Classifications

• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
  • D21H17/43—Carboxyl groups or derivatives thereof
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
  • D21H17/20—Macromolecular organic compounds
  • D21H17/33—Synthetic macromolecular compounds
  • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
  • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
  • D21H17/45—Nitrogen-containing groups
• • D—TEXTILES; PAPER
  • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
  • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
  • D21H19/00—Coated paper; Coating material
  • D21H19/10—Coatings without pigments
  • D21H19/14—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12
  • D21H19/20—Coatings without pigments applied in a form other than the aqueous solution defined in group D21H19/12 comprising macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• This invention relates to an additive for the production of paper. More particularly, it relates to an amphoteric polymeric additive for the production of paper, which is capable of retaining in the paper a water drainage-­improving action and such additives as filler and sizing agent in high yields under neutral conditions.
• the neutral paper production has come to prevail in the place of the conventional acidic paper production.
• the neutral paper production is advantageous in (1) improving the durability of paper, (2) decreasing the possibility of corroding machines, (3) allowing safe use of inexpensive calcium carbonate as a filler, and (4) permitting a paper producing machine to be operated in a closed system, for example.
• amphoteric polymeric compounds such as Mannich reaction products of acrylic acid-acrylamide copolymers, copolymers of tertiary amino group- or quaternary ammonium salt group-containing polymerizable monomers with acrylic acid, and Hofmann degradation products of polyacrylamides have been finding utility in this practice.
• these cationic or amphoteric polymeric compounds are used as water permeation-improving agents and as yield-improving agents such as filler and sizing agent under neutral conditions, they have the problem that they are still short of sufficiently fulfiling their roles or they are retained ununiformly in paper.
• An object of this invention is to provide a novel additive for the production of paper.
• Another object of this invention is to provide an amphoteric polymeric additive for the production of paper, which enables the water drainage improving action and such additives as filler and sizing agent to be retained in high yields in paper.
• Yet another object of this invention is to provide a novel pulp composition.
• an additive for the production of paper comprising an amphoteric polymeric electrolyte having as an essential component thereof a structural unit represented by the general formula I: wherein n is an integer in the range of 1 to 5, R1, R2, and R3 are independently hydrogen atom or an alkyl group, R4 is hydrogen atom, an alkyl group, or a hydroxyalkyl group, and a and b jointly are relative numerals such that a/b is in the range of 0.2 to 45, having at least part of the amino group of the amphoteric polymeric electrolyte neutralized, and possessing a cation equivalent value (Cv) in the range of 1.0 to 15.0 meq/g, an anion equivalent value (Av) in the range of 0.1 to 7.0 meq/g, and a Cv/Av ratio in the range of 0.2 to 45.0.
• Cv cation equivalent value
• n is an integer in the range of 1 to 5, preferably 1 to 3
• R1, R2, and R3 are independently a hydrogen atom or an alkyl group, providing that the number of carbon atoms of the alkyl group is in the range of 1 to 3, preferably 1 to 2
• R4 is hydrogen atom, an alkyl group, or a hydroxyalkyl group, providing that the number of carbon atoms of the alkyl group or hydroxyalkyl group is in the range of 1 to 3, preferably 1 to 2
• a and b are jointly relative numerals such that the a/b ratio is in the range of 0.2 to 45, preferably 0.5 to 40.
• Viscosity of an aqueous 10 % solution of amphoteric polymeric electrolyte is in the range of 50 to 100,000 cps, preferably 100 to 20,000 cps.
• copolymerization of a nonionic monomer may be resorted to for the purpose of adjusting the molecular weight and the ion equivalent.
• the vinyl type carboxylic acid monomers which are advantageously usable herein include acrylic acid, methacrylic acid, and ammonium salts of such acids, for example.
• the vinyl type anionnic monomer is preferable to be an ammonium salt.
• the neutralization ratio of the vinyl type anionic monomer is in the ratio of 5 to 100 mol%, preferably 20 to 95 mol%.
