WO2016085836A1 - Paper-making aid composition and process for increasing tensile strength of paper - Google Patents
Paper-making aid composition and process for increasing tensile strength of paper Download PDFInfo
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- WO2016085836A1 WO2016085836A1 PCT/US2015/062081 US2015062081W WO2016085836A1 WO 2016085836 A1 WO2016085836 A1 WO 2016085836A1 US 2015062081 W US2015062081 W US 2015062081W WO 2016085836 A1 WO2016085836 A1 WO 2016085836A1
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- aid composition
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- resin
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- 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
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- 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
- D21H17/38—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing crosslinkable 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
- D21H17/41—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
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- 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
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- 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
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/55—Polyamides; Polyaminoamides; Polyester-amides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/46—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/54—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
- D21H17/56—Polyamines; Polyimines; Polyester-imides
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
- D21H21/20—Wet strength agents
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- 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
- D21H23/00—Processes or apparatus for adding material to the pulp or to the paper
- D21H23/02—Processes or apparatus for adding material to the pulp or to the paper characterised by the manner in which substances are added
- D21H23/22—Addition to the formed paper
- D21H23/24—Addition to the formed paper during paper manufacture
- D21H23/26—Addition to the formed paper during paper manufacture by selecting point of addition or moisture content of the paper
- D21H23/28—Addition before the dryer section, e.g. at the wet end or press section
Definitions
- the present invention which is in the field of paper-making process, relates to a paper-making aid composition and its preparation process, to a process for increasing tensile strength, especially dry tensile strength and wet tensile strength of paper, and to a paper-making process.
- Strength (including dry strength, wet strength and temporary wet strength, etc.) is a structural property of paper, which mainly depends on the interfiber bond and the nature of fibers in the paper sheet. During the paper making process, the strength properties of paper can be improved by adding strengh agents to the paper stock by adjusting the ratio of fibers and pulping to fibrillate as well as by virtue of film-forming properties of a surface sizing agent. Strength agents have become increasingly important as they can improve the strength properties of paper and avoid the defect of pulping which accompanied with a deterioration in drainage property of paper stock and change the paper properties.
- the paper and paper board will lose alomost all mechinical strength after soaking in water and only 4%-10% of dry paper strength can be retained due to the interfiber bonding force from hydrogen bonding in celluloses.
- some types of paper are required to not only possess a certain dry strength but also retain notable mechanical strength and characteristics after being soaked in water, such as photo paper, military map paper, banknote paper, paper tableware, wallpaper base, etc.
- a special strength agent can be added to the paper to impart it with essential wet strength. Therefore, a strength agent is usually divided into a dry strength and a wet strength agent.
- dry strength agents include natural polymers, such as cationic starch, Carboxymethyl Cellulose (CMC) and guar gum, and synthetic polymers such as polyacrylamide (cationic, anionic and amphoteric) , glyoxalated polyacrylamides (GPAMs), polyvinylamine, etc.
- Di-aldehyde functionalized polyacrylamide which was prepared from di-aldehyde and polyacrylamide, was developed first as a temporary wet strength resin (see US3556932A, US4605702A) back in the 1970's and 1980's. It was then developed as a dry strength resin used in combination with a wet strength resin.
- glyoxalated polyacrylamide prepared from glyoxal and backbone polyacrylamide
- GPAM glyoxalated polyacrylamide
- Anionic and amphoteric (WO0011046A1), as well as cationic (US7641766B2, US7901543B2) di-aldehyde functionalized polyacrylamides (mostly GPAMs) usually could be used separately, and they were developed to impart paper with enhanced dry strength, wet strength or drainage ability.
- Di-aldehyde functionalized polymers including cationic, anionic and amphoteric acrylamide polymers, particularly the glyoxalated modified diallyldimethylammonium chloride (DADMAC)/acrylamide copolymers, are widely used as a dry strength and temporary wet strength aid in the paper and paperboard area.
- DMDMAC diallyldimethylammonium chloride
- Such polymer strength aid is of great interest for paper and paperboard manufacturer since (1) it provides good temporary wet strength together with good dry strength, and (2) it also helps improve the drainage ability and the paper machine runnability.
- Wet strength agents are commonly used in the paper-making industry, including polyamide polyamine - epichlorohydrin (PAE) resin, melamine-formaldehyde (MF) resin, urea-formaldehyde (UF) resin and other types of wet strength agents .
