホン酸、スチレンスルホン酸、2-アクリルアミド-2-メチルプロパンスルホン酸等の不飽和スルホン酸;ビニルホスホン酸、α-フェニルビニルホスホン酸等の不飽和ホスホン酸;前記のアニオン性ビニルモノマーのナトリウム、カリウム塩等のアルカリ金属塩類またはアンモニウム塩等が挙げられる。これらのアニオン性ビニルモノマーは1種単独で用いられていても良いし、2種以上を併用されていても良い。 Examples of the anionic vinyl monomer in the present invention include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 2- (meth) acrylamide-N-glycolic acid and N-acryloylglycine; maleic acid, fumaric acid, itaconic acid, citracone Unsaturated dicarboxylic acids such as acids; unsaturated tricarboxylic acids such as aconitic acid and 3-butene-1,2,3-tricarboxylic acid; 1-pentene-1,1,4,4-tetracarboxylic acid and 4-pentene- Unsaturated tetracarboxylic acids such as 1,2,3,4-tetracarboxylic acid and 3-hexene-1,1,6,6-tetracarboxylic acid; vinyl sulfonic acid, styrene sulfonic acid, 2-acrylamido-2-methyl Unsaturated sulfonic acids such as propanesulfonic acid; unsaturated phosphonic acids such as vinylphosphonic acid and α-phenylvinylphosphonic acid; Sodium serial anionic vinyl monomers include alkali metal salts or ammonium salts or potassium salts. These anionic vinyl monomers may be used individually by 1 type, and may use 2 or more types together.
 上記のアニオン性ビニルモノマーの中でも、紙力増強向上効果の点で不飽和モノカルボン酸、不飽和ジカルボン酸が適しており、具体的には、アクリル酸、2-アクリルアミド-N-グリコール酸、イタコン酸及びその塩類が特に好ましい。 Among the above anionic vinyl monomers, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are suitable from the viewpoint of improving paper strength, and specifically include acrylic acid, 2-acrylamide-N-glycolic acid, itacone. Acids and their salts are particularly preferred.
 本発明における(メタ)アリル基を有するモノマーとしては、(メタ)アリル基を有しているモノマーであればよく、(メタ)アリル基以外にアニオン性基やカチオン性基などの他の官能基を有していたとしても(メタ)アリル基を有しているモノマーとして分類する。具体例としては、(メタ)アリルスルホン酸またはその塩、(メタ)アリルアルコール、(メタ)アリルアミン、(メタ)アリルアンモニウム塩等が挙げられる。中でも、(メタ)アリルスルホン酸またはその塩、ジメチルヒドロキシエチルメタリルアンモニウムクロライドが好ましい。 The monomer having a (meth) allyl group in the present invention may be a monomer having a (meth) allyl group, and other functional groups such as an anionic group and a cationic group in addition to the (meth) allyl group. Even if it has, it is classified as a monomer having a (meth) allyl group. Specific examples include (meth) allylsulfonic acid or a salt thereof, (meth) allyl alcohol, (meth) allylamine, (meth) allyl ammonium salt, and the like. Of these, (meth) allylsulfonic acid or a salt thereof and dimethylhydroxyethyl methallyl ammonium chloride are preferable.
 本発明の両性ポリアクリルアミド共重合体(a)におけるモノマーとして、本発明の効果を阻害しない範囲において、その他のモノマーが用いられていても構わない。ここで本発明の効果を阻害しない範囲とは、両性ポリアクリルアミド共重合体(a)における(メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、(メタ)アリル基を有するモノマーの合計100mol%に対して、更にその他モノマー0~3.0mol%が好ましい。 As the monomer in the amphoteric polyacrylamide copolymer (a) of the present invention, other monomers may be used as long as the effects of the present invention are not impaired. Here, the range that does not inhibit the effect of the present invention is a total of 100 mol% of (meth) acrylamide, cationic vinyl monomer, anionic vinyl monomer, and monomer having a (meth) allyl group in the amphoteric polyacrylamide copolymer (a). In contrast, 0 to 3.0 mol% of other monomers are more preferable.
 その他のモノマー成分としては、例えば、ノニオン性ビニルモノマー、架橋剤、連鎖移動剤を挙げることができる。ノニオン性ビニルモノマーとしては、例えば、(メタ)アクリル酸エステル、(メタ)アクリロニトリル、スチレン、スチレン誘導体、酢酸ビニル、プロピオン酸ビニル、及びメチルビニルエーテル等を挙げることができる。これらは1種単独で用いられていても良いし、2種以上を併用されていても良い。 Examples of other monomer components include nonionic vinyl monomers, crosslinking agents, and chain transfer agents. Examples of nonionic vinyl monomers include (meth) acrylic acid esters, (meth) acrylonitrile, styrene, styrene derivatives, vinyl acetate, vinyl propionate, and methyl vinyl ether. These may be used individually by 1 type and may use 2 or more types together.
 架橋剤としては、例えば、N-メチル(メタ)アクリルアミド、N-エチル(メタ)アクリルアミド、N,N-ジメチル(メタ)アクリルアミド、N,N-ジエチル(メタ)アクリルアミド、N-イソプロピル(メタ)アクリルアミド等のN置換(メタ)アクリルアミド;エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、等のジ(メタ)アクリレート類;N,N’-メチレンビス(メタ)アクリルアミド、エチレンビス(メタ)アクリルアミド、ヘキサメチレンビス(メタ)アクリルアミド等のビス(メタ)アクリルアミド類;トリアクリルホルマール、トリアリルイソシアヌレート、N,N-ジアリルアクリルアミド、N,N-ジアリルメタクリルアミド、トリアリルアミン、テトラメチロールメタンテトラアクリレート等の3~4官能性ビニルモノマーのような多官能性モノマー等を挙げることができる。また、水溶性アジリジニル化合物、水溶性多官能エポキシ化合物、シリコン系化合物等も挙げることができる。これらは1種単独で用いられていても良いし、2種以上を併用されていても良い。これらの中でもN 置換(メタ)アクリルアミドが好ましい。 Examples of the crosslinking agent include N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide. N-substituted (meth) acrylamides such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and other di (meth) acrylates; Bis (meth) acrylamides such as N, N′-methylenebis (meth) acrylamide, ethylenebis (meth) acrylamide, hexamethylenebis (meth) acrylamide; triacryl formal, triallyl isocyanurate, N, N Diallyl acrylamide, N, N-diallyl methacrylamide, triallylamine, mention may be made of polyfunctional monomers such as 3-4 functional vinyl monomers such as tetramethylolmethane tetraacrylate. Moreover, a water-soluble aziridinyl compound, a water-soluble polyfunctional epoxy compound, a silicon compound, etc. can be mentioned. These may be used individually by 1 type and may use 2 or more types together. Among these, N-substituted (meth) acrylamide is preferable.
 連鎖移動剤としては、アルキルメルカプタン類、2,4-ジフェニル-4-メチル-1-ペンテン等公知の連鎖移動剤が挙げられる。これらは1種単独で用いられていても良いし、2種以上を併用されていても良い。 Examples of the chain transfer agent include known chain transfer agents such as alkyl mercaptans and 2,4-diphenyl-4-methyl-1-pentene. These may be used individually by 1 type and may use 2 or more types together.
 両性ポリアクリルアミド共重合体(a)におけるモノマーの割合は、イオンバランスや、後のアミド基に対するジアルデヒド化合物の反応を考慮すると、好ましくは(メタ)アクリルアミド74.0~99.7mol%、カチオン性ビニルモノマー0.1~12.0mol%、アニオン性ビニルモノマー0.1~10.0mol%、(メタ)アリル基を有するモノマー0.1~4.0mol%の範囲であり、より好ましくは(メタ)アクリルアミド83.0~99.7mol%、3級アミノ基を有するカチオン性ビニルモノマー0.1~8.0mol%、アニオン性ビニルモノマー0.1~7.0mol%および(メタ)アリル基を有するモノマー0.1~2.0mol%の範囲である。 The proportion of the monomer in the amphoteric polyacrylamide copolymer (a) is preferably 74.0 to 99.7 mol% of (meth) acrylamide, considering the ion balance and the reaction of the dialdehyde compound with respect to the amide group. The range is 0.1 to 12.0 mol% of vinyl monomer, 0.1 to 10.0 mol% of anionic vinyl monomer, and 0.1 to 4.0 mol% of monomer having (meth) allyl group, more preferably (meta ) 83.0 to 99.7 mol% of acrylamide, 0.1 to 8.0 mol% of cationic vinyl monomer having tertiary amino group, 0.1 to 7.0 mol% of anionic vinyl monomer, and (meth) allyl group The monomer is in the range of 0.1 to 2.0 mol%.
