WO1992000417A1 - Procede de fabrication de papier et additif associe - Google Patents

Procede de fabrication de papier et additif associe Download PDF

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Publication number
WO1992000417A1
WO1992000417A1 PCT/JP1991/000869 JP9100869W WO9200417A1 WO 1992000417 A1 WO1992000417 A1 WO 1992000417A1 JP 9100869 W JP9100869 W JP 9100869W WO 9200417 A1 WO9200417 A1 WO 9200417A1
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WIPO (PCT)
Prior art keywords
acrylamide
reaction
cationic
polymer
general formula
Prior art date
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PCT/JP1991/000869
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English (en)
Japanese (ja)
Inventor
Toshihiko Takaki
Hideaki Takahashi
Hirotoshi Doki
Hiroshi Itoh
Haruki Tsutsumi
Original Assignee
Mitsui Toatsu Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
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Application filed by Mitsui Toatsu Chemicals, Inc. filed Critical Mitsui Toatsu Chemicals, Inc.
Priority to EP91912068A priority Critical patent/EP0489930B1/fr
Priority to DE69109639T priority patent/DE69109639T2/de
Priority to KR1019950702627A priority patent/KR950011186B1/ko
Priority to KR1019920700461A priority patent/KR950009738B1/ko
Publication of WO1992000417A1 publication Critical patent/WO1992000417A1/fr
Priority to FI920866A priority patent/FI920866A0/fi

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
    • D21H17/45—Nitrogen-containing groups
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
    • D21H17/375—Poly(meth)acrylamide
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20—Macromolecular organic compounds
    • D21H17/33—Synthetic macromolecular compounds
    • D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
    • D21H17/42—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups anionic
    • D21H17/43—Carboxyl groups or derivatives thereof