- PAE polyamide polyamine - epichlorohydrin
- MF melamine-formaldehyde
- UF urea-formaldehyde
- MF resin and UF resin can't be used widely since each can only be used in acidic conditions and contains harmful and volatile formaldehyde.
- Another type of wet strength agent such as polyethyleneimine (PEI), has not been commercialized in a large scale due to the unrefined technology.
- PAE resin is a water-soluble, cationic and thermosetting resin featured with good wet strength property, formaldehyde-free, less yellowing of paper, easy to use, and the like, so it is particularly suitable for hand sheet in neutral and alkaline condition.
- PAE resin dosage exceeds a certain range, the increase in wet strength of paper will be greatly reduced.
- PAE resin has drawbacks including a long time for curing, difficult for waste paper recovery, high level of organochlorine, and not environmentally friendly.
- US6294645B1 reported a dry strength agent for paper which comprises PAE, amphoteric polyacrylamide and wet strength resin, wherein the wet strength resin could be GPAM. Furthermore, US5783041 also disclosed a dry strength agent for paper, comprising PAE resin, glyoxylated cationic polyacrylamide copolymer, and a high charge density cationic polymer resin.
- WO0011046 disclosed the synthesis of amphoteric and anionic glyoxylated polyacrylamide copolymers, and suggested that the anionic or amphoteric GPAM could be used alone or in combination with a cationic promoter, wherein the cationic promoter could be starch, PAE resin, polyamines.
- a cationic promoter could be starch, PAE resin, polyamines.
- this document does not pay special attention to the optimized combination of anionic GPAM with PAE resin.
- CN103215853 disclosed a wet strength agent, and pointed out that the combination of a permanent wet strength agent with a temporary wet strength agent in a ratio between 0.02-0.5: 0.2-5 could impart to the paper both wet tensile strength and good water solubility, wherein the permanent wet strength agent could be PAE resin and the temporary wet strength agent could be glyoxylated polyacrylamide resin.
- PAE polyamide polyamine-epichlorohydrin
- GPAM anionic dialdehyde-modified polyacrylamide
- each of the anionic dialdehyde-modified polyacrylamide and the polyamide polyamine-epichlorohydrin, i.e. the active substances is contained in the paper-making aid composition in an amount ranging from 1 to 50 mass- , preferably 10 to 30 mass-%.
- the present inventors have unexpectedly found that, the dry/ wet strength of paper could be further improved by separate feeding of the anionic dialdehyde-modified polyacrylamide (GPAM) strength agent and the polyamide polyamine-epichlorohydrin (PAE) resin as compared with the pre-mixing addition method.
- GPAM anionic dialdehyde-modified polyacrylamide
- PAE polyamide polyamine-epichlorohydrin
- One aspect of the present invention is to provide a paper-making aid composition, comprising an anionic dialdehyde-modified polyacrylamide (GPAM) and a polyamide polyamine-epichlorohydrin (PAE) resin, wherein the mass ratio of the PAE resin to the anionic GPAM is between about 5: 1 and about 1: 1.6.
- the composition does not contain an amphoteric or cationic dialdehyde-modified polyacrylamide. More preferably, the composition may only consist of these two components and water as a medium.
- the mass ratio of the PAE resin and the anionic dialdehyde-modified polyacrylamide is between about 3.5 : 1 and about 1 : 1.6, preferably between about 2 : 1 and about 1 : 1.23, more preferably between about 1.2 : 1 and about 1 : 1.
- aspects of the present invention provide a process to increase strength of paper, especially dry strength and wet strength, wherein the mentioned paper-making aid composition is added to the liquor comprising pulp in the paper-making process.
- the components of above strength aid composition especially the polyamide polyamine-epichlorohydrin (PAE) and the anionic dialdehyde-modified polyacrylamide (GPAM), are dosed into the pulp in the separate addition manner (i.e., they are not pre-mixed or not added simultaneously).
- PAE polyamide polyamine-epichlorohydrin
- GPAM anionic dialdehyde-modified polyacrylamide
- Another aspect of the present invention is to provide a paper-making process, comprising the steps of:
- step (f) drying the wet paper sheet obtained in the step (e) to obtain a paper sheet.
- the two components can be added to a pulp separately or simultaneously, or the two components can be first mixed with each other to form a pre-mixed strength agent and then added into a pulp. However, it is preferred that the two components are fed in the separate addition method as described above.