• the nonionic monomers which are usable herein include (meth)acryl amides, N,N-dimethyl (meth)acryl amides, N,N-diethyl (meth)acryl amides, hydroxyethyl (meth)acrylates, hydroxypropyl (meth)acrylates, hydroxyethyl (meth)acryl amides, hydroxypropyl(meth)acryl amides, and acrylonitrile, for example.
• alkylene imines which are used preferably herein are 1,2-alkylene imine (aziridines).
• 1,2-propylene imine and ethylene imine prove to be particularly desirable on account of their ready availability and relative inexpensiveness.
• other substituted 1,2-aziridines may be used.
• the polymerization in any of the aforementioned methods of (1), (2), (3), and (4) can be carried out by the conventional method using a peroxide type, an azo type, or a redox type polymerization initiator as popularly practised.
• the amount of the polymerization initiator to be used in the polymerization is in the range of 0.001 to 10 % by weight, preferably 0.01 to 0.5 % by weight.
• Ammonium persulfate, potassium persulfate, hydrogen peroxide, and cumene hydroperoxide may be cited as examples of the peroxide type initiator.
• Azobis-isobutyronitrile, 2,2′-azobis(2amidinopropane) dihydrochloridel, 2,2′-­azobis(2,4-dimethylvaleronitrile), and 4,4′-azobis(4-­cyanopentanoic acid) may be cited as examples of the azo type initiator.
• Formaldehyde sodium sulfoxylate, thioglyconic acid, L-ascorbic acid, dimethyl aminopropionitrile, sodium hydrogen sulfite, B-­mercaptoethanol, and combinations of divalent iron salts with reducing agents may be cited as examples of the redox type initiator. It is permissible to use a peroxide type initiator or a redox type initiator in combination with an azo type initiator.
• the polymerization system may incorporate therein any of the well-known chain transfer agents such as isopropyl alcohol, erythruvic acid, and 2-mercaptoethanol.
• the conventional nonionic surfactants may be cited as examples of the surfactant to be used for the water-in-­oil emulsification involved in the aforementioned methods of (3) and (4).
• These nonionic surfactants include sorbitan monooleate, sorbitan monostearate, sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, and glycerol monooleate, for example.
• These nonionic surfactants may be used either singly or in the form of a combination of two or more members.
• nonionic surfactant may be used in combination with ordinary anionic and cationic surfactants.
• Hydrophobic aliphatic and aromatic hydrocarbons and plant and animal oils and modified oils thereof may be cited as examples of the hydrophobic organic solvent.
• These hydrophobic organic solvents are represented by normal paraffin, isoparaffin, cyclohexane, naphthene, toluene, xylene, mineral oils, and kerosene.
• the total concentration of the salt of an aminoalkyl ester monomer, the vinyl type anionic monomer, and the nonionic monomer in the method of (3) and the total concentration of the vinyl type anionic monomer and the nonionic monomer in the method of (4) are each desired to be in the range of 20 to 80% by weight, based on the amount of water.
• the concentration of the surfactant to be used therein is preferable to be in the range of 5 to 30% by weight, based on the amount of the hydrophobic organic solvent.
• the ratio of the hydrophobic organic solvent to water is in the range of 1 : 10 to 10 : 1, preferably 1 : 5 to 3 : 1.
• the polymer concentration is preferable approximately in the range of 5 to 80% by weight, specifically 10 to 60 % by weight. Any polymer concentration less than 5% by weight is undesirable because the productivity is unduly low. Any polymer concentration exceeding 80% by weight is undesirable because the polymerization heat is generated in a large volume such as to elevate the temperature of the system excessively.
• the polymerization temperature is desired to be in the range of 100 to 120°C, preferably 300 to 90°C.
• the polymerization time is approximately in the range of 10 minutes to 10 hours, preferably 1 to 7 hours, though it is variable with the concentration of the monomer, the polymerization temperature, and the polymerization degree aimed at.