Definitions

  • the present invention relates to a papermaking method, and more specifically, to a cationic acrylonitrile obtained by a Hofmann decomposition reaction at a high temperature for a short time.
  • Paper-based paper characterized in that a cadmium-based polymer is used in combination with an anionic inorganic substance or a cationic polyacrylinoleamide produced by copolymerization. It is produced by a cationic method, a cation-containing acrylnoreamide-based polymer obtained by the papermaking method and a Hofmann decomposition reaction, and an anionic inorganic substance or a copolymer. It relates to papermaking additives composed of cationic polyacrylamide. Background technology
  • Hofmann decomposition product of polyacrylinoleamide (hereinafter referred to as E) Fumane AM) is a cationic resin having a ⁇ -amino group directly bonded to the polymer main chain, and has conventionally been used for drainage in paper manufacturing processes. It has been used as an enhancer and paper strength agent.
  • the feature of Hoffman PAM is its strong cohesive strength, but it does not merely improve drainage, but also depends on the hydrogen bonding of the primary amino group, which is also a cation group. Thus, the strength between fibers is improved.
  • Hoffman PAM when Hoffman PAM is used alone, effective fixation to pulp fibers may not be achieved depending on the papermaking conditions. Was not able to be fully demonstrated. In such a case, increasing the amount of Hoffman PAM can solve the problem of drainage, but the paper on the other hand loses the texture of the paper. It was not always possible to obtain satisfactory results in terms of strength and printing characteristics, etc.o Disclosure of the invention
  • the present inventors have studied various additives having an additive effect in combination with Hofmann-decomposed PAM, and as a result, have found that anionic inorganic materials or copolymerization can be used.
  • anionic inorganic materials or copolymerization By adding a cationic acrylamide-based polymer to be manufactured in combination, it is possible to control the drainage without lowering the paper strength performance. And found the present invention.
  • the present invention provides an acrylamide-based polymer and a hypohalogenate in an alkaline region from 50 to 110.
  • Acrylic amide-based polymer and anionic inorganic substance obtained by reacting in a short time at a temperature of ' )
  • R ⁇ is hydrogen or a methyl group
  • R 2 and R 3 are hydrogen or an alkyl group having 1 to 6 carbon atoms
  • X is 0 or NH
  • n is 2 to 4
  • CH 2 C (R 5 )-C ⁇ 2 ( ⁇ )
  • R 5 represents hydrogen or a methyl group
  • R 5 is a cationic polymer obtained by copolymerizing with an acrylinoleamide monomer represented by the formula:
  • a papermaking method characterized by being added to parvularia in combination with acrylic acid, and an acrylamide polymer in the alkaline region. And a hypohalogenate are reacted in a temperature range of 50 to 110 in a short time to obtain a cationic acrylate.
  • R 1 is hydrogen or a methyl group
  • R 2 and R 3 are hydrogen or an alkyl group having 1 to 6 carbons
  • X is 0 or NH
  • n is 2 to 4
  • the present invention relates to a papermaking additive composed of cationic polyacrylamide, which is obtained by polymerization, and strength.
  • the acrylamide-based polymer used in the present invention is a homopolymer of acrylamide (or metacrylinoleamide) or a acrylamide polymer.
  • Cryllamide (or metacryl) h) means one or more unsaturated monomers copolymerizable with h), and further, a copolymer of water-soluble polymers such as starch with a daraft copolymer.
  • the copolymerizable monomer examples include a hydrophilic monomer, an ionic monomer, a lipophilic monomer, and the like.
  • a hydrophilic monomer for example, diacetone acrylamide, N, N-dimethylacrylamide, N, N- Crystal medium, N-methyl alcohol, N-methyl alcohol, N, N-ethyl alcohol, N, N-ethyl alcohol Linoleamide, N-propynyl amide, N-acrylonitrile pyridine, N-acrylonitrile pyridine, N- Cryroyl mono hollin, hydrocyanic methacrylate, hydrocyanic create, hydroxypro Pinore methacrylate, hydroxypro pinore create, various methoxy polyethylene glycol (meta) Li-les-over door, N - vinyl Norre - 2 - pin and Russia that Ki out and re-de-down, such as Ru Oh under the call.
  • ionic monomer examples include, for example, acrylinoleic acid, methacrylinoleic acid, vinylinolenolefonic acid, alinolenolenofonate, and methylolinolenate.
  • lipophilic monomer examples include N, N-di-n-butanol, phenolic amide, N-n-butyl acrylate, N-n- Hexinore cryamide, N-n- Hexin methacrylate, amide, N-n- octane linole, N-n-ok Cinoremeta cinnamate, N-tert-octane cinnamate, N-dodecyl cinnamate, N-n-dodecineme N-alkynole (meta) acrylinamide derivatives, such as tackinoleamide, N, N-diglycinoleamide amide, N, N- ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ N-- ⁇ --- ⁇ ⁇ - ⁇ Chill) Metal acryl , N- (5-Glycid pentant) acrylamide, N- (6-Glycid pendant) acrylamide, etc.
  • N- ( ⁇ -glycidyl alkanol) (methyl) acrylate derivative methine (meta) acrylate, methyl (meta) Accelerate, butyl (meta) Accelerate, Laurenole (meta) Accelerate, 2-ethyl alcohol (meta) Accelerate, Gresigir
  • (Meta) acrylate such as acrylate, derivative, acrylonitrile, methacrylonitrile, vinyl acetate, vinyl acetate, chloride Vinyl, vinylidene chloride, ethylene, pro Olefins such as hillen and butene, styrene, n-benzenzen, ⁇ -methyl styrene, butadiene, isoprene Can be used.
  • the amount of the unsaturated monomer used for the copolymerization varies depending on the type of the unsaturated monomer and the combination thereof, and cannot be said unconditionally, but is generally 0 to 50. % By weight.
  • any of a natural type and a synthetic type can be used as a water-soluble polymer which is obtained by copolymerizing the above-mentioned monomer with a graphite.