- the dialdehyde-modified polyacrylamide is a strength agent for paper-making, which may be prepared by modifying a base polymer of polyacrylamide type with a dialdehyde.
- the dialdehyde modified polyacrylamide-type strength agents are usually used as dry strength agents while some of them can be used to provide the paper with wet strength and drainage properties.
- the dialdehyde-modified polyacrylamide used herein is anionic.
- the polyacrylamide-type base polymer is also anionic.
- the anionic polyacrylamide-type base polymer is a copolymer of one or more acrylamide monomer(s) and one or more anionic monomer(s).
- the anionic polyacrylamide-type base polymers disclosed in WO0011046A1 are applicable to the present invention and corresponding dialdehyde-modified polyacrylamides, and their preparation methods. The contents disclosed in this document are all incorporated herein by reference.
- Acrylamide monomer means the monomer of formula
- H 2 C C-CNHR 2 wherein Ri is H or C1-C4 alkyl and R 2 is H, C1-C4 alkyl, aryl or arylalkyl.
- acrylamide monomers are, for example, acrylamide or methacrylamide.
- Alkyl means a monovalent group derived from a straight or branched chain saturated hydrocarbon by the removal of a single hydrogen atom.
- Representative alkyl groups include methyl, ethyl, n- and iso-propyl, cetyl, and the like.
- Alkylene means a divalent group derived from a straight or branched chain saturated hydrocarbon by the removal of two hydrogen atoms. Representative alkylene groups include methylene, ethylene, propylene, and the like.
- Aryl means an aromatic monocyclic or multicyclic ring system of about 6 to about 10 carbon atoms.
- the aryl is optionally substituted with one or more C1-C2 0 alkyl, alkoxy or haloalkyl groups.
- Representative aryl groups include phenyl or naphthyl, or substituted phenyl or substituted naphthyl.
- Arylalkyl means an aryl-alkylene-group where aryl and alkylene are as defined above.
- Representative arylalkyl groups include benzyl, phenylethyl, phenylpropyl, 1-naphthylmethyl, and the like, e.g., benzyl.
- the di-aldehyde may be selected from glyoxal, malonaldehyde, succinic aldehyde and glutaraldehyde, preferably glyoxal.
- the anionic monomer can be one or more selected from a group consisting of acrylic acid, methacrylic acid, itaconic acid, maleic acid, and maleic anhydrid and the salts thereof.
- the anionic monomer can be acrylic acid, itaconic acid, a salt of acrylic acid, and/or a salt of itaconic acid.
- the sum of the anionic monomers there is no special limitation to the sum of the anionic monomers, as long as a stable polymer is prepared.
- the sum of the anionic monomers can be 0.1-50 mol , such as 5-30 mol , of the copolymer, depending on the practical application, but without being limited to those.
- the ratio of dialdehyde, especially glyoxal, to acrylamide (G/A ratio) in the dialdehyde modified polyacrylamide can be 0.01 :1-1: 1 (molar ratio), e.g., 0.1 :1-0.8: 1 (molar ratio).
- GPAM refers to a dialdehyde modified polyacrylamide, especially glyoxal-modified polyacrylamide.
- the weight average molecular weight of the dialdehyde modified polyacrylamide can be 100,000-10,000,000 Dalton, or 500,000-2,000,000 Dalton, or 800,000-1,500,000 Dalton, or 1,000,000-1,200,000 Dalton.
- the dialdehyde-modified polyacrylamide can be prepared according to the known technology, for example, the process disclosed in US Patent No. 7641766 B2, the contents disclosed in this document being incorporated by reference into the present application in their entirety. It shoud be noted that, in the process of producing the dialdehyde-modified polyacrylamide, a cross-linking agent and / or a chain transfer agent can be used to provide a branched / cross-linked structure of the copolymer.
- PAE resin is generally formed by reacting a carboxylic acid, especially a dicarboxylic acid, with a polyalkylene polyamine under conditions which produce a water-soluble, long-chain aminopolyamide containing the recurring groups: — NH(C n H 2n HN) x — CORCO—
- n and x are more than 2 and R is the divalent, organic radical of the dicarboxylic acid
- Dicarboxylic acids used in preparing the aminopolyamide could be saturated aliphatic dicarboxylic acids, preferably containing about 3 to 8 carbon atoms, such as malonic, succinic, glutaric, adipic, and so on, together with diglycolic acid. Of these, the saturated aliphatic dicarboxylic acids having about 4 to 6 carbon atoms in the molecule, such as adipic acid, are preferred. Blends of two or more dicarboxylic acids may be used, as well as blends which include a suitable amount of higher saturated aliphatic dicarboxylic acids, such as azelaic and sebatic acids, as long as the resulting long-chain polyamide is water soluble or at least water dispersible.