 両性ポリアクリルアミド共重合体(a)は、特にその製造方法に関して限定されず、公知の重合方法により得ることができる。本発明の製紙用添加剤としてパルプへの定着性が向上するため、モノマー成分を分割あるいは滴下により重合することが好ましい。 The amphoteric polyacrylamide copolymer (a) is not particularly limited with respect to its production method, and can be obtained by a known polymerization method. In order to improve the fixability to pulp as the papermaking additive of the present invention, it is preferable to polymerize the monomer component by dividing or dropping.
 両性ポリアクリルアミド共重合体(a)の数平均分子量、分子量分布に関しては特に制限はないが、ジアルデヒド化合物と反応させる際に分子量が上昇し、適切な数平均分子量、分子量分布の範囲を超えるため、数平均分子量5万~300万、分子量分布2.0~7.0が好ましい。 There are no particular restrictions on the number average molecular weight and molecular weight distribution of the amphoteric polyacrylamide copolymer (a), but the molecular weight increases upon reaction with the dialdehyde compound and exceeds the appropriate number average molecular weight and molecular weight distribution range. A number average molecular weight of 50,000 to 3,000,000 and a molecular weight distribution of 2.0 to 7.0 are preferred.
 本発明のアルデヒド官能化ポリアクリルアミド(A)は、その製造方法に関して限定されるものではない。例えば、両性ポリアクリルアミド共重合体(a)に下記(1)~(5)の条件となるようにジアルデヒド化合物(b)を反応させることで得られるアルデヒド官能化ポリアクリルアミド(A’)とすることができる。
(1)両性ポリアクリルアミド共重合体(a)のアミド基に対してジアルデヒド化合物(b)がモル比率で10~60%であること、
(2)pHが7.5~12.5であること、
(3)温度が1~60℃であること、
(4)両性ポリアクリルアミド共重合体(a)の反応前の濃度が0.5~11.0質量%であること、
(5)時間が20秒~4時間であること
The aldehyde functionalized polyacrylamide (A) of the present invention is not limited with respect to its production method. For example, an aldehyde-functionalized polyacrylamide (A ′) obtained by reacting an amphoteric polyacrylamide copolymer (a) with a dialdehyde compound (b) so as to satisfy the following conditions (1) to (5): be able to.
(1) The dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
(2) the pH is 7.5 to 12.5,
(3) The temperature is 1 to 60 ° C.
(4) The concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass,
(5) The time is 20 seconds to 4 hours
 両性ポリアクリルアミド共重合体(a)と反応させるジアルデヒド化合物(b)は、グリオキサール、グルタルアルデヒド、2,5-ジホルミルフラン、2-ヒドロキシアジパルデヒド、スクシンアルデヒド、及びその組み合わせからなる群から選択される。反応性や濾水効果の観点から、グリオキサールが最も好ましい。 The dialdehyde compound (b) to be reacted with the amphoteric polyacrylamide copolymer (a) is a group consisting of glyoxal, glutaraldehyde, 2,5-diformylfuran, 2-hydroxyadipaldehyde, succinaldehyde, and combinations thereof Selected from. Glyoxal is most preferable from the viewpoint of reactivity and drainage effect.
 両性ポリアクリルアミド共重合体(a)と反応させるジアルデヒド化合物(b)の使用量は、本発明の製造方法においては、反応効率と効果の観点から、両性ポリアクリルアミド共重合体(a)のアミド基に対してモル比率で10~60%混合して反応させることが好ましい(製造条件1)。このような反応を行うことで、アルデヒド官能化ポリアクリルアミド(A)中の、アミド基及びアルデヒド化合物が付加しているアミド基に対して、ジアルデヒド化合物が付加しているアミド基の割合であるアミド反応率が3~20モル%となりやすくなる。 In the production method of the present invention, the amount of the dialdehyde compound (b) to be reacted with the amphoteric polyacrylamide copolymer (a) is the amide of the amphoteric polyacrylamide copolymer (a) from the viewpoint of reaction efficiency and effect. It is preferable to react by mixing 10 to 60% in molar ratio with respect to the group (production condition 1). By performing such a reaction, it is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the aldehyde compound in the aldehyde-functionalized polyacrylamide (A). The amide reaction rate tends to be 3 to 20 mol%.
 両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)を反応させる工程は、必要により塩基を添加して、反応溶液のpHを7.5~12.5に調整すると、両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)との反応が促進されるため好ましい(製造条件2)。 In the step of reacting the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b), if the base is added as necessary to adjust the pH of the reaction solution to 7.5 to 12.5, the amphoteric polyacrylamide copolymer is reacted. This is preferable because the reaction between the polymer (a) and the dialdehyde compound (b) is promoted (production condition 2).
 両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)を反応させる際の温度が1~60℃の範囲内であると、両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)の反応が促進されるため好ましい。(製造条件3)。 When the temperature at which the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) are reacted is in the range of 1 to 60 ° C., the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) This is preferable because the reaction of (Production conditions 3).
 両性ポリアクリルアミド共重合体(a)の反応前の濃度が、0.5~11.0質量%の範囲内であると、反応溶液の増粘を抑制しつつ、所定の分子量、固有粘度、アルデヒド官能化アミド量に調整しやすいため好ましい。(製造条件4)。 When the concentration of the amphoteric polyacrylamide copolymer (a) is within the range of 0.5 to 11.0% by mass, the predetermined molecular weight, intrinsic viscosity, aldehyde is suppressed while suppressing the thickening of the reaction solution. This is preferable because it is easy to adjust the amount of functionalized amide. (Production condition 4).
 両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)の反応時間は、20秒~4時間の範囲内であることが、ポリアクリルアミドとジアルデヒド化合物の反応が促進されるため好ましい。(製造条件5)。 The reaction time of the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) is preferably in the range of 20 seconds to 4 hours, since the reaction between the polyacrylamide and the dialdehyde compound is promoted. (Production conditions 5).
 本発明のアルデヒド官能化ポリアクリルアミド(A)を含むポリアクリルアミド系製紙用添加剤は、下記(1)~(3)全てを満足する。
(1)アルデヒド官能化ポリアクリルアミド(A)中の、ジアルデヒド付加前の(メタ)アクリルアミド構成単位のアミド基に対して、ジアルデヒド化合物が付加しているアミド基の割合であるアミド反応率が3~20モル%
(2)アルデヒド官能化ポリアクリルアミド(A)の数平均分子量が50万~400万
(3)pH3.5~8.5の間でイオン化度が0meq/gになる等電点が存在する
The polyacrylamide papermaking additive containing the aldehyde-functionalized polyacrylamide (A) of the present invention satisfies all of the following (1) to (3).
(1) In the aldehyde functionalized polyacrylamide (A), the amide reaction rate, which is the ratio of the amide group added by the dialdehyde compound to the amide group of the (meth) acrylamide structural unit before the dialdehyde addition, 3 to 20 mol%
(2) There is an isoelectric point where the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) is 500,000 to 4,000,000 (3) pH is 3.5 to 8.5 and the degree of ionization is 0 meq / g.