  • Denaturation of natural and various types of starch, oxidized starch, canolepoxinole starch, guanolede starch, cationized starch, etc. Objects, methylcellulose, ethanol phenolic, phenolic phenolic, phenolic phenolic, phenolic phenolic, phenolic, phenolic, etc.
  • Cellulose derivatives arginic acid, agar, galactin, carrageenan, dextran, punolan, konjac, arabianago , Casein, gelatin, etc.
  • Examples of the synthetic system include polyvinyl phenol, polyvinyl phenol, polyvinyl phenol, polyethylene lip, polyethylene porcine, polyethylene Polyethylene, Polyethylene glycol, Polypropylene glycol, Polymalinic acid copolymer, Polyacrylic acid Acid, polyacrylamide, etc. may be exposed.
  • the amount of the monomer added to the above water-soluble polymer is based on the water-soluble polymer.
  • the range is L0.0 times.
  • the polymerization method is radical weight.
  • a polymerization solvent such as water, phenolic alcohol, dimethylformamide, etc. can be applied.However, the Hofmann decomposition reaction is carried out in an aqueous solution. Therefore, aqueous polymerization is preferred.
  • the monomer concentration is 2 to 30% by weight, preferably 5 to 30% by weight.
  • the polymerization initiator is not particularly limited as long as it is water-soluble, and is usually used after being dissolved in a monomer aqueous solution.
  • peroxides for example, ammonium persulfate, calcium persulfate, hydrogen peroxide, tert-butyl peroxyside, and the like can be used. In this case, it can be used alone, but it can also be used as a redox polymerization agent in combination with a reducing agent.
  • the reducing agent include salts of lower ionization such as sulfites, bisulfites, iron, copper, cobalt and the like, N, N, N ', N'-tetramethylethyl It can release organic amines such as range amines, as well as reducing sugars such as aldoses and ketoses.
  • azo compound 2,2′-azobis-2-amidinoprono is used. Hydrochloride, 2,2'-azobis -2,4 -dimethorenol relonitrile, 4,4'-azobis --4 -cyanovaleic acid And its salts can be used. Furthermore, two or more of the above-mentioned polymerization initiators can be used in combination. In addition, in the case where the water-soluble polymer is to be subjected to daft polymerization, in addition to the above-mentioned polymerization initiator, a polymerization initiator such as a second cerium ion or a ferric ion is used as the polymerization initiator. It is also possible to use transition metal ions, as described above. Tari SI ⁇ may be used in combination with initiator. The weight of the initiator added is from 0.01 to 10% by weight, based on the monomers, preferably
  • the amount of the reducing agent added to the initiator is 0.1 to 100% on a molar basis, preferably 0.2 to 100%. 80% at o
  • the polymerization temperature is lower, generally about 30 to 90, in the case of a single polymerization initiator, and lower, generally about —5 to 5, in the case of a redox polymerization initiator. It is 0 ° C. Further, it is not necessary to keep the same temperature during the polymerization, and the temperature may be appropriately changed as the polymerization proceeds, and the temperature is generally raised by the heat of polymerization generated as the polymerization proceeds. At that time, the atmosphere in the polymerization vessel is not particularly limited, but it is better to substitute an inert gas such as nitrogen gas for prompt polymerization.
  • the polymerization time is not particularly limited, but is generally 1 to 20 hours.
  • the polyacrylamide produced by the above-described method is subjected to a Hofmann decomposition reaction.
  • the polyacrylamide may be used as it is or after dilution as necessary. And can be done.
  • non-graphitized polyacrylamide is also produced as a by-product, but it is usually subjected to the reaction without being separated.
  • the Hofmann decomposition reaction is carried out by allowing hypoamide to act on the amide group of polyacrylamide in the presence of an alkaline substance.
  • hypohalogenic acid is Kei ffi? , Hypobromous acid and hypoiodic acid.
  • chlorite include hypochlorous acid metal or alkaline earth metal salts. Specifically, sodium hypochlorite, hypochlorite, etc.
  • calcium acid lithium hypochlorite, calcium hypochlorite, magnesium hypochlorite, barium hypochlorite, etc.
  • Hypobromite and hypoiodite can also be used to remove hypobromite and hypoiodite alkali metal or alkaline earth metal salts It is also possible to inject halogen gas into the anorecalic solution to generate hypohalogenite.
  • halogen gas e.g., halogen gas into the anorecalic solution.
  • sodium hydroxide, potassium hydroxide, lithium hydroxide, etc. are used.
  • Polyacrylamide of the above substances is used.
  • the addition amount of hypohalous acid is 0.05 to 2.0 moles, preferably 5 moles, per amido group.
  • the pH at that time is generally in the range of 11 to 14.
  • the concentration of polyacrylinoleamide is about 0.1 to 17.5% by weight, but when the reaction concentration becomes high, stirring becomes difficult, and gelation becomes difficult.
  • the amount be in the range of 1 to 10% by weight, since it is easy to cause the chemical conversion.
  • the reaction temperature is less than 1% Field S: Since there are problems such as a decrease in speed, it is more preferable that the amount be ⁇ to 10% by weight.
  • the reaction temperature is in the range of 5110 ° C, preferably in the range of 6100 ° C.
  • the Hofmann decomposition reaction is performed within a short time within the above temperature range, but the reaction time depends on the reaction temperature and the polymer concentration in the reaction solution. Although it cannot be said unconditionally, for example, when the polymer concentration is 1% by weight, it is 50. Within ten minutes is C, within a few minutes in the 6 5 e C, Ru sufficient der within several tens of seconds in the 8 0 ° C. In addition, the higher the polymer concentration, the shorter the reaction time.