- the polyalkylene polyamines useful in preparing the aminopolyamide include polyamines containing two primary amine groups and at least one secondary amine group in which the nitrogen atoms of the secondary amine group are linked together by groups of the formula -C n H2 n - (where n is an integer of 1 to 6, and preferably 2 to 4), and the number of such groups in the molecule ranges from up to eight, preferably four.
- the nitrogen atoms of the secondary amine group may be attached to adjacent carbon atoms in the -C n H2 n - group or to carbon atoms further apart, but not to the same carbon atom.
- polyalkylene polyamines examples include but are not limited to diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, and the like. These polyalkylene polyamines can be used alone or in mixtures of two or more of them.
- the method for preparing the PAE resin entails reacting the obtained aminopolyamide with epichlorohydrin in a mole ratio of epichlorohydrin to free amino groups of about 0.5: 1.8, preferably 0.5:1.5 and more preferably 1 :1.25 in aqueous solution.
- the temperature may vary from about 45°C to about 100°C.
- the preparation of a PAE resin starting from preferred adipic acid and diethylenetriamine as well as epichlorohydrin is performed according to the following reaction scheme: « ⁇ > ⁇ - i ' .:n. : : COOH+ : ⁇ ; ⁇ 3 ⁇ 4) ⁇ > ⁇ C3 ⁇ 4 : ⁇ 3 ⁇ 4
- PAE resin carries a strong positive charge, tends to be retained on the fiber surface and can also further attract negatively charged GPAM, which enables PAE resin to play an excellent bridging role between fiber and anionic GPAM.
- the mass ratio of PAE resin to anionc dialdehyde-modified polyacrylamide is between about 5 : 1 and about 1 : 1.6, advantageously between about 3.5 : 1 and about 1 : 1.6, preferably between about 2 : 1 and 1 : 1.23 , more preferably between about 1.2 : 1 and about 1 : 1.
- PAE resin and anionic dialdehyde-modified polyacrylamide are used in one of the foregoing ratios, it is possible to the achieve dry tensile strength and wet tensile strength superior to those achieved by analog products comprising cationic or amphoteric dialdehyde-modified polyacrylamide.
- the paper-making aid composition according to the invention may contain or may not contain other chemical aids for paper-making, especially synthetic polymer aids for paper- making, e.g., polyvinyl alcohol (PVA), urea-formaldehyde resin, melamine formaldehyde resin, polyethyleneimine (PEI), polyethylene oxide (PEO), etc.
- the paper-making aid composition according to the invention may contain or may not contain other dry strength agents.
- the paper-making aid composition contains other chemical aids for paper-making, those skilled in the art can select the suitable kinds and amounts of the other chemical aids for paper-making as required.
- the amount of the other chemical aids for paper-making is in the range of 0-50%, preferably 0-20%, and more preferably 0-5%.
- the paper-making aid composition may only consist of a combination of the PAE resin and anionic dialdehyde-modified polyacrylamide and water as a medium.
- the paper-making aid composition may contain a cationic polyacrylamide polymer as a retention aid.
- the cationic polyacrylamide polymer is a copolymer formed by one or more acrylamide monomers and one or more cationic monomers.
- They can be one or more selected from the group consisting of diallyldimethylammonium chloride, N-(3-dimethylaminopropyl) methacrylamide, N-(3-dimethylaminopropyl) acrylamide, methacryloyloxyethyl trimethylammonium chloride, acryloyloxyethyl trimethylammonium chloride, methacryloyloxyethyl dimethylbenzylammonium chloride, acryloyloxyethyl dimethylbenzylammonium chloride,
- the paper-making aid composition of the present invention may not contain a cationic polyacrylamide polymer, as the inventors have surprisingly found that the paper-making aid composition not compising a cationic polyacrylamide polymer according to the present invention might lead to a better tensile strength.
- Another aspect of the present invention is to provide a paper-making process, comprising the steps of:
- step (f) drying the wet paper sheet obtained in the step (e) to obtain a paper sheet.