 アルデヒド官能化ポリアクリルアミド(A)中の、アミド基及びアルデヒド化合物が付加しているアミド基に対して、ジアルデヒド化合物が付加しているアミド基の割合であるアミド反応率は3~20モル%である必要があり(ポリアクリルアミド(A)条件1)、より好ましくは3~15モル%である。本発明でいうアミド反応率は、13C-NMR測定により、179~181ppm(アルデヒド官能化アミドのピーク)と182ppm~185ppm(アミド基のピーク)の積分比率から算出したものである。アミド反応率が3%未満の場合はポリマー中のアルデヒド基量が不十分であり、20%より高い場合は反応の過度な進行により、ポリマー同士がジアルデヒド化合物により架橋反応を起こし、やはりポリマー中のアルデヒド基量が不十分である。このため、アルデヒド基によるセルロース間の共有結合を形成できず、紙力向上効果あるいは濾水性に不利である。 In the aldehyde-functionalized polyacrylamide (A), the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the aldehyde compound, is 3 to 20 mol%. (Polyacrylamide (A) condition 1), more preferably 3 to 15 mol%. The amide reaction rate referred to in the present invention is calculated from an integration ratio of 179 to 181 ppm (aldehyde functionalized amide peak) and 182 ppm to 185 ppm (amide group peak) by 13 C-NMR measurement. When the amide reaction rate is less than 3%, the amount of aldehyde groups in the polymer is insufficient, and when it is higher than 20%, the polymers cause a cross-linking reaction with the dialdehyde compound due to excessive progress of the reaction. Insufficient amount of aldehyde groups. For this reason, the covalent bond between the cellulose by an aldehyde group cannot be formed, but it is disadvantageous for the paper strength improvement effect or drainage.
 アルデヒド官能化ポリアクリルアミド(A)の数平均分子量は、50万~400万である必要があり(ポリアクリルアミド(A)条件2)、より好ましくは50万~300万である。数平均分子量が50万未満であると、パルプへの定着に対する寄与が小さい低分子量のポリマー成分の含まれる割合が多くなるので定着効果に劣る。また400万を超えると、パルプを凝集させ紙の地合いの悪化を引き起こし、ひいては紙力増強効果に不利となる。
本発明における数平均分子量は、GPC に多角度光散乱検出器を接続したGPC-MALS法により得られるものをいう。
The number average molecular weight of the aldehyde-functionalized polyacrylamide (A) needs to be 500,000 to 4,000,000 (polyacrylamide (A) condition 2), more preferably 500,000 to 3,000,000. When the number average molecular weight is less than 500,000, the proportion of the low molecular weight polymer component that has a small contribution to fixing to the pulp is increased, resulting in poor fixing effect. On the other hand, if it exceeds 4 million, the pulp is agglomerated to cause deterioration of the paper texture, which is disadvantageous for the paper strength enhancing effect.
The number average molecular weight in the present invention refers to that obtained by GPC-MALS method in which a multi-angle light scattering detector is connected to GPC.
 アルデヒド官能化ポリアクリルアミド(A)はpH3.5~8.5の間でイオン化度が0meq/gになる等電点を示す必要がある(ポリアクリルアミド(A)条件3)。等電点がpH3.5~8.5の間にあると、抄紙系においてポリマー同士がカチオンとアニオンのイオン相互作用によりコンプレックスを形成し、パルプへの定着効果が高まるため、紙力増強効果あるいは濾水性に有利である。本発明でいう等電点とは、PCD電位計により測定するものであるが、同様の原理の測定ができるのであれば前記装置に限定はしない。 Aldehyde functionalized polyacrylamide (A) needs to exhibit an isoelectric point where the ionization degree is 0 meq / g between pH 3.5 and 8.5 (polyacrylamide (A) condition 3). When the isoelectric point is between pH 3.5 and 8.5, the polymer forms a complex by the ionic interaction of the cation and anion in the papermaking system, and the fixing effect to the pulp is enhanced. It is advantageous for drainage. The isoelectric point as used in the present invention is measured by a PCD electrometer, but is not limited to the above apparatus as long as the same principle can be measured.
 アルデヒド官能化ポリアクリルアミド(A)の分子量分布は、好ましくは2.0~8.0、より好ましくは2.0~7.0である。分子量分布は数平均分子量(Mn)に対する重量平均分子量(Mw)の比(Mw/Mn)であり、8.0を超える場合は過度なパルプの凝集を引き起こしやすい。適切な分子量分布を有するアルデヒド官能化ポリアクリルアミド(A)は、過度なパルプの凝集による紙の地合いの悪化を引き起こしにくく、紙力増強効果に有利である。分子量分布を求めるために必要となる本発明における重量平均分子量は、GPC に多角度光散乱検出器を接続したGPC-MALLS法により得られるものをいう。 The molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) is preferably 2.0 to 8.0, more preferably 2.0 to 7.0. The molecular weight distribution is the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and if it exceeds 8.0, it tends to cause excessive pulp aggregation. The aldehyde-functionalized polyacrylamide (A) having an appropriate molecular weight distribution is less likely to cause deterioration of the paper texture due to excessive pulp agglomeration, and is advantageous for the paper strength enhancing effect. The weight average molecular weight in the present invention required for obtaining the molecular weight distribution refers to that obtained by GPC-MALLS method in which a multi-angle light scattering detector is connected to GPC.
 本発明のポリアクリルアミド系製紙用添加剤は、アルデヒド官能化ポリアクリルアミド(A)が主要成分であり、全固形分当りに占める割合が60質量%以上であることが好ましく、更に好ましくは80質量%であることが好ましい。
 また、本発明のポリアクリルアミド系製紙用添加剤は、未反応のジアルデヒド化合物を含んでいてもよい。その場合、酸を添加して、pH2.5~4.5に調整してジアルデヒド化合物との反応を停止して製紙用添加剤とすることが好ましいが、反応後直ちに用いる場合には、pHを下げずにそのまま反応溶液をパルプスラリーに添加することもできる。pH調整に用いられる塩基としては、水酸化ナトリウム、水酸化カリウム、アンモニア等、酸としては、硫酸、塩酸、酢酸等が挙げられる。また、防腐剤、消泡剤等を含有していてもよい。
In the polyacrylamide papermaking additive of the present invention, the aldehyde-functionalized polyacrylamide (A) is a main component, and the proportion of the polyacrylamide based paper is preferably 60% by mass or more, more preferably 80% by mass based on the total solid content. It is preferable that
Further, the polyacrylamide papermaking additive of the present invention may contain an unreacted dialdehyde compound. In that case, it is preferable to add an acid to adjust the pH to 2.5 to 4.5 to stop the reaction with the dialdehyde compound to make an additive for papermaking. The reaction solution can be added to the pulp slurry as it is without lowering. Examples of the base used for pH adjustment include sodium hydroxide, potassium hydroxide, ammonia and the like, and examples of the acid include sulfuric acid, hydrochloric acid, acetic acid and the like. Moreover, antiseptic | preservative, an antifoamer, etc. may be contained.
 好ましくは、本発明のポリアクリルアミド系製紙用添加剤をパルプスラリーに添加(以下、「内添」と略することがある)して用いることが好ましい。 Preferably, the polyacrylamide papermaking additive of the present invention is preferably added to the pulp slurry (hereinafter sometimes abbreviated as “internal addition”).
 パルプスラリーはパルプを水で希釈してスラリー状にしたものである。パルプとしては、クラフトパルプ及びサルファイトパルプ等の晒、又は未晒化学パルプ;砕木パルプ、機械パルプ、サーモメカニカルパルプ等の晒、又は未晒高収率パルプ;新聞古紙、雑誌古紙、段ボール古紙及び脱墨古紙等の古紙パルプが挙げられる。 Pulp slurry is a slurry of pulp diluted with water. As pulp, bleached or unbleached chemical pulp such as kraft pulp and sulfite pulp; bleached or unbleached pulp such as groundwood pulp, mechanical pulp, thermomechanical pulp, etc .; waste newspaper, magazine waste paper, corrugated paper Examples include waste paper pulp such as deinked waste paper.
 本発明のポリアクリルアミド系製紙用添加剤は、パルプ固形分当たり通常0.01~3.0質量%、好ましくは0.05~2.5質量% 、さらに好ましくは0.1~2.0質量%を添加して使用する。硫酸バンドやポリ塩化アニミニウム(PAC)などのアルミニウム化合物を添加する場合には、パルプ固形分当たり0.1~1.0質量%を添加することが好ましい。また、ポリアクリルアミド系製紙用添加剤をパルプスラリーに添加する方法としては、アルミニウム化合物を全く用いずにポリアクリルアミド系製紙用添加剤を添加する方法、アルミニウム化合物を添加した後にポリアクリルアミド系製紙用添加剤を添加する方法、ポリアクリルアミド系製紙用添加剤を添加した後にアルミニウム化合物を添加する方法、アルミニウム化合物とポリアクリルアミド系製紙用添加剤を同時に添加する方法などが挙げられ、いずれの方法を用いてもよい。 The polyacrylamide paper additive of the present invention is usually 0.01 to 3.0% by mass, preferably 0.05 to 2.5% by mass, more preferably 0.1 to 2.0% by mass per pulp solid content. % Is used. When an aluminum compound such as a sulfuric acid band or polyaninium chloride (PAC) is added, it is preferable to add 0.1 to 1.0% by mass per pulp solid content. Also, as a method of adding a polyacrylamide paper additive to a pulp slurry, a method of adding a polyacrylamide paper additive without using any aluminum compound, a polyacrylamide paper additive after adding an aluminum compound A method of adding an agent, a method of adding an aluminum compound after adding a polyacrylamide-based papermaking additive, a method of simultaneously adding an aluminum compound and a polyacrylamide-based papermaking additive, and the like. Also good.