  • the relationship between the reaction time and the reaction temperature may be approximately within the range between the following two relational expressions, and a favorable result can be obtained if the reaction is carried out within that range.
  • the cationic polyacrylamide produced under the above conditions has a cation equivalent of about 0 to 1 measured by a colloid titration at ⁇ ⁇ 2. ⁇ It is in the range of O meq / g, and the cation equivalent is controlled by the amount of hypohalogenate added. You can use your legs.
  • the reaction since the reaction is carried out in an alkaline form, the amide group is hydrolyzed, and a carboxyl group is by-produced.
  • the amount of by-product is indicated by an anion equivalent measured by a colloid titration at pH 10 and is approximately 0 to
  • the amount of the by-product can be controlled by the amount of the alkaline substance added.
  • the methods for terminating the reaction include (1) adding a reducing agent, (2) cooling, and (3) lowering the pH of the solution by adding an acid. Or they can be used in combination.
  • (1) is a method for inactivating remaining hypohalogenates by reacting with a reducing agent.
  • a compound having active chlorine such as unreacted hypohalous acid salt, remains. If such a reaction solution is used as a paper strengthening agent, it may cause the paper machine to lose its strength. Therefore, a reducing agent is usually used to deactivate active chlorine.
  • hypohalogenate reacts at less than or equal to the number of acrylamide units in the polymer and at higher temperatures. At the end of the reaction, almost no unreacted hypohalogenate remains.
  • '(2) is a method of monitoring the reaction progress by cooling, and there are methods such as cooling using a heat exchanger and diluting with cold water. .
  • the temperature at that time is usually 50 or less, preferably 45 or less, more preferably 40 ⁇ !
  • the solution at the end of the reaction which usually shows an alloy of ⁇ 12 to 13 at the end of the reaction, is prepared by lowering ⁇ by using an acid to lower the ⁇ .
  • the decomposition reaction is stopped, and at the same time, the progress of the hydrolysis reaction is suppressed.
  • ⁇ ⁇ ⁇ ⁇ ⁇ should be less than neutral, and preferably ⁇ ⁇ 4 to 6.
  • the method for terminating the reaction can be appropriately selected from (1) to (3) depending on the reaction conditions, or a combination of these methods may be used.
  • the anionic inorganic substance to be added in combination with the Hofmann-decomposed PA ⁇ produced by the above-described method is soda silicate, anionic inorganic particulate substance, or both. It is a mixture of Sodium gaylate is obtained by melting silicon dioxide and sodium carbonate or caustic soda at high temperature, and is usually sold as water glass. Anything can be used.
  • the structure is represented by the following general formula,
  • n 1 to 4, and specifically, sodium metasilicate, sodium onoletosilicate, water glass of No. 1, No. 2 and No. 3, etc. can give . Flakes, powders, etc. may be used by dissolving them in water, or they may be used in the form of an aqueous solution.
  • the anionic particulate inorganic substance water and / may be used as long as they are anionically charged in water, and various kinds of substances can be used. Specifically, for example, silicon dioxide, aluminum oxide, antimony oxide, titanic oxide, and monmorillonites, bentonites, Clay minerals such as alumina silicate such as kaolin, activated clay, gay sand, and keisoh soil, and magnesium silicate such as evening lime. Examples of the oxide include carbonates such as calcium carbonate.
  • the particle size of the above particles is too large, the combined effect will be small, and the particle size will generally be less than 100 / zm, preferably less than or equal to, more preferably Is less than l O m.
  • the combined use ratio of the Hofmann-decomposed PAM and the anionic inorganic substance is 1 to 500%, preferably 2 to 400%, based on the weight of the Hofman-decomposed PAM. More preferably, it is 3 to 300%. If the combined ratio is too small, the combined effect will not appear, while if too large, the properties of Hoffman-decomposed PAM will be impaired.
  • the Hoffman decomposition rate at that time is not particularly limited, but is generally about 5 to 60 mol%, preferably about 10 to 50 mol%.
  • the Hofmann-decomposed PAM used in the present invention reacts at high temperature and in a short time, and can be added as it is.
  • the reaction solution at that time is strongly alkaline.
  • any method can be used in combination.
  • any method can be used in combination.
  • the addition ratio of the Hofmann-decomposed PAM and the anionic inorganic substance to the pulp is about 0.05 to 5.0%, preferably 0. 05% by dry weight of the pulp. It is in the range of 0 1-2.0%.
  • the ratio of Hoffman-decomposed PAM to the anionic inorganic substance varies depending on the papermaking conditions. Specifically, for example, when the drainage rate is increased to increase the papermaking speed, the ratio of the anionic inorganic substance is reduced, while the formation of the formation and the production of homogeneous paper are improved. Conversely, if desired, the ratio of addition may be increased.
  • the combined use of a sulfate sulfate and a water-soluble anionic resin may further increase the effect in some cases.