- paper-making process or “process for paper-making” means a method of making paper products from pulp comprising forming an aqueous cellulosic papermaking furnish, draining the furnish to form a sheet and drying the sheet.
- pulp slurry or “pulp” is intended to mean a product obtained from a pulping process.
- Pulp involves a production process of dissociating the plant fiber raw materials by a chemical method or a mechanical method, or a combination of the both, to form a paper pulp with an inherent color (unbleached pulp) or further to form a bleached pulp.
- the pulp can be any known pulp, including but not limited to, mechanical pulp, chemical pulp, chemical mechanical pulp, and recycled waste paper pulp, for example, a pulp containing mechanical pulp and / or recycled fiber.
- the pulp is subject to the pulping and additive adjustment, producing a fiber suspension which can be used in handsheeting.
- a fiber suspension is called as "paper stock”, so as to be distinguished from the paper slurry which is not subject to a pulping and an additive adjustment.
- wet paper sheet refers to a product obtained after the pulp stock passed the headbox, the forming section and the press section to be formed and partially drained, wherein the dryness of the wet paper sheet can be in a range of from about 35% to 50%.
- wet paper web the product which comes from the forming section but is not subject to drainage in the press section is called as “wet paper web”, which can have a dryness in a range of from about 15% to 25%.
- paper sheet refers to a product obtained after the wet paper sheet is dried in the dryer section.
- the dryness of the paper sheet can be in a range of from about 92% to 97%.
- the paper-making process according to the invention can be carried out by the following procedure, but not limited to this, i.e., the paper- making process according to the invention can be also carried out by other known paper-making procedures in the art.
- the treatment before the paper stock flowing onto the wire comprises:
- the preparation of paper stock the paper slurry can be made into a paper stock, and the preparation of the paper stock comprises pulping and additive adjustment (adding additives such as sizings, fillers, pigments and aids).
- the paper slurry is first subject to pulping wherein the fiber of the paper slurry undergoes treatments such as necessary cutting, swelling and fine fibrosis, so as to render the paper having physical properties and mechanical properties required by a certain sort of paper and meeting the requirements of a paper-making machine.
- the paper slurry can undergo sizing, adding filler and staining.
- various chemical aids can be added to provide the paper with some special properties (for example, enhancing the dry strength, wet strength and eliminating bubbles).
- the paper stock is supplied into the slurry supply system, undergoes treatments such as storing, screening, purifying, de-slagging, de-sanding, de-gasing, and dischages the metal, nonmetal impurities, fiber bundle, lump and air, etc., so as to avoid the adverse effect on the quality of the paper and hinder the paper-making process.
- the slurry pass undergoes slurry proportion, dilution, concentration adjustment, dosage and pressure elimination, and then flow into the head box and onto the wire for making paper.
- the paper-making of paper comprises:
- (1) stock flow approching the paper stock is delivered to the forming section (wire section) through the headbox.
- the headbox is useful in dispering the fiber homogeneouly and flowing the slurry onto the wire smoothly.
- the additives for paper making such as the dry strength aids for paper, the wet strength aids for paper, can be added in the process of stock flow approching.
- the forming section in the forming section, the paper stock delivered by headboxis formed into a wet paper web by draining on the wire.
- the forming section is also referred to as wire section.
- the dryness of the wet paper web can be in range of from about 15% to 25%.
- the dryness of the wet paper sheet can be in a range of from about 35% to 50%.
- the wet paper sheet from the pressing section is dried with a dry cylinder to form a paper sheet.
- the dryness of the paper sheet can be in a range of from about 92% to 97%.
- the step (f) can be carried out by the above 2.(4).
- the paper sheet can undergo, as required, finishing procedures such as calendering, winding and cutting, paper-sorting or rewinding, packaging, etc., so as to produce the paper sheet in to a finished paper in the form of flat or roller.
- finishing procedures such as calendering, winding and cutting, paper-sorting or rewinding, packaging, etc.
- surface sizing, coating and online soft calender or offline supercalender can be carried out in the dryer section.
- the paper slurry provied by a paper stock preparation system is generally subject to a slurry supply system (undergoing a treatment before the paper stock flows onto the wire), the headbox and the forming section, the press section, dryer section, etc.