 本発明の紙の製造にあたっては、硫酸アルミニウムを用いる酸性系、または、硫酸アルミニウムを全く用いないかあるいは少量用いる中性系、のいずれのパルプスラリーを用いても良い。また、パルプスラリーに対して、酸性ロジン系サイズ剤、中性ロジン系サイズ剤、アルキルケテンダイマー系サイズ剤、アルケニルもしくはアルキルコハク酸無水物系サイズ剤などを添加しても良い。これらサイズ剤の添加方法としては、パルプスラリーにサイズ剤を添加した後に、ポリアクリルアミド系製紙用添加剤を添加する方法、ポリアクリルアミド系製紙用添加剤を添加した後に、サイズ剤を添加する方法、サイズ剤にポリアクリルアミド系製紙用添加剤を希釈して予め混合した後に、添加する方法などが挙げられる。また、他に、パルプスラリーにクレー、カオリン、炭酸カルシウム、硫酸バリウム、酸化チタン等の填料;前記サイズ剤以外のサイズ剤、サイズ定着剤、本発明以外の内添紙力剤(乾燥紙力増強剤、湿潤紙力増強剤)、消泡剤、pH調整剤、染料、蛍光増白剤、歩留り向上剤等を適宜含有させてもよい。また、製造される紙は、通常、坪量が10~400g/m程度である。 In the production of the paper of the present invention, either an acidic system using aluminum sulfate or a neutral system using no or a small amount of aluminum sulfate may be used. Further, an acidic rosin sizing agent, a neutral rosin sizing agent, an alkyl ketene dimer sizing agent, an alkenyl or alkyl succinic anhydride sizing agent, and the like may be added to the pulp slurry. As a method for adding these sizing agents, after adding a sizing agent to a pulp slurry, a method of adding a polyacrylamide papermaking additive, a method of adding a sizing agent after adding a polyacrylamide papermaking additive, Examples include a method of adding a polyacrylamide paper additive to a sizing agent after diluting and premixing. Besides, fillers such as clay, kaolin, calcium carbonate, barium sulfate, titanium oxide, etc. in pulp slurry; sizing agents other than the above sizing agents, size fixing agents, internal paper strength agents other than the present invention (increasing dry paper strength) Agent, wet paper strength enhancer), antifoaming agent, pH adjusting agent, dye, fluorescent whitening agent, yield improving agent, and the like may be appropriately contained. The paper to be produced usually has a basis weight of about 10 to 400 g / m 2 .
 更にサイズプレス、ゲートロールコーター、ビルブレードコーター、キャレンダー等で、澱粉、ポリビニルアルコール、アクリルアミド系ポリマー等の表面紙力増強剤、表面サイズ剤、染料、コーティングカラー、防滑剤等を必要に応じて塗布しても良い。 Furthermore, with a size press, gate roll coater, bill blade coater, calendar, etc., surface paper strength enhancer such as starch, polyvinyl alcohol, acrylamide polymer, surface sizing agent, dye, coating color, anti-slip agent, etc. as required It may be applied.
 上記のように本発明のポリアクリルアミド系製紙用添加剤をパルプスラリーに添加し、必要に応じて他の添加剤などを加えたパルプスラリーの抄紙pHは3.5~8.5であることが紙力増強効果の点から好ましく、6.5~8.5であることが更に好ましい。なお、本発明における抄紙pHとは、抄紙機にて脱水する直前のパルプスラリーのpHであり、抄紙機にて脱水する直前のパルプスラリーのpHは、一般的に実機ではインレットにおけるpHに相当する。 As described above, the papermaking pH of the pulp slurry obtained by adding the polyacrylamide papermaking additive of the present invention to the pulp slurry and adding other additives as necessary is 3.5 to 8.5. From the viewpoint of the paper strength enhancing effect, it is preferably 6.5 to 8.5. The papermaking pH in the present invention is the pH of the pulp slurry immediately before dewatering with the papermaking machine, and the pH of the pulp slurry immediately before dewatering with the papermaking machine generally corresponds to the pH at the inlet in the actual machine. .
 本発明のポリアクリルアミド系製紙用添加剤を用いて製造される紙としては、PPC用紙・感光紙原紙・感熱紙原紙のような情報用紙、アート紙、キャストコート紙、上質コート紙等のコート原紙、ティシュペーパー、タオルペーパー、ナプキン原紙のような衛生用紙、果樹袋原紙、クリーニングタグ原紙、化粧板原紙・壁紙原紙、印画紙用紙、積層板原紙、食品容器原紙のような加工原紙、重袋用両更クラフト紙・片艶クラフト紙などの包装用紙、電気絶縁紙、ライナー、中芯、紙管原紙、石膏ボード原紙、新聞用紙、紙器用板紙等を挙げることができ、いずれの抄紙工程においても、抄造された紙に有用な紙力増強効果を与えることができる。この中でも特に紙力が必要とされる紙や硫酸バンドの使用が制限される紙(情報用紙、コート原紙、紙器用板紙)に用いることが好ましい。なお、本発明でいう紙には板紙も含まれる。 The paper produced using the polyacrylamide papermaking additive of the present invention includes information paper such as PPC paper, photosensitive paper base paper, and thermal paper base paper, art base paper, cast coated paper, coated base paper such as high-quality coated paper, etc. Sanitary paper such as tissue paper, towel paper, napkin base paper, fruit bag base paper, cleaning tag base paper, decorative board base paper / wall paper base, photographic paper base, processed base paper such as base paper for food containers, heavy paper Examples include wrapping paper such as bifuran kraft paper and single gloss kraft paper, electrical insulation paper, liner, core, paper tube base paper, gypsum board base paper, newsprint paper, paperboard board, etc. Therefore, it is possible to give a useful paper strength enhancing effect to the paper made. Among these, it is particularly preferable to use paper that requires paper strength or paper that restricts the use of sulfuric acid bands (information paper, coated base paper, paperboard board). The paper referred to in the present invention includes paperboard.
 以下、実施例及び比較例を挙げて本発明をより具体的に説明するが、本発明はこれら各例に限定されるものではない。尚、各例中、部及び%は特記しない限りすべて質量基準である。各例の物性値は、以下の方法により測定した値である。 Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, all parts and% are based on mass unless otherwise specified. The physical property value of each example is a value measured by the following method.
 数平均分子量、重量平均分子量、分子量分布は、以下の測定条件でGPCに多角度光散乱検出器を接続したGPC-MALLS法により得た。
HPLC:Agilent1100シリーズ
カラム:昭和電工(株)製SHODEX SB806MHQ
溶離液:硝酸ナトリウムを含むリン酸緩衝液(pH3)
流速:1.0ml/分
検出器1:ワイアットテクノロジー社製 多角度光散乱検出器DAWN
検出器2:昭和電工(株)製 示唆屈折率検出器RI-101
The number average molecular weight, weight average molecular weight, and molecular weight distribution were obtained by GPC-MALLS method in which a multi-angle light scattering detector was connected to GPC under the following measurement conditions.
HPLC: Agilent 1100 series column: SHODEX SB806MHQ manufactured by Showa Denko K.K.