  • the water-soluble anionic resin used in this case may be an anionic substituent such as a carboxyl group, a sulfonate group, a phosphoric acid group or the like. It is a water-soluble resin containing a salt of, for example, anionic acrylamide-based resin, anionic polyvinylamine-based resin, and carboxy resin. Mention may be made of methinocellulose, oleoresinated starch, sodium anoregate, and the like.
  • Addition site There are no particular restrictions on the location, and it is possible to add the Hofmann-decomposed PAM and soda silicate to the pulp slurry before, during, or simultaneously with the pulp slurry. It is also possible to mix each of Hofmann-decomposed PAM and soda maleate, or to mix them.
  • the chemical is sufficiently diluted and mixed with the pulp slurry and added near the papermaking wire section. More specifically, it is selected from a machine chest, mixing box, seed box, white water pit, screen outlet, etc.
  • the paper machine used for papermaking either a fourdrinier paper machine or a circular net paper machine may be used. After adding this papermaking additive to the pulp slurry at a concentration of 0.55.0%, pH 4.09.0 and a temperature of 270, wet the sheet with a wire sheet. The water is formed, and then the water is removed by the pressurized water.
  • the dip pressure at the prespart is in the range of 240 kg cm.
  • the wet paper web that has passed through the press part moves to the dry part and is dried by steam. At this time, a material having a vapor pressure of 21.5 kg / cm 2 is dried by a drum of 800,000. After that, it is possible to process with chemicals for the purpose of improving printability, surface strength, water resistance and water repellency in size press and force renderer. .
  • the papermaking additive in the present invention is a water-soluble additive containing Hofmann-decomposed PAM and an anionic inorganic substance as active ingredients. It is a liquid mixture having an active ingredient concentration of 0.01 to 50%.
  • the mixing ratio of the anionic inorganic substance to the Hofmann-decomposed PAM is from 1 to 500%, preferably from 2 to 400%, more preferably from 3 to 300%. %. If the mixing ratio is too small, the mixing effect will not appear, and if it is too large, the properties of the Hoffman-decomposed PAM will be impaired.
  • the Hofman decomposition rate is not particularly limited, but is generally about 5 to 60% by mole, and preferably about 10 to 50% by mole.
  • Hofmann decomposition As a method of mixing PAM with anionic inorganic substances, (i) caustic soda and hypochlorite soda may be used for the Hofman decomposition reaction. Are added and dissolved in the mixed solution in advance, and the resulting mixture is used to carry out the Hofmann decomposition reaction. (Ii) mixing with the reaction solution after the Hofmann decomposition reaction.
  • the solution after the Hofmann decomposition reaction usually has a pH in the range of 12 to 13, but before mixing with the anionic inorganic substance, the pH is adjusted with an inorganic or organic acid. The pH can be lowered, or the pH can be lowered after mixing with the anionic inorganic substance.
  • the papermaking additive in the present invention has a pH in the range of pH 2 to 14. It is in .
  • the cationic monomer represented by (I) is a dimethylaminoamine (meth) acrylate, a methylamino, or the like.
  • (Meth) acrylic acid ester derivatives represented by ethyl (meta) acrylates, and dimethylaminopropyl (meta) In the case of clean media, or in the case of jet rea no mine (meta) Substituted (meta) acrylamide derivatives are exemplified.
  • the salt of an organic or inorganic acid means a salt of an inorganic acid such as sulfuric acid, hydrochloric acid, or phosphoric acid, or a salt of an organic acid such as acetic acid or formic acid.
  • the quaternary ammonium salt obtained by the reaction of the general formula (I) with a quaternizing agent contains a vinyl monomer having the tertiary amino group.
  • Monomer and methyl chloride, methyl bromide, methyl iodide, methyl sulphate, epichlorozole hydrin or benzyl chloride examples thereof include vinyl monomers having a quaternary ammonium salt obtained by reaction with a quaternizing agent such as a vinyl monomer.
  • a vinyl monomer having a tertiary amino group or a salt of an organic or inorganic acid thereof can be obtained by reaction with a quaternizing agent. It does not matter if it is used in combination with 4th ammonium salt.
  • the mixing ratio of these is not particularly limited.
  • the content of these cationic monomers is usually 0.5 to 70 ra%, preferably 2 to 50 mol%.
  • ⁇ -unsaturated carboxylic acid or a salt thereof for example, an alkali metal salt or an ammonium salt is a vinylamine having an anionic property.
  • Nomers such as maleic acid, fumanoleic acid, itaconic acid, (meth) acrylic acid, crotonic acid or citraconic acid
  • unsaturated carboxylic acids or alkali metal salts such as sodium salts or potassium salts thereof, or ammonium salts such as ammonium salts.
  • the amount of monomer used is between 0.5 and 20 mol%, preferably between 2 and 20 raol%.
  • the monomer represented by the general formula ( ⁇ ) of the present invention includes acrylorea mida and meta linolea midoka, and is commercially available in the form of a powder or an aqueous solution. It is sufficient if they are used properly. The amount of these monomers used is from 10 to 90%.
  • a crosslinkable monomer (d) can be used as the fourth component.
  • a crosslinkable monomer is a monomer having at least two or more load bonds in the molecule, and an N-anoloxymethyl (meta) acrylinole amide derivative Can be extended.
  • the former examples include: methyl visacryl amide, amide acrylamide, triacrylamide holmal , Jig relo in reminder, ethylene glycol recreation, ethylene glycol re Recording Recall, 1,3-Butyling Recall, 1,4-Butyling Recall Tactile rate, grease cell recollection, neo-repair, grease recollection, recreation, trimethylo