- the paper-making aid composition is added into the pulp slurry in an amount of between about 0.01 kg/ton dry fiber and 50 kg/ton dry fiber, e.g., 0.1 kg/ton dry fiber and 10 kg/ton dry fiber, based on the weight ratio of the sum of the dialdehyde-modified polyacrylamide and PAE resin to the dry fiber in the pulp slurry.
- the pulp slurry (thick stock) is obtained from a paper mill.
- the thick stock comprises a mixed slurry of softwood bleached kraft pulp and hardwood bleached kraft pulp, or other pulp, as main component.
- Sheet-making is performed after the thick stock is diluted with tap water or white water from paper-making plant to a concentration of about 0.7%.
- the pulp added with the agents is poured into a forming cylinder of paper-making machine and undergoes filtering and forming. Afterwards, the forming cylinder is opened, and a bibulous paper is taken to cover the wet paper sheet which is then covered with a flat clamp to remove part of water. Then the paper sample is transferred to a new bibulous paper which is then covered with stainless steel clamp, onto which a bibulous paper is covered again, the wet paper sample is thus accumulated. When accumulating 5 to 10 paper samples, they are provided into a special press machine to perform a two-section pressing, further removing water from paper.
- the pressed paper is transferred to a constant temperature and humidity lab (about 50% humidity at 23°C), and every single paper sample is placed into a special metal ring. Piling up the metal rings and placing a heavy object onto the metal ring where the paper sample lies on. After air drying for about 24 hours, the paper sample can be peeled successively from stainless steel clamp for corresponding test.
- the principle of the internal bond impact tester is to measure the energy required to separate the paper sheet by a mechanical equipment so as to reflect the magnitude of the internal bonding strength.
- the measurement of the internal bonding strength is to express the resistant force that is required to overcome for separating the single or multiple fiber layer(s), which is frequently used to discuss the delamination problem of the paper sheet or paperboard.
- the test method adopted in the experiment comprises the determination of the force applied by a pendulum to splitting the paper along Z-direction. When the fibers of a hand sheet align in X-Y plane, the exhausted energy is mainly used for the bonding of the fiber, and the length of the fiber and the strength of the fiber itself have no influence on the Scott bonding.
- the equipment used in the experiment was purchased from PTI company.
- the test method refers to Tappi T569.
- a paper with a size of around 25.4 mmx200 mm is cut out previously, and then tape and paper sample are attached to a base following a sequence of tape-paper sample-tap, and the double-sided adhesive tape and the paper sample are attached to each other closely by applying a force. Afterwards, a pendulum is released to knock and separate the paper sample when the equipment automatically records the force that is required to separate the bonding of the fiber layers for each time, expressed in kg»cm/in 2 , J/m 2 .
- Brookfield Programmable LVDV-II+viscometer manufactured by Brookfield Engineering Laboratories, Inc, Middleboro, Mass., is utilized in this experiment.
- PAE resin used in the examples and comparative examples was polyamide polyamine epichlorohydrin, manufactured and sold by Nalco. Co., which was prepared according to the following process:
- the system was cooled to below 100°C, and about 160 kg of water was added and stirred until a uniform bright red, transparent viscous liquid was obtained, having a solids content of about 50% and a viscosity (25°C) of about 600 ⁇ 1000mPa»s.
- About 400 kg of water was added to the above-obtained polyamide, and about 80 kg of epichlorohydrin was added with stirring.
- acetic acid was added to adjust pH to about 3-5, giving the PAE resin.
- GPAM copolymer used in the examples and comparative examples was prepared according to the following process:
- the solution was incubated at about 100°C.
- the reaction ended in about 1 hour, affording an intermediate 1 with a solids content of about 41 wt% and a viscosity of about 2000 cps, wherein the concentration of cationic monomelic units was about 12 mol%.
- the cationic polyacrylamide copolymer used in the examples was prepared according to the following process:
- the PAE resin solution and GPAM 2 were respectively diluted 15 times by adding the ionized water.
- the diluted PAE resin solution and GPAM2 solution were added into the furnish in sequence in an active concentration mass ratio of about 1.25 : 1.
- the interval of adding the components was about 60 s.
- the hand sheet samples of the invention were prepared according to the hand sheet preparation method as described above with two different dosages (about 3 kg/ton or about 6 kg/ton).
- the thick stock used in this Example was a mixed slurry of softwood bleached kraft pulp and hardwood bleached kraft pulp.