• the aminoalkylation in the methods of (2) and (4) can be carried out by causing an alkylene imine to react with a vinyl type carboxylic acid polymer.
• a divalent metal ion may be added, when necessary, to the vinyl type carboxylic acid polymer to induce partial formation of a chelate of the metal ion with carboxylic acid before the polymer is subjected to the aminoalkylation.
• a method of performing the aminoalkylation by alternately adding an alkylene imine and a neutral acid portionwise to the vinyl type carboxylic acid copolymer.
• the aminoalkylation is preferable to proceed at a temperaturebelow 65°C, preferably in the range of 10° to 55°C. If this reaction temperature exceeds 65°C, the reaction solution undergoes gelation while the reaction i9 in process and the reaction product is opacified with insolubles. Conversely, if the reaction temperature is below 10°C, the reaction time is elongated infinitely and the reaction is consequently rendered meaningless.
• the neutralization of the aminoalkyl group is effected to an extent in the range of 50 to 150 mol%, preferably 50 to 100 mol%, based on the amount of the added alkylene imine. It is effected collectively or divisionally during the course of the aminoalkylation.
• the neutral acid is not specifically defined, it is preferable to be hydrochloric acid, nitric acid, or sulfuric acid, for example.
• the relative amounts of the vinyl type carboxylic acid monomer and the salt of an aminoalkyl ester monomer, the relative amounts of the vinyl carboxylic acid polymer and the alkylene imine, and the amount of the nonionic monomer must be fixed so that the cation equivalent amount, Cv, will be in the range of 1.0 to 15.0 meq/g, preferably 2.0 to 12.0 meq/g, the anionic equivalent amount, Av, in the range of 0.1 to 7.0 meq/g, preferably 0.2 to 6.0 meq/g, and the Cv/Av ratio in the range of 0.2 to 45.0, preferably 0.5 to 40.0.
• the terms "cation equivalent amount” and “anion equivalent amount” as used herein refer to the relevant effective components of solids of a sample minus the amounts of the neutral acid and the surfactant.
• the additive of this invention for the production of paper is particularly excellent in the retention of the filler when the Cv/Av ratio is below 20. Any Cv/Av ratio below 0.2 is undesirable because the interreactivity of the additive with pulp is unduly weak, the drainage is poor, and the yield of the filler is ununiform. When the Cv/Av ratio exceeds, the additive particularly excels in water drainage and yield of the sizing agent. Any Cv/Av ratio exceeding 45 is undesirable because the cohesive force of the filler and the yield of the filler are both unduly low.
• compositions of the component monomers and the conditions of polymerization are desired to be suitably set so that the viscosity of an aqueous 10% solution of the additive will be in the range of 50 to 100,000 cps, preferably 100 to 20,000 cps (Brookfield viscosity measured at pH 3.5 and 25°C).
• the kinds of pulp for which the additive for the production of paper according with this invention include ground pulp, thermomechanical pulp, sulfite pulp, semichemical pulp, Kraft pulp, various species of synthetic pulp, and the pulp produced by digesting used paper, for example. It is permissible to use the additive in combination with various adjuvants such as sizing agent, drainage aid, retention aid, slime controlling agent, defoaming agent, pitch-control agent, and pH adjusting agent, for example.
• a pulp composition for the production of paper is obtained by adding to the pulp the additive for the production of paper according with the present invention in an amount in the range of 0.01 to 0.2% by weight, preferably 0.01 to 0.1 % by weight, based on the amount of dry pulp.
• the drainage of the pulp slurry can be improved and the additives such as filler and sizing agent can be uniformly retained in the paper in high yields.
• Varying monomers indicated in Table 1 were placed in a reaction vessel in the weight ratio indicated correspondingly in a total amount calculated to account for a concentration of 20% by weight, based on the finished polymer.
• a reaction vessel 167 g of the hydrochloride of aminoethyl methacrylate obtained by the reaction of methacrylic acid and ethylene imine and 33 g of acrylic acid were placed in a total proportion calculated to account for a concentration of 20 % by weight based on the finished additive.