  • Examples of the N-alkoxymethyl (methyl) acrylate derivative include N-hydroxymethyl (methyl) acrylate.
  • the derivative examples of the derivative include N-hydroxymethyl (methyl) acrylate.
  • N-methylol (meta) clean amide N-methyl Tokishime (meta) acrylamide, N-ethoxymethyl (meta) acrylate, N-n-butymethyl (meta) Ta) Acrynorea amide, N-tert, -butoxymethyl (meta) atainorea amide, etc.
  • the amount of the cross-linking agent used depends on the type of the cross-linkable monomer and cannot be specified unconditionally, but is usually 0.001 to 20 fliol%, which is preferable. Is 0.001 to: L 0 mol%.
  • a method for obtaining the cationic polyacrylamide (B) of the present invention a method known in the art for use in the polymerization of this kind of water-soluble vinyl monomer can be used. Method is used.
  • a radical polymerization is preferred as the polymerization method.
  • the monomer concentration is 2 to 30% by weight, preferably 5 to 30% by weight.
  • the polymerization initiator is not particularly limited as long as it is water-soluble, and is usually used after being dissolved in an aqueous monomer solution.
  • peroxides such as hydrogen peroxide and benzoyl peroxide, sodium persulfate, persulfate such as potassium persulfate, and ammonium persulfate.
  • Salts bromates such as sodium bromate, potassium bromate, sodium perborate, potassium perborate, and ammonium perborate Perborate, such as monium, sodium percarbonate, percarbonate rim, percarbonate, such as ammonium percarbonate, sodium percarbonate , Potassium permonate, ammonium perphosphate And tert.-butyl butoxide, and the like. In this case, it can be used alone, but it can also be used as a redox polymerization agent in combination with a reducing agent.
  • reducing agent examples include low-order ionizing salts such as sulfites, bisulfites, iron, copper, cobalt, and the like, N, N, N ','-tetramethylethyl Organic amines such as thilesamine and further reducing sugars such as aldose and ketose can be added.
  • azo compound 2,2'-azobis-4-amidinopropane hydrochloride and 2,2'-isozobis-2,4-dimension It is also possible to use lanolin linoleic acid, 4,4'-azobis-4-cyanovaleic acid and salts thereof. Further, two or more of the above-mentioned polymerization initiators can be used in combination.
  • the polymerization temperature is lower in the case of a single polymerization initiator and is generally in the range of 30 to 90, and is lower in the case of a redox-based polymerization initiator and is generally in the range of 5 to 50.
  • the temperature may be appropriately changed as the polymerization proceeds, and the temperature is generally raised by the heat of polymerization generated as the polymerization proceeds.
  • the atmosphere in the polymerization vessel at that time is not particularly limited, but it is better to substitute an inert gas such as nitrogen gas in order to promptly carry out the polymerization.
  • the polymerization time is not particularly limited, but is generally 1 to 20 hours.
  • the method of the present invention is used in a pulp papermaking process, and improves drainage to improve drainage during papermaking. It has a great effect on paper strength, which enhances the mechanical strength of paper and paper.
  • the use ratio of Hofmann-decomposed PAM and cationic polyacrylamide (B) is optional depending on the pulp raw material and white water, but the mixing effect is not limited. Thus, the ratio is 95: 5 to 5:95, preferably 80:20 to 20:80.
  • the method of adding the cationic polyacrylinamide is Hofmann-decomposed PAM and cationic polyacrylamide (B), respectively.
  • the pulp slurry may be added to the pulp slurry alone or after the Hofmann-degraded PAM is mixed with the cationic polyacryloniamide (B). There is a method of adding to the mixture, and either method may be used.
  • the water-soluble anionic resin used in this case may be an anionic substituent such as a carboxylic acid group, a sulfonate group, a phosphoric acid group or the like. It is a water-soluble resin containing salt, for example, anionic acrylamide resin, anionic polyvinyl alcohol resin, carboxymethylcellulose Examples include cellulose, carboxyl methylated cellulose, sodium alginate, and the like. There are no particular restrictions on the location of the addition, and Hoffman-decomposed PAM and ionic polyacrylamide (B) can be added.
  • Lup slurry It can be added to the pulp slurry before, after or simultaneously with the pulp slurry. Also, a mixture of Hofmann-degraded PAM and cationic polyacrylamide (B), or a mixture of Hofmann-degraded PAM and cationic polyacrylamide (B) It is also possible to mix with a mixture of linoleamide (B).
  • the wet sheet can be added anywhere before the wet sheet is formed, and it should be added in a place where the chemical is sufficiently diluted and mixed with the pulp slurry and close to the papermaking wire section. More specifically, it is selected from machine chests, mixing boxes, seed boxes, white water pits, and screen outlets.
  • As the paper machine used for papermaking either a fourdrinier paper machine or a circular net paper machine may be used. After adding this papermaking additive to the pulp slurry at a concentration of 0.5 to 5.0%, pH 4.0 to 9.0, and a temperature of ⁇ 20 to 70, the wire was added. A wet sheet is formed at the part, and then the water is pressed at the pre-part. Presno ,. The dip pressure at the port ranges from 20 to 400 kg / cm.
  • the wet paper web that has passed through the press part moves to the dry part and is dried by steam.
  • a material having a vapor pressure of 2 to 15 kg / cm 2 is used and dried by a drum of 80 to 200.
  • processing with chemicals aimed at improving printability, surface strength, water resistance, and water repellency in the size press and force renderer is also possible. is there .