- the dosage of the tested additive herein refers to the amount of the active ingredient in the solution (agent) relative to the dry fiber in the pulp slurry.
- the meaning of dosage also applies to the following examples.
- the composition and amount ratios of different paper-making aids used in the example and the measured properties were listed in Table 1.
- the use of a combination of PAE resin and anionic GPAM2 in a mass ratio of about 1.25 : 1 according to the present invention as strength agent will result in better dry tensile strength and wet tensile strength and higher tensile strength increase as compared with the use of the PAE resin or GPAM2 alone at the same dosage. Meanwhile, in the case of comparable dry tensile strength and wet tensile strength and tensile strength increase, the amount of the strength aids, especially the amount of polluting PAE resin, can be significantly reduced by using the paper-making aid according to the present invention as strength agent.
- the PAE solution and GPAM 2 were respectively diluted 15 times by adding the ionized water, and added into the furnish in sequence in different active concentration mass ratios (see Table 2 below). The interval of adding the components was about 60 s.
- the hand sheet samples of the invention were prepared according to the hand sheet preparation method as described above with two different dosages (about 2 kg/ton or about 4 kg/ton).
- the thick stock used in the Example was a mixed slurry of softwood bleached kraft pulp and hardwood bleached kraft pulp.
- the operation of Example 2 was repeated except for using further specified mass ratios as shown in Table 3 below. The data of tensile strength as measured were listed in this table.
- This example was carried out to compare the addition manners of the PAE resing and GPAM2.
- the PAE resin and GPAM2 as prepared above were added to a pulp in a active mass ratio of about 1 :1 in two different manners, i.e. separate addition (separately) or pre-mixing addition (pre-mixing).
- PAE resin and GPAM2 were added separately, PAE resing was added first and then, after about 60 s, GPAM2 was added.
- Table 4 Comparison of addition manners of PAE resin and GPAM2
- PAE resing , GPAM 1, GPAM 2 and GPAM 3 were diluted 15 times respectively using ionized water first, the PAE resin combined with GPAM1, GPAM2 and GPAM3 were used as test additives with about 1.2:1 mass ratio in two dosages (about3 kg/t and about 6 kg/t) in the preparation of the handsheet samples of the invention according to the handsheet preparation method described above.
- the other steps of the experiment are the same as Example 1.
- This example was focused on a comparison between a dual component strength solution composed of the PAE resin and GPAM 2 and a ternary component strength program composed of PAE resin, GPAM 2 and cationic polyacrylamide copolymer.
- the PAE resin and GPAM2 was added with about 1 :1 mass ratio, followed by the cationic polyacrylamide copolymer. The addition of chemistries was done in about 60 second intervals.
- the dual and ternary component strength solutions were used as test additives in the preparation of the handsheet samples of the invention according to the handsheet preparation method described above. Specific dosage of the additives was presented in Table 6.
- the thick stock used in the Example was a mixed slurry of softwood bleached kraft pulp and hardwood bleached kraft pulp.
- the ternary component strength program composed of the PAE resin, GPAM2 and the cationic polyacrylamide copolymer was less effective than the dual component strength program composed of the PAE resin and GPAM2. Moreover, the higher dose of the cationic polyacrylamide copolymer was the worst with respect to 5 strength performance.
- the invented strength solution in carton board furnish was studied in this 10 experiment, wherein the active mass ratio of PAE resing to GPAM 2 was about 1 : 1 , the addition of chemistries was done in about 60 second intervals.
- the new strength solutions were used as test additives in two dosages(about 3 kg/t and about 6 kg/t) in the preparation of the handsheet samples of the invention according to the handsheet preparation method described.
- the thick stock used in the Example was a mixed slurry of 15 bleached chemi-mechanical pulp, de-inked pulp, hardwood bleached kraft pulp and waste paper pulp.
