CN108026699B - Polyacrylamide-based additive for papermaking, method for producing same, and method for producing paper - Google Patents
Polyacrylamide-based additive for papermaking, method for producing same, and method for producing paper Download PDFInfo
- Publication number
- CN108026699B CN108026699B CN201680049404.7A CN201680049404A CN108026699B CN 108026699 B CN108026699 B CN 108026699B CN 201680049404 A CN201680049404 A CN 201680049404A CN 108026699 B CN108026699 B CN 108026699B
- Authority
- CN
- China
- Prior art keywords
- polyacrylamide
- aldehyde
- paper
- meth
- vinyl monomer
- Prior art date
- Legal status (The legal status 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 status listed.)
- Active
Links
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
-
- 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
Abstract
The present invention relates to an aldehyde-functional polyacrylamide-containing additive for papermaking having an excellent paper strength-enhancing effect and good drainage properties, and a method for producing paper using the same. The polyacrylamide-based papermaking additive contains aldehyde-functional polyacrylamide (A), and is characterized by being a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having, as polymer constituent units, (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a monomer having a (meth) allyl group, and satisfying various requirements.
Description
Technical Field
The present invention relates to an aldehyde-functional polyacrylamide-containing additive for papermaking having an excellent paper strength-enhancing effect and good drainability, a method for producing the same, and a method for producing paper using the same.
Background
In order to improve paper productivity and paper quality with high paper machine speeds, various aldehyde-functionalized polyacrylamide-based papermaking additives are used in the papermaking process. Aldehyde-functionalized polyacrylamides are generally produced by a process of reacting a dialdehyde compound, i.e., glyoxal (glyoxal), with polyacrylamide (polyacrylamide). Aldehyde-functionalized polyacrylamides contain not only amino groups having high hydrogen bonding capability in the polymer structure, but also aldehyde groups having reactivity with cellulose. Therefore, a covalent bond can be formed with a cellulose hydroxyl group, and thus, excellent paper strength-enhancing effect and drainage are expected.
As an aldehyde-functional polyacrylamide-based additive for papermaking, for example, a method of improving drainability in a papermaking machine by adding a polymer having a weight-average molecular weight of 100000 g/mol or more, in which an amino group or an amide group of a polyamine, a (nonionic, cationic, anionic, or amphoteric) polyamide, or the like is introduced into an aldehyde functional group by 15 mol% or more, to a pulp slurry has been proposed (see patent document 1). There has also been proposed a method for producing a cellulose-reactive functionalized polyvinylamide adduct by reacting a cellulose-reactive agent with a vinylamide polymer (see patent document 2). Further, a dialdehyde-modified polyacrylamide having an excellent paper strength-enhancing effect has been proposed in which amphoteric or anionic polyacrylamide using a divinyl monomer is reacted with glyoxal (see patent document 3).
However, these are not satisfactory in terms of both the paper strength-enhancing effect and the drainability.
Prior art documents
Patent document
Patent document 1: japanese Kohyo publication No. 2007-518896
Patent document 2: japanese patent application publication No. 2010-502800
Patent document 3: WO2000/011046 publication
Disclosure of Invention
Technical problem
The invention aims to provide a polyacrylamide papermaking additive containing aldehyde functional polyacrylamide with excellent paper strength enhancement effect and good drainability, a manufacturing method thereof and a paper manufacturing method using the papermaking additive.
Means for solving the problems
The present inventors have made intensive studies in view of solving the above-mentioned problems concerning the improvement of the adhesion of a polyacrylamide-based papermaking additive containing an aldehyde-functional polyacrylamide to pulp. Specifically, the (1) addition ratio of aldehyde compound, (2) number average molecular weight, and (3) isoelectric point with respect to ionic characteristics of aldehyde-functionalized polyacrylamide were investigated. The results are known as follows: the aldehyde-functionalized polyacrylamides of the above (1) to (3) in a specific range have a better paper strength-enhancing effect and a better drainage performance than the conventional aldehyde-functionalized polyacrylamides even under the conditions of no addition of alumina sulfate which is unfavorable for the pulp adhesion efficiency or high conductivity, and thus the present invention has been completed. It is also known: by using the aldehyde-functional polyacrylamide-containing papermaking additive of the present invention, the wet water content of the paper web before drying of the paper pulp sheet is reduced, and the effect of improving the water squeezing performance can be obtained.