Eluent: phosphate buffer containing sodium nitrate (pH 3)
Flow rate: 1.0 ml / min Detector 1: Multi-angle light scattering detector DAWN manufactured by Wyatt Technology
Detector 2: Suggested refractive index detector RI-101 manufactured by Showa Denko KK
(両性ポリアクリルアミド共重合体(a)の製造)
製造例1
 撹拌機、温度計、還流冷却管、及び窒素ガス導入管を付した1リットル四つ口フラスコに、水260.00g、モノマー類(1)として、50%アクリルアミド水溶液126.81g、ジメチルアクリルアミド0.10g、30%硫酸水溶液15.60g、ジメチルアミノエチルメタクリレート15.72g、メタリルスルホン酸ナトリウム1.27gを仕込んだ。次いで、窒素ガス雰囲気下、60℃に昇温し、重合開始剤として過硫酸アンモニウム0.24gを加え、重合を開始させ反応温度を90℃まで昇温させた。その後、水180.00g、モノマー類(2)として、50%アクリルアミド水溶液132.49g、ジメチルアクリルアミド0.10g、アクリル酸5.40g、メタリルスルホン酸ナトリウム1.27gを加え、更に過硫酸アンモニウム0.48g を加え、25℃における推定粘度が3000mPa・sになった時点で、水290.00を投入し、固形分15.0%の両性ポリアクリルアミド共重合体(a-1)を得た。両性ポリアクリルアミド共重合体(a-1)を構成するモノマー単位の割合(mol%)と、数平均分子量、重量平均分子量、および分子量分布を測定した結果を表1に示す。
(Production of amphoteric polyacrylamide copolymer (a))
Production Example 1
In a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, 260.00 g of water and 126.81 g of 50% acrylamide aqueous solution as monomer (1) 10 g, 30% sulfuric acid aqueous solution 15.60 g, dimethylaminoethyl methacrylate 15.72 g, and sodium methallylsulfonate 1.27 g were charged. Next, the temperature was raised to 60 ° C. in a nitrogen gas atmosphere, 0.24 g of ammonium persulfate was added as a polymerization initiator, polymerization was started, and the reaction temperature was raised to 90 ° C. Thereafter, 180.00 g of water and 132.49 g of 50% acrylamide solution, 0.10 g of dimethylacrylamide, 5.40 g of acrylic acid, and 1.27 g of sodium methallyl sulfonate were added as monomers (2), and further, ammonium persulfate was added in an amount of 0.8. When 48 g was added and the estimated viscosity at 25 ° C. reached 3000 mPa · s, water 290.00 was added to obtain an amphoteric polyacrylamide copolymer (a-1) having a solid content of 15.0%. Table 1 shows the results of measuring the ratio (mol%) of the monomer units constituting the amphoteric polyacrylamide copolymer (a-1), the number average molecular weight, the weight average molecular weight, and the molecular weight distribution.
製造例2~14、比較用製造例1~6
 モノマー類(1)、モノマー類(2)の組成を表1に示すように変えたこと以外は、製造例1と同様に行い、固形分15.0%の両性ポリアクリルアミド共重合体(a-2)~(a-14)、(ra-1)~(ra-6)を得た。両性ポリアクリルアミド共重合体(a-2)~(a-14)、(ra-1)~(ra-6)を構成するモノマー単位の割合(mol%)と、数平均分子量、重量平均分子量、分子量分布を測定した結果を表1に示す。
Production Examples 2-14, Comparative Production Examples 1-6
The amphoteric polyacrylamide copolymer (a-) having a solid content of 15.0% was prepared in the same manner as in Production Example 1 except that the compositions of the monomers (1) and monomers (2) were changed as shown in Table 1. 2) to (a-14) and (ra-1) to (ra-6) were obtained. The ratio (mol%) of the monomer units constituting the amphoteric polyacrylamide copolymers (a-2) to (a-14) and (ra-1) to (ra-6), the number average molecular weight, the weight average molecular weight, The results of measuring the molecular weight distribution are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
 表1中の略号は以下の通りである。
AAm:アクリルアミド
DM :ジメチルアミノエチルメタクリレート
DMC:2‐(メタクリロイルオキシ)‐N, N, N‐トリメチルエタンアンモニウム・クロライド
DPA:N‐(2‐ジメチルアミノエチル)アクリルアミド
DADMAC:ジアリルジメチルアンモニウムクロライド
IA:イタコン酸
AGA:2‐アクリルアミド-N -グリコール酸
AAc:アクリル酸
SMAS:メタリルスルホン酸ナトリウム
HEMAC:ジメチルヒドロキシエチルメタリルアンモニウムクロライド
MET:メルカプトエタノール
MBAAm:メチレンビスアクリルアミド
DMAAm:ジメチルアクリルアミド
Mn:数平均分子量
Mw:重量平均分子量
Mw/Mn:分子量分布
Abbreviations in Table 1 are as follows.
AAm: Acrylamide DM: Dimethylaminoethyl methacrylate DMC: 2- (methacryloyloxy) -N, N, N-trimethylethaneammonium chloride DPA: N- (2-dimethylaminoethyl) acrylamide DADMAC: Diallyldimethylammonium chloride IA: Itacone Acid AGA: 2-acrylamide-N-glycolic acid AAc: acrylic acid SMAS: sodium methallylsulfonate HEMAC: dimethylhydroxyethylmethallyl ammonium chloride MET: mercaptoethanol MBAAm: methylenebisacrylamide DMAAm: dimethylacrylamide Mn: number average molecular weight Mw : Weight average molecular weight Mw / Mn: Molecular weight distribution
(両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)との反応)
実施例1
 200mLビーカーに製造例1において調製した両性ポリアクリルアミド共重合体(a-1)の15%水溶液12.69g、163.00gのイオン交換水、およびジアルデヒド化合物(b)としてグリオキサールの40%水溶液1.16g(共重合体(a)のアミド基に対して35mol%)を添加し、180rpmで攪拌しつつ35℃に昇温した。この際のpHは3.8であった。次いで、5.0%水酸化ナトリウム水溶液2.66gを添加してpH10.0に調整することで反応を開始させた。30分攪拌させた後、30%硫酸水溶液0.67gを加えてpH を3.0に調整し、反応を停止させた。両性ポリアクリルアミド共重合体(a)とジアルデヒド化合物(b)との反応条件を表2に示す。また、得られたポリアクリルアミド系製紙用添加剤(A-1)について、数平均分子量、重量平均分子量、分子量分布、アミド反応率を測定した結果を表3に示す。なお、アミド反応率はVARIAN製INOVA(400MHz)にて13C-NMR測定を行うことにより得た。
(Reaction of amphoteric polyacrylamide copolymer (a) with dialdehyde compound (b))
Example 1
In a 200 mL beaker, 12.69 g of 15% aqueous solution of amphoteric polyacrylamide copolymer (a-1) prepared in Production Example 1, 163.00 g of ion-exchanged water, and 40% aqueous solution of glyoxal as dialdehyde compound (b) 1 .16 g (35 mol% with respect to the amide group of copolymer (a)) was added, and the temperature was raised to 35 ° C. while stirring at 180 rpm. The pH at this time was 3.8. Subsequently, 2.66 g of 5.0% sodium hydroxide aqueous solution was added to adjust the pH to 10.0, thereby starting the reaction. After stirring for 30 minutes, 0.67 g of 30% aqueous sulfuric acid solution was added to adjust the pH to 3.0, and the reaction was stopped. Table 2 shows the reaction conditions between the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b). Table 3 shows the results of measuring the number average molecular weight, the weight average molecular weight, the molecular weight distribution, and the amide reaction rate for the obtained polyacrylamide-based paper additive (A-1). The amide reaction rate was obtained by performing 13 C-NMR measurement with INOVA (400 MHz) manufactured by VARIAN.
 ポリアクリルアミド系製紙用添加剤(A-1)のイオン化度は、PCD電位計PCD02(MUTEC社製)を用い、ポリマーの濃度を0.1重量%に調整し、酸塩基成分によりpHを調整した水溶液を測定した。その結果、0meq/gになる等電点はpH4.4であり、pH3.5~8.5の範囲で等電点が存在することを確認した。結果を表3に示す。 The degree of ionization of the polyacrylamide paper additive (A-1) was adjusted by adjusting the polymer concentration to 0.1% by weight using a PCD electrometer PCD02 (manufactured by MUTEC) and adjusting the pH with an acid-base component. The aqueous solution was measured. As a result, the isoelectric point at which 0 meq / g was reached was pH 4.4, and it was confirmed that an isoelectric point was present in the pH range of 3.5 to 8.5. The results are shown in Table 3.