  • the papermaking additive in the present invention includes Hoffman-decomposed PAM and cationic polyacrylinoamide (B). It is a water-soluble mixture as an active ingredient, and the active ingredient concentration is in the range of 0.001 to 50%. Hofmann decomposition
  • the mixing ratio of cationic polyacrylamide (B) to PAM is by weight, 95: 5 to 5:95, preferably 80:20 to 20: 8. It is 0. If the mixing ratio is too small, the mixing effect does not appear, while if it is too large, the properties of Hoffman-decomposed PAM are impaired.
  • the Hofman decomposition rate at this time is not particularly limited, but is generally about 5 to 60 mol%, preferably about 10 to 50 mol%.
  • the solution after the Hofmann-decomposition reaction is usually pH 12 to 13
  • the pH can be reduced with an inorganic or organic acid before mixing with cationic polyacrylamide (B). It is also possible to lower the pH after mixing with cationic polyacrylamide (B), and the papermaking additive in the present invention falls in the pH range of 2 to 14. is there .
  • the drainage strength can be improved without lowering the paper strength, specifically, the burst strength, the Z-axis strength, the compressive strength, and the like. Will be possible. Therefore, if the method of the present invention is applied, it will be very effective if used in a material such as corrugated cardboard or newspaper which has a high proportion of used paper. Paper with high strength can be manufactured.
  • corrugated paper and newsprint are not limited to paper that requires strength, and drainage is required in the papermaking process. By applying the present invention to such cases, it is possible to produce paper with good productivity and excellent paper strength.
  • BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described with reference to examples, but the present invention is not necessarily limited to the following examples. All percentages are by weight unless otherwise specified.
  • the reaction was stopped by adding 25.2 g of a 0.001% aqueous solution of sodium sulfite to obtain lwt% of an acrylamide polymer (hereinafter referred to as Hoffman PAM). (B)). A part of the reaction product is taken in an aqueous solution of pH2, and is used as an indicator in an aqueous solution of 1Z400N-polyvinyl sulfonate using toluidine blue. When the colloid titration was performed, the cationic value was 4.4 neq. Zg.
  • Example 1 A hand-made test was performed in the same manner as in Example 1, except that 0.6% of No. 3 water glass was added on a dry weight basis. The results are shown in Table 1.
  • Example 1 A hand-made test was conducted in the same manner as in Example 1 except that No. 3 water glass was added in an amount of 0.90% on a dry weight basis. The results are shown in Table 1.
  • Example 1 A hand-made test was performed in the same manner as in Example 1, except that 1.5% of No. 3 water glass was added on a dry weight basis. The results are shown in Table 1.
  • CSF Canadian Standard * Freeness
  • a handsheet test was performed in the same manner as in Example 5 except that 0.01% of colloidal silica was added on a dry weight basis. The results are shown in Table 2.
  • reaction product A portion of the reaction product is taken up in an aqueous solution of pH 2 and 1 /
  • colloid titration was carried out with an aqueous solution of 40 ON-polyvinyl phenol norephonic acid, the cationic value was 3.8 meq./g. .
  • Hoffman PAM (C) was used immediately after production.
  • CSSF Waste corrugated paper
  • 0.15% of a commercially available rosin emulsion size agent was added to the pulp on a dry weight basis, and the mixture was stirred for 2 minutes.
  • 1.0% of aluminum sulfate based on dry weight was added, and the mixture was stirred for 1 minute.
  • the pH of the pulp slurry at this time was 5.1.
  • the acrylamide-based polymer obtained in Production Example 3 was added in an amount of 0.30% on a dry weight basis, and the mixture was stirred for 1 minute, and then the Hofmann PAM ( C) was added in an amount of 0.10% on a dry weight basis.
  • the polyacrylamide-based polymer obtained in Production Example 3 was added in an amount of 0.20% on a dry weight basis, and the Hofmann PAM (C) obtained in Production Example 4 was dried.
  • a hand-drawing test was performed in the same manner as in Example 8, except that 0.20% was added on a weight basis. The results are shown in Table 3.
  • Example 8 The same test as in Example 8 was carried out, except that 0.4% was added, and the acrylnoreamide-based polymer obtained in Production Example 3 was not added. The results are shown in Table 3.
  • the paper made under the conditions within the scope of the claims of the present invention uses the acrylnorea amide-based polymer obtained in Production Example 4 alone.
  • the acrylamide-based polymer obtained in Production Example 3 or 4 is more ruptured than when the acrylamide-based polymer obtained in Production Example 3 or 4 is used alone, It has an excellent effect on performance such as strength, specific compressive strength, and ⁇ $ ⁇ strength.
  • Paper made by the method of the present invention has excellent paper strength performance such as specific burst strength, specific compression strength, and Z-axis strength.
  • it is suitable for adjusting the formation and producing a paper having excellent strength, even at the expense of drainage.
  • the water-repelling power and the water-repelling power are maintained while maintaining the level of drainage when the acrylamide-based polymer is used alone. It is not affected by the deterioration of the formation as expected, and is superior in the paper strength performance even when the acrylinoleamide polymer is used alone. .