In order to solve the technical problems, the technical scheme of the invention is as follows:
[ claim 1] A polyacrylamide-based papermaking additive containing an aldehyde-functionalized polyacrylamide (A), which is a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having, as a polymer constituent unit, (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a (meth) allyl group-containing monomer, and which satisfies all of the following conditions (1) to (3):
(1) the ratio of the amide group of the aldehyde-functionalized polyacrylamide (A) to the amide group of the dialdehyde compound, i.e., the amide reaction rate, is 3 to 20 mol%,
(2) the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) is 50 to 400 ten thousand,
(3) the aldehyde-functionalized polyacrylamide (A) has an isoelectric point with a pH value of 3.5-8.5 and an ionization degree of 0 meq/g.
<2> the polyacrylamide-based papermaking additive as stated in <1>, wherein the molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) is 2.0 to 8.0.
<3> the polyacrylamide-based papermaking additive according to <1> or <2>, wherein the ratio of the polymer constituent units is: 74.0 to 99.7 mol% of (meth) acrylamide, 0.1 to 12.0 mol% of a cationic vinyl monomer, 0.1 to 10.0 mol% of an anionic vinyl monomer, and 0.1 to 4.0 mol% of a (meth) allyl group-containing monomer.
<4> the polyacrylamide-based papermaking additive as stated in any one of <1> to <3>, wherein the cationic vinyl monomer of the polymer constituent unit has a tertiary amino group.
<5> a process for producing an aldehyde-functionalized polyacrylamide (A') containing a polyacrylamide-based papermaking additive, characterized in that a dialdehyde compound (b) is reacted with an amphoteric polyacrylamide copolymer (a) obtained by polymerizing (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer and a (meth) allyl group-containing monomer, and the following conditions (1) to (5) are satisfied:
(1) the molar ratio of the dialdehyde compound (b) to the amide group of the amphoteric polyacrylamide copolymer (a) is 10-60%,
(2)pH7.5～12.5，
(3) the temperature is 1-60 ℃,
(4) the concentration of the amphoteric polyacrylamide copolymer (a) before reaction is 0.5 to 11.0 mass%,
(5) the time is 20 seconds to 4 hours.
<6> A method for producing a polyacrylamide-based papermaking additive, wherein the aldehyde-functional polyacrylamide (A') according to <5> is the aldehyde-functional polyacrylamide (A) according to any one of <1> to <4 >.
<7> the process for producing the polyacrylamide-based papermaking additive according to <5>, wherein the dialdehyde compound (b) is glyoxal.
<8> A method for producing paper, characterized by adding the polyacrylamide-based papermaking additive according to any one of <1> to <4> to a pulp slurry in an amount of 0.01 to 3 mass% relative to the solid content of the pulp.
ADVANTAGEOUS EFFECTS OF INVENTION
The present invention provides an aldehyde-functional polyacrylamide-containing additive for papermaking, which has an excellent paper strength-enhancing effect and good drainage properties, a method for producing the same, and a method for producing paper using the same.
Detailed Description
The aldehyde-functional polyacrylamide (A) -containing polyacrylamide-based papermaking additive of the present invention is a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having, as polymer constituent units, (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer, and a (meth) allyl group-containing monomer.
The present invention is a method for producing an aldehyde-functional polyacrylamide (a') -containing polyacrylamide-based papermaking additive, characterized in that a dialdehyde compound (b) is reacted with an amphoteric polyacrylamide copolymer (a) obtained by polymerizing (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer and a monomer having a (meth) allyl group, and the following conditions (1) to (5) are satisfied:
(1) the molar ratio of the dialdehyde compound (b) to the amide group of the amphoteric polyacrylamide copolymer (a) is 10-60%,
(2)pH7.5～12.5，
(3) the temperature is 1-60 ℃,
(4) the concentration of the amphoteric polyacrylamide copolymer (a) before reaction is 0.5 to 11.0 mass%,
(5) the time is 20 seconds to 4 hours.
The (meth) acrylamide in the present invention is acrylamide or methacrylamide.
In the present invention, examples of the cationic vinyl monomer include vinyl monomers having a primary amino group, a secondary amino group, a tertiary amino group, or a quaternary ammonium salt. These cationic vinyl monomers may be used alone in 1 kind or in combination of 2 or more kinds. The cationic vinyl monomer constituting the amphoteric polyacrylamide copolymer (a) is preferably used because the use of a vinyl monomer having a tertiary amino group is likely to improve the effect of adhesion to pulp when used as an additive for papermaking.
Examples of the vinyl monomer having a tertiary amino group include: dialkylaminoalkyl (meth) acrylate species such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, and diethylaminopropyl (meth) acrylate; dialkyl aminoalkyl (meth) acrylamides such as dimethylaminopropyl (meth) acrylamide and diethylaminopropyl (meth) acrylamide; inorganic acid salts such as hydrochloride and sulfate of the vinyl monomer