実施例2~16 、比較例1~10
 両性ポリアクリルアミド共重合体(a)の種類、反応時の温度、pH、濃度、時間、グリオキサール量(mol%対共重合体(a)のアミド基)を表2に示すように変えたこと以外は、実施例1と同様に行い、アルデヒド官能化ポリアクリルアミド(A-2)~(A-16)、(RA-1)~(RA-10)を含むポリアクリルアミド系製紙用添加剤を得た。得られたアルデヒド官能化ポリアクリルアミドについて、実施例1と同様に数平均分子量、分子量分布、アミド反応率、等電点を測定した結果を表3に示す。
Examples 2 to 16 and Comparative Examples 1 to 10
Except that the amphoteric polyacrylamide copolymer (a) type, reaction temperature, pH, concentration, time, glyoxal amount (mol% vs. amide group of copolymer (a)) were changed as shown in Table 2. Was carried out in the same manner as in Example 1 to obtain polyacrylamide-based papermaking additives containing aldehyde-functionalized polyacrylamides (A-2) to (A-16) and (RA-1) to (RA-10) . Table 3 shows the results of measuring the number average molecular weight, molecular weight distribution, amide reaction rate, and isoelectric point of the obtained aldehyde-functionalized polyacrylamide in the same manner as in Example 1.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
<低電気伝導度古紙パルプスラリーで硫酸バンドを用いた板紙の作製及び評価>
応用実施例1
 濃度2.4%、叩解度(カナディアンスタンダード・フリーネス)350、電気伝導度200mS/mの段ボール古紙パルプスラリーに、パルプ固形分に対し、硫酸バンドを0.5質量%添加した。次いで、実施例1で得られたポリアクリルアミド系製紙用添加剤を固形分換算でパルプ固形分に対し、0.3質量%添加した。このパルプスラリーを撹拌後、pH7.0の水でパルプ濃度を0.8%に希釈した後、ノーブル・アンド・ウッド(The Noble&Wood)製シートマシンにて抄紙し、プレス後、ドラムドライヤーで100℃、120秒間乾燥させて、坪量80g/mの紙を得た。得られた紙は、以下に記載する、比破裂強さ、及びインターナルボンドにて評価を行った。結果を表4に示す。また、パルプ濃度を0.8%にするまでは上記と同様にしてパルプスラリーを調整した上で濾水性の評価(DDT)を行った。結果を表4に示す。
<Production and Evaluation of Paperboard Using Sulfuric Acid Band in Low Electrical Conductivity Waste Paper Pulp Slurry>
Application Example 1
0.5% by mass of a sulfuric acid band was added to a pulp slurry of corrugated waste paper having a concentration of 2.4%, a beating degree (Canadian Standard Freeness) of 350, and an electric conductivity of 200 mS / m based on the pulp solid content. Next, 0.3% by mass of the polyacrylamide-based papermaking additive obtained in Example 1 was added to the pulp solid content in terms of solid content. After stirring this pulp slurry, the pulp concentration was diluted to 0.8% with water of pH 7.0, and then paper was made with a sheet machine made by The Noble & Wood, and after pressing, 100 ° C. with a drum dryer. For 120 seconds to obtain a paper having a basis weight of 80 g / m 2 . The obtained paper was evaluated by the specific burst strength and internal bond described below. The results are shown in Table 4. Further, drainage was evaluated (DDT) after adjusting the pulp slurry in the same manner as described above until the pulp concentration was 0.8%. The results are shown in Table 4.
 比破裂強さ:JIS P8112に準拠して行った。
 インターナルボンド:JAPAN TAPPI 18-2に準拠して行った。
Specific burst strength: Performed according to JIS P8112.
Internal bond: Performed according to JAPAN TAPPI 18-2.
 DDT:Tappi、第56巻、第10号(1973年)の第46頁に記載されている「ダイナミック ドレネージ ジャー(Dynamic Drainage Jar)」用と同様な装置を用いて、希釈後のパルプスラリー(濃度0.8%)500mLを直径7.5cmのジャーに注ぎ、600rpmで撹拌しつつ下部コックを開き、100メッシュの金網にて濾過させ、一定の濾液量になるまでの時間を測定するものであり、濾水性の評価に用いることができる。濾液量が100gに達するまでの時間を測定した。数値が小さいほど、濾水性が良いことを示している。 DDT: Tappi, Vol. 56, No. 10 (1973), page 46 of “Dynamic Drainage Jar”. 0.8%) Pour 500 mL into a 7.5 cm diameter jar, open the lower cock while stirring at 600 rpm, filter through a 100-mesh wire mesh, and measure the time to reach a certain filtrate volume. It can be used for evaluation of drainage. The time until the filtrate amount reached 100 g was measured. The smaller the value, the better the drainage.
応用実施例2~32、応用比較例1~24
 応用実施例1 において、表4のようにポリアクリルアミド系製紙用添加剤の種類、および質量%を変えた以外は、応用実施例1と同様な操作を行い、坪量80g/mの紙を得た。得られた紙は、応用実施例1と同様に評価を行った。結果を表4に示す。また、応用実施例1と同様にして濾水性の評価(DDT)を行った。結果を表4に示す。
Application Examples 2-32 and Application Comparison Examples 1-24
In Application Example 1, the same operation as in Application Example 1 was carried out except that the type of polyacrylamide paper additive and the mass% were changed as shown in Table 4, and a paper having a basis weight of 80 g / m 2 was obtained. Obtained. The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 4. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
<低電気伝導度古紙パルプスラリーで硫酸バンドを用いない板紙の作製及び評価>
応用実施例33
 濃度2.4%、叩解度(カナディアンスタンダード・フリーネス)350、電気伝導度200mS/mの段ボール古紙パルプスラリーに、実施例1で得られたポリアクリルアミド系製紙用添加剤を固形分換算でパルプ固形分に対し、0.3質量% 添加した。このパルプスラリーを撹拌後、pH7.0の水でパルプ濃度を0.8%に希釈した後、ノーブル・アンド・ウッド(TheNoble&Wood)製シートマシンにて抄紙し、プレス後、ドラムドライヤーで100℃、120秒間乾燥させて、坪量80g/mの紙を得た。得られた紙は、応用実施例1と同様に評価を行った。結果を表5に示す。また、応用実施例1と同様に濾水性の評価(DDT)を行った。結果を表5に示す。
<Preparation and Evaluation of Paperboard with Low Electrical Conductivity Waste Paper Pulp Slurry and No Sulfuric Acid Band>
Application Example 33
Corrugated waste paper pulp slurry with a concentration of 2.4%, a beating degree (Canadian Standard Freeness) of 350, and an electrical conductivity of 200 mS / m is added with the polyacrylamide-based papermaking additive obtained in Example 1 as a solid in terms of solid content. 0.3% by mass was added to the minute. After stirring this pulp slurry, the pulp concentration was diluted to 0.8% with water of pH 7.0, and then papermaking was performed with a sheet machine made by The Noble & Wood. After pressing, 100 ° C with a drum dryer, The paper was dried for 120 seconds to obtain a paper having a basis weight of 80 g / m 2 . The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 5. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 5.