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

Abstract

Additif destiné à la fabrication du papier et comportant (A) un polymère acrylamide cationique obtenu par la réaction d'un polymère acrylamide avec un hypohalite sous des conditions alcalines, à une température comprise entre 50 et 110 °C, et pendant une courte durée; et (B) soit une substance inorganique anionique soit un polyacrylamide cationique obtenu par la copolymérisation d'un monomère cationique tel qu'un ester acrylique ou un dérivé d'acrylamide, un acide carboxylique insaturé-α,β ou un sel, et l'acrylamide.
PCT/JP1991/000869 1990-06-28 1991-06-27 Procede de fabrication de papier et additif associe WO1992000417A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP91912068A EP0489930B1 (fr) 1990-06-28 1991-06-27 Procede de fabrication de papier et additif associe
DE69109639T DE69109639T2 (de) 1990-06-28 1991-06-27 Verfahren zum herstellen von papier und zusatz dafür.
KR1019950702627A KR950011186B1 (ko) 1990-06-28 1991-06-27 제지방법 및 제지용 첨가제
KR1019920700461A KR950009738B1 (ko) 1990-06-28 1991-06-27 제지방법 및 제지용 첨가제
FI920866A FI920866A0 (fi) 1990-06-28 1992-02-27 Foerfarande foer framstaellning av papper och tillsatsaemnen till framstaellningen.

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2/168379 1990-06-28
JP16837990 1990-06-28
JP16837690 1990-06-28
JP2/168376 1990-06-28

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WO1992000417A1 true WO1992000417A1 (fr) 1992-01-09

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

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CN114481692A (zh) * 2022-03-01 2022-05-13 山东博汇纸业股份有限公司 一种复合纸力增强剂及其制备方法

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DE69501988T2 (de) * 1994-08-19 1998-09-10 Nippon Paint Co Ltd Amidmonomer und dessen Polymer
JPH08269890A (ja) * 1995-03-30 1996-10-15 Nippon P M C Kk 製紙用添加剤及び製紙方法
FI120881B (fi) * 2004-12-10 2010-04-15 Metso Paper Inc Menetelmä aallotuskartongin tai testlainerin valmistamiseksi
KR101395270B1 (ko) * 2012-08-03 2014-05-15 (주)기륭산업 친환경적 제지용 지력증강제의 제조방법

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JPS6065195A (ja) * 1983-09-19 1985-04-13 星光化学工業株式会社 製紙工程に於ける填料歩留向上方法
JPS6215391A (ja) * 1985-07-12 1987-01-23 星光化学工業株式会社 製紙方法

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JPH086008B2 (ja) * 1985-11-18 1996-01-24 星光化学工業株式会社 置換コハク酸無水物の水性分散液
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JPS58108206A (ja) * 1981-12-21 1983-06-28 Konan Kagaku Kogyo Kk 安定なポリアクリルアミドカチオン変性物水溶液の製造方法
JPS6065195A (ja) * 1983-09-19 1985-04-13 星光化学工業株式会社 製紙工程に於ける填料歩留向上方法
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CN114481692A (zh) * 2022-03-01 2022-05-13 山东博汇纸业股份有限公司 一种复合纸力增强剂及其制备方法

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EP0489930A1 (fr) 1992-06-17
CA2065282C (fr) 1996-10-22
DE69109639D1 (de) 1995-06-14
EP0489930A4 (en) 1992-12-09
CA2065282A1 (fr) 1991-12-29
DE69109639T2 (de) 1995-09-07
KR920702453A (ko) 1992-09-04
FI920866A0 (fi) 1992-02-27
EP0489930B1 (fr) 1995-05-10
KR950011186B1 (ko) 1995-09-29
KR950009738B1 (ko) 1995-08-26

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