• the monomers in the reaction vessel, with the entrapped air displaced with nitrogen, and 0.2% by weight, based on the total amount of the monomers, of 2,2′-azobis(2-­amidinopropane) dihydrochloride added thereto were polymerized for 4 hours, to obtain an additive A for the production of paper according with the present invention.
• Example 2 The procedure of Example B was repeated, except that the conditions indicated in Table 2 were used instead.
• Table 2 Example Polymer Weight of polymer (g) Weight of ethylene imine (g) Final concentration (%) Neutralizing acid kind of acid Weight of acid (g)
• C Referential Example 1 100 6.0 15 61% HNO3 14.4
• D Referential Example 1 100 12.0 15 35% HCl 29.1
• E Referential Example 1 100 17.7 20 61% HNO3 29.7
• F Referential Example 1 100 20.0 20 95% H2SO4 16.8
• G Referential Example 2 100 20.1 20 61% HNO3 33.7
• H Referential Example 4 100 20.1 20 61% HNO3 33.7
• methacryloyloxyethyl trimethyl ammonium chloride (4DAM), AAm, and AA are combined in a 4DAM/AAm/AA weight ratio of 30/60/10 were placed in a total proportion calculated to account for a final concentration of 20% by weight were placed.
• the monomers in the reaction vessl, with the interior of the reaction vessel displaced with nitrogen and heated to 50°C, and 0.2% by weight, based on the total weight of the monomers, of 2,2′-azobis(2-­amidinopropane) dihydrochloride added thereto were left polymerizing for 4 hours, to obtain an aqueous solution of amphoteric polymeric compound C for comparison.
• Cation equivalent amount (Cv) [meq/g] (amount of sample titration [ml] - amount of blank titration [ml]) x potency of N/400 PVSK/2
• available components refers to the components of the solids of the sample minus the neutral acid.
• Anion equivalent amount (Av) [meq/g] 0.1 x potency of N/10 NaOH x titration amount of N/10 NaOH [ml] - amount of neutralizing acid in accurately weighed sample [ml])/amount of available components in accurately weighed sample [g]
• Paper sheets were produced by using the additives for paper production obtained in Examples A to K and tested for retension of calcium carbonate and dispersibility of calcium carbonate in paper. The results are shown in Table 5.
• Paper sheets were produced by using respectively the additives for paper production obtained in Controls A to C, commercially avilable polyacrylamide Hofmann degradation product and poly ethylene imine and were tested for retention of calcium carbonate and dispersibility of calcium carbonate in paper. The results are shown in Table 5.
• the paper used for the test was produced under the following conditions.
• Pulp NBKP
• filler heavy calcium carbonate (commercially available), pulp/filler ratio : 100/30, pH : 9.3
• sizing agent AKD sizing agent (commercially available) used in a concentration of 0.2% based on pulp slurry.
• Paper sheet Tuppy square sheet machine.
• Retention of calcium carbonate This property was determined by subjecting a sample paper produced under the conditions described above to a heat treatment at 600°C x 20 minutes and consequently finding the ash content.
• Dispersibility of calcium carbonate This property was determined by coloring calsium carbonate with a dye, producing paper sheet containing the colored calcium carbonate under the conditions described above, and visually examining the produced paper sheet as to the dispersion of the dye, and rating the result on the two-point scale, wherein ⁇ is satisfactory dispersion and ⁇ is rejectable dispersion.
• Stöckigt sizing degree This property was determined by measuring the sizing degree based on JIS P8122.

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

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• 1989
  • 1989-11-16 JP JP1296239A patent/JP2790497B2/ja not_active Expired - Fee Related
• 1990
  • 1990-08-02 CA CA 2022607 patent/CA2022607C/en not_active Expired - Fee Related
  • 1990-08-03 DE DE1990616299 patent/DE69016299T2/de not_active Expired - Fee Related
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