応用実施例34~64、応用比較例25~48
 応用実施例33において、表5のようにポリアクリルアミド系製紙用添加剤の種類、および質量%を変えた以外は、応用実施例33と同様な操作を行い、坪量80g/mの紙を得た。得られた紙は、応用実施例1と同様に評価を行った。結果を表5に示す。また、応用実施例1と同様にして濾水性の評価(DDT)を行った。結果を表5に示す。
Application Examples 34 to 64, Application Comparison Examples 25 to 48
In Application Example 33, the same operation as in Application Example 33 was performed except that the type and mass% of the polyacrylamide papermaking additive were changed as shown in Table 5, and a paper having a basis weight of 80 g / m 2 was obtained. Obtained. The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 5. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 5.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
<高電気伝導度古紙パルプスラリーで硫酸バンドを用いた板紙の作製及び評価>
応用実施例65
 濃度2.4%、叩解度(カナディアンスタンダード・フリーネス)350、電気伝導度800mS/mの段ボール古紙パルプスラリーに、パルプ固形分に対し、硫酸バンドを0.5質量%添加した。次いで、実施例1で得られたポリアクリルアミド系製紙用添加剤を固形分換算でパルプ固形分に対し、0.3質量% 添加した。このパルプスラリーを撹拌後、pH7.0の水でパルプ濃度を0.8%に希釈した後、ノーブル・アンド・ウッド(TheNoble&Wood)製シートマシンにて抄紙し、プレス後、ドラムドライヤーで100℃、120秒間乾燥させて、坪量80g/mの紙を得た。得られた紙は、応用実施例1と同様に評価を行った。結果を表6に示す。また、応用実施例1と同様に濾水性の評価(DDT)を行った。結果を表6に示す。
<Preparation and Evaluation of Paperboard Using Sulfuric Acid Band in High Electrical Conductivity Waste Paper Pulp Slurry>
Application Example 65
A 0.5% by mass sulfuric acid band was added to a pulp slurry of corrugated used paper having a concentration of 2.4%, a beating degree (Canadian Standard Freeness) of 350, and an electric conductivity of 800 mS / m based on the solid content of the pulp. Subsequently, the polyacrylamide type papermaking additive obtained in Example 1 was added in an amount of 0.3% by mass with respect to the pulp solid content in terms of solid content. After stirring this pulp slurry, the pulp concentration was diluted to 0.8% with water of pH 7.0, and then papermaking was performed with a sheet machine made by The Noble & Wood. After pressing, 100 ° C with a drum dryer, The paper was dried for 120 seconds to obtain a paper having a basis weight of 80 g / m 2 . The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 6. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 6.
応用実施例66~85、応用比較例49~60
 応用実施例65において、表6のようにポリアクリルアミド系製紙用添加剤の種類を変えた以外は、応用実施例65と同様な操作を行い、坪量80g/mの紙を得た。得られた紙は、応用実施例1と同様に評価を行った。結果を表6に示す。また、応用実施例1と同様にして濾水性の評価(DDT)を行った。結果を表6に示す。
Application Examples 66 to 85, Application Comparative Examples 49 to 60
In application example 65, except having changed the kind of polyacrylamide type papermaking additive as shown in Table 6, operation similar to application example 65 was performed and the paper of basic weight 80g / m < 2 > was obtained. The obtained paper was evaluated in the same manner as Application Example 1. The results are shown in Table 6. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 6.
Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006
<BKPを用いた紙の作製及び評価>
応用実施例81
 濃度2.4%叩解度(カナディアンスタンダード・フリーネス)410、電気伝導度100mS/mの広葉樹晒クラフトパルプ(LBKP)/コートブローク(CB)=8/2の混合パルプスラリーに、パルプ固形分に対し、硫酸バンドをアルミナ換算で0.1質量%添加し、次いで、実施例1で得られたポリアクリルアミド系内添紙力剤を固形分換算で0.3質量%添加した。このパルプスラリーを撹拌後、pH7.5の水でパルプ濃度を0.8% に希釈し、さらに撹拌下炭酸カルシウム(タマパール121:奥多摩工業(株)製)10%を添加し、ノーブル・アンド・ウッド(TheNoble&Wood)製シートマシンにて抄紙し、プレス後、ドラムドライヤーで100℃、100秒間乾燥させて、坪量60g/mの紙を得た。得られた紙は、応用実施例1と同様の評価を行った。結果を表7に示す。また、応用実施例1と同様にして濾水性の評価(DDT)を行った。結果を表7に示す。
<Production and evaluation of paper using BKP>
Application Example 81
Concentrated 2.4% beating degree (Canadian Standard Freeness) 410, electric conductivity 100mS / m hardwood bleached kraft pulp (LBKP) / coat broke (CB) = 8/2 mixed pulp slurry, based on pulp solids Then, 0.1% by mass of a sulfuric acid band was added in terms of alumina, and then 0.3% by mass of the polyacrylamide internal paper strength agent obtained in Example 1 was added in terms of solid content. After stirring this pulp slurry, the pulp concentration is diluted to 0.8% with water at pH 7.5, and further 10% of calcium carbonate (Tama Pearl 121: manufactured by Okutama Kogyo Co., Ltd.) is added with stirring. Paper was made with a sheet machine made by Wood (TheNoble & Wood), and after pressing, dried with a drum dryer at 100 ° C. for 100 seconds to obtain paper with a basis weight of 60 g / m 2 . The obtained paper was evaluated in the same manner as in Application Example 1. The results are shown in Table 7. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 1. The results are shown in Table 7.
応用実施例82~112、応用比較例61~84
 応用実施例81において、表7のように硫酸バンドの質量%およびポリアクリルアミド系内添紙力剤の種類を変えた以外は、応用実施例81と同様な操作を行い、坪量60g/mの紙を得た。得られた紙は、応用実施例81と同様に評価を行った。結果を表7に示す。また、応用実施例81と同様にして濾水性の評価(DDT)を行った。結果を表7に示す。
Application Examples 82 to 112, Application Comparative Examples 61 to 84
In Application Example 81, except that the mass% of the sulfuric acid band and the type of polyacrylamide internal paper strength agent were changed as shown in Table 7, the same operation as in Application Example 81 was performed, and the basis weight was 60 g / m 2. I got the paper. The obtained paper was evaluated in the same manner as in Application Example 81. The results are shown in Table 7. In addition, the drainage evaluation (DDT) was performed in the same manner as in Application Example 81. The results are shown in Table 7.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
<板紙における搾水性向上評価>
応用実施例113、応用比較例85
 濃度2.4%、叩解度(カナディアンスタンダード・フリーネス)350、電気伝導度200mS/mの段ボール古紙パルプスラリーに、パルプ固形分に対し、硫酸バンドを0.5質量%添加した。次いで、実施例1で得られたポリアクリルアミド系製紙用添加剤を固形分換算でパルプ固形分に対し、0.3質量% 添加した。このパルプスラリーを撹拌後、pH7.0の水でパルプ濃度を0.8%に希釈した後、パルスシートフォーマーで真空脱水を行い(真空度30kpa、60秒)、坪量400gのシートを作成した。このシート上にスポンジ、濾紙を重ね、平面プレス機にて4.2kgf-1で1秒間プレスを行った。プレス後のシート、および110℃、2時間の条件で乾燥させたシートの重量からプレス後の湿紙水分率を計算した。結果を表8に示す。
<Evaluation of water squeezing improvement in paperboard>
Application Example 113, Application Comparative Example 85
0.5% by mass of a sulfuric acid band was added to a pulp slurry of corrugated waste paper having a concentration of 2.4%, a beating degree (Canadian Standard Freeness) of 350, and an electric conductivity of 200 mS / m based on the pulp solid content. Subsequently, the polyacrylamide type papermaking additive obtained in Example 1 was added in an amount of 0.3% by mass with respect to the pulp solid content in terms of solid content. After stirring this pulp slurry, the pulp concentration was diluted to 0.8% with water at pH 7.0, and then vacuum dehydration was performed with a pulse sheet former (vacuum degree 30 kpa, 60 seconds) to produce a sheet having a basis weight of 400 g. did. Sponge and filter paper were placed on this sheet and pressed with a flat press at 4.2 kgf-1 for 1 second. The wet paper web moisture content after pressing was calculated from the weight of the sheet after pressing and the sheet dried at 110 ° C. for 2 hours. The results are shown in Table 8.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
 表4~7より、実施例に記載された本発明のポリアクリルアミド系製紙用添加剤は、本発明の構成や条件をひとつでも満足しない比較例のポリアクリルアミド系製紙用添加剤に比べて、パルプの電気伝導度や硫酸バンドの有無に関わらず、パルプへの定着性に優れるため、紙力、濾水性が満足するレベルで優れる。 From Tables 4 to 7, the polyacrylamide papermaking additive of the present invention described in the examples is more pulpy than the polyacrylamide papermaking additive of the comparative example that does not satisfy even one of the configurations and conditions of the present invention. Regardless of the electrical conductivity and the presence or absence of a sulfuric acid band, it has excellent fixability to pulp, and is excellent at a level that satisfies paper strength and drainage.