Abstract
Description
Claims
Priority Applications (7)
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KR1020177017388A KR20170086642A (en) | 2014-11-27 | 2015-11-23 | Paper-making aid composition and process for increasing tensile strength of paper |
EP15863087.1A EP3224413A4 (en) | 2014-11-27 | 2015-11-23 | Paper-making aid composition and process for increasing tensile strength of paper |
CA2968668A CA2968668A1 (en) | 2014-11-27 | 2015-11-23 | Paper-making aid composition and process for increasing tensile strength of paper |
BR112017011294A BR112017011294A2 (en) | 2014-11-27 | 2015-11-23 | papermaking aid composition and process for increasing paper tensile strength |
MX2017006965A MX2017006965A (en) | 2014-11-27 | 2015-11-23 | Paper-making aid composition and process for increasing tensile strength of paper. |
US15/531,234 US20180298556A1 (en) | 2014-11-27 | 2015-11-23 | Paper-Making Aid Composition and Process for Increasing Tensile Strength of Paper |
CN201580064778.1A CN107109799A (en) | 2014-11-27 | 2015-11-23 | Paper making auxiliary agent composition and the method for improving paper tensile strength |
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CN201410698600.XA CN105696414B (en) | 2014-11-27 | 2014-11-27 | Papermaking aid composition and method for improving tensile strength of paper |
CN201410698600.X | 2014-11-27 |
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WO2016085836A1 true WO2016085836A1 (en) | 2016-06-02 |
WO2016085836A8 WO2016085836A8 (en) | 2016-12-15 |
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US (1) | US20180298556A1 (en) |
EP (1) | EP3224413A4 (en) |
KR (1) | KR20170086642A (en) |
CN (2) | CN105696414B (en) |
BR (1) | BR112017011294A2 (en) |
CA (1) | CA2968668A1 (en) |
MX (1) | MX2017006965A (en) |
WO (1) | WO2016085836A1 (en) |
Cited By (10)
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WO2018097822A1 (en) * | 2016-11-23 | 2018-05-31 | Kemira Oyj | A paper strength system and a process of making paper or the like |
WO2018229345A1 (en) * | 2017-06-16 | 2018-12-20 | Kemira Oyj | Strength additive system and method for manufacturing a web comprising cellulosic fibres |
WO2019063881A1 (en) * | 2017-09-29 | 2019-04-04 | Kemira Oyj | Surface treatment composition, its use and a method for producing paper, board or the like |
WO2019143519A1 (en) | 2018-01-16 | 2019-07-25 | Solenis Technologies, L.P. | Process for making paper with improved filler retention and opacity while maintaining wet tensile strength |
WO2019221692A1 (en) * | 2018-05-14 | 2019-11-21 | Kemira Oyj | Paper strength improving composition, manufacture thereof and use in paper making |
CN111705543A (en) * | 2020-05-28 | 2020-09-25 | 仙鹤股份有限公司 | Preparation method of high-whiteness high-strength carbonless copy paper base paper |
WO2020205907A1 (en) * | 2019-04-02 | 2020-10-08 | Kemira Oyj | Paper strength improvement using metal chelates and synthetic cationic polymers |
CN113501898A (en) * | 2021-07-28 | 2021-10-15 | 胡子和 | Polyacrylamide modified polymer capable of improving paper strength and preparation method thereof |
US11242653B2 (en) | 2017-06-16 | 2022-02-08 | Kemira Oyj | Strength additive system and method for manufacturing a web comprising cellulosic fibres |
EP4202119A1 (en) * | 2021-12-22 | 2023-06-28 | Billerud Aktiebolag (publ) | Reclable paper of high wet strength |
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US11028538B2 (en) * | 2019-02-28 | 2021-06-08 | Solenis Technologies, L.P. | Composition and method for increasing wet and dry paper strength |
US20230313467A1 (en) * | 2020-07-07 | 2023-10-05 | Ecolab Usa Inc. | Strength improvement via sprayboom application |
CN112223473B (en) * | 2020-10-20 | 2022-03-08 | 深圳市瑞洲实业股份有限公司 | Modified wood fiber, preparation method thereof and application thereof in papermaking |
CN112663385A (en) * | 2020-12-28 | 2021-04-16 | 冠宏化工(扬州)有限公司 | Paper pulp papermaking auxiliary agent and preparation method thereof |
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Also Published As
Publication number | Publication date |
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CN105696414A (en) | 2016-06-22 |
CN105696414B (en) | 2022-08-16 |
WO2016085836A8 (en) | 2016-12-15 |
KR20170086642A (en) | 2017-07-26 |
BR112017011294A2 (en) | 2017-12-26 |
EP3224413A4 (en) | 2018-04-25 |
CN107109799A (en) | 2017-08-29 |
MX2017006965A (en) | 2017-08-14 |
CA2968668A1 (en) | 2016-06-02 |
US20180298556A1 (en) | 2018-10-18 |
EP3224413A1 (en) | 2017-10-04 |
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