 実施例1、実施例6、実施例7のポリアクリルアミド系製紙用添加剤を用いた応用例の結果から、分子量分布がより好ましいとする2.0~8.0の範囲内にあるポリアクリルアミド系製紙用添加剤は、範囲外のポリアクリルアミド系製紙用添加剤に比べて、紙力増強効果に優れていることがわかる。 From the results of application examples using the polyacrylamide type papermaking additive of Example 1, Example 6, and Example 7, the polyacrylamide type having a molecular weight distribution in the range of 2.0 to 8.0, which is more preferable. It can be seen that the papermaking additive is superior in the paper strength enhancing effect compared to the polyacrylamide type papermaking additive which is out of the range.
 実施例1、実施例9、実施例10、実施例11、実施例12のポリアクリルアミド系製紙用添加剤を用いた応用例の結果から、両性アクリルアミド共重合体(a)を構成するモノマー単位の割合が、より好ましいとする範囲内であると、紙力増強効果がより優れることがわかる。 From the results of application examples using the polyacrylamide-based papermaking additive of Example 1, Example 9, Example 10, Example 11, and Example 12, the monomer units constituting the amphoteric acrylamide copolymer (a) It can be seen that when the ratio is within the more preferable range, the paper strength enhancing effect is more excellent.
 実施例1、実施例8、実施例15、実施例16のポリアクリルアミド系製紙用添加剤を用いた応用例の結果から、両性ポリアクリルアミド共重合体を構成するカチオン性ビニルモノマー単位がより好ましいとする3級アミンであると、紙力増強効果および濾水性がより優れることがわかる。 From the results of the application examples using the polyacrylamide-based paper additive of Example 1, Example 8, Example 15, and Example 16, the cationic vinyl monomer unit constituting the amphoteric polyacrylamide copolymer is more preferable. It can be seen that the tertiary amine is more excellent in paper strength enhancing effect and drainage.
 表8より、実施例1と比較例1のポリアクリルアミド系製紙用添加剤を用いた応用例の結果から、本発明のポリアクリルアミド系製紙用添加剤は、ポリマー構造中にアルデヒド基を導入することにより、モノマー組成、数平均分子量が同程度であっても湿紙水分率が低く、紙力増強効果および濾水性に加え、搾水性向上効果も優れていることがわかる。 From Table 8, from the results of the application examples using the polyacrylamide papermaking additive of Example 1 and Comparative Example 1, the polyacrylamide papermaking additive of the present invention introduces an aldehyde group into the polymer structure. Thus, it can be seen that even when the monomer composition and the number average molecular weight are approximately the same, the moisture content of the wet paper is low, and in addition to the paper strength enhancing effect and drainage, the water squeezing improving effect is also excellent.

Claims (8)

  1. (メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、および(メタ)アリル基を有するモノマーをポリマー構成単位として有する両性ポリアクリルアミド共重合体(a)のジアルデヒド化合物付加物であり、下記(1)~(3)全てを満足することを特徴とするアルデヒド官能化ポリアクリルアミド(A)を含む、ポリアクリルアミド系製紙用添加剤。
    (1)アルデヒド官能化ポリアクリルアミド(A)中の、アミド基及びジアルデヒド化合物が付加しているアミド基に対して、ジアルデヒド化合物が付加しているアミド基の割合であるアミド反応率が3~20モル%
    (2)アルデヒド官能化ポリアクリルアミド(A)の数平均分子量が50万~400万
    (3)アルデヒド官能化ポリアクリルアミド(A)がpH3.5~8.5の間でイオン化度が0meq/gになる等電点が存在する
    (Meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having a monomer having a (meth) allyl group as a polymer constituent unit, 1)-(3) A polyacrylamide papermaking additive comprising an aldehyde-functionalized polyacrylamide (A) characterized in that all of the above are satisfied.
    (1) In the aldehyde-functionalized polyacrylamide (A), the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the amide group and the dialdehyde compound, is 3 ~ 20 mol%
    (2) Aldehyde-functionalized polyacrylamide (A) has a number average molecular weight of 500,000 to 4,000,000 (3) Aldehyde-functionalized polyacrylamide (A) has a pH of 3.5 to 8.5 and an ionization degree of 0 meq / g There is an isoelectric point
  2. アルデヒド官能化ポリアクリルアミド(A)の分子量分布が2.0~8.0であることを特徴とする、請求項1に記載のポリアクリルアミド系製紙用添加剤。 The additive for polyacrylamide papermaking according to claim 1, wherein the molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) is 2.0 to 8.0.
  3. ポリマー構成単位の割合が、(メタ)アクリルアミド:74.0~99.7mol%、カチオン性ビニルモノマー:0.1~12.0mol%、アニオン性ビニルモノマー:0.1~10.0mol%、(メタ)アリル基を有するモノマー:0.1~4.0mol%であることを特徴とする、請求項1又は2に記載のポリアクリルアミド系製紙用添加剤。 The proportion of the polymer structural unit is (meth) acrylamide: 74.0 to 99.7 mol%, cationic vinyl monomer: 0.1 to 12.0 mol%, anionic vinyl monomer: 0.1 to 10.0 mol%, ( The additive for polyacrylamide papermaking according to claim 1 or 2, wherein the monomer has a (meth) allyl group: 0.1 to 4.0 mol%.
  4. ポリマー構成単位のカチオン性ビニルモノマーが、3級アミノ基を有することを特徴とする、請求項1~3いずれか一項に記載のポリアクリルアミド系製紙用添加剤。 The polyacrylamide papermaking additive according to any one of claims 1 to 3, wherein the cationic vinyl monomer of the polymer constituent unit has a tertiary amino group.
  5. (メタ)アクリルアミド、カチオン性ビニルモノマー、アニオン性ビニルモノマー、および(メタ)アリル基を有するモノマーを重合することによって得られる両性ポリアクリルアミド共重合体(a)に下記(1)~(5)の条件となるようにジアルデヒド化合物(b)を反応させることを特徴とするアルデヒド官能化ポリアクリルアミド(A’)を含む、ポリアクリルアミド系製紙用添加剤の製造方法。
    (1)両性ポリアクリルアミド共重合体(a)のアミド基に対してジアルデヒド化合物(b)がモル比率で10~60%であること、
    (2)pHが7.5~12.5であること、
    (3)温度が1~60℃であること、
    (4)両性ポリアクリルアミド共重合体(a)の反応前の濃度が0.5~11.0質量%であること、
    (5)時間が20秒~4時間であること
    The amphoteric polyacrylamide copolymer (a) obtained by polymerizing (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group has the following (1) to (5): The manufacturing method of the additive for polyacrylamide type paper manufacture containing the aldehyde functionalized polyacrylamide (A ') characterized by making a dialdehyde compound (b) react so that it may become conditions.
    (1) The dialdehyde compound (b) has a molar ratio of 10 to 60% with respect to the amide group of the amphoteric polyacrylamide copolymer (a).
    (2) the pH is 7.5 to 12.5,
    (3) The temperature is 1 to 60 ° C.
    (4) The concentration of the amphoteric polyacrylamide copolymer (a) before the reaction is 0.5 to 11.0% by mass,
    (5) The time is 20 seconds to 4 hours
  6. 請求項5に記載のアルデヒド官能化ポリアクリルアミド(A’)が、請求項1~請求項4のいずれか一項に記載のアルデヒド官能化ポリアクリルアミド(A)であることを特徴とする、ポリアクリルアミド系製紙用添加剤の製造方法。 A polyacrylamide characterized in that the aldehyde-functionalized polyacrylamide (A ') according to claim 5 is the aldehyde-functionalized polyacrylamide (A) according to any one of claims 1 to 4. Of manufacturing additive for papermaking.
  7. ジアルデヒド化合物(b)が、グリオキサールであることを特徴とする、請求項5に記載のポリアクリルアミド系製紙用添加剤の製造方法。 The method for producing an additive for polyacrylamide papermaking according to claim 5, wherein the dialdehyde compound (b) is glyoxal.
  8. パルプスラリーに、請求項1~4いずれか一項に記載のポリアクリルアミド系製紙用添加剤をパルプ固形分に対して0.01~3質量%添加することを特徴とする、紙の製造方法。 A method for producing paper, characterized in that 0.01 to 3% by mass of the polyacrylamide papermaking additive according to any one of claims 1 to 4 is added to the pulp slurry based on the pulp solid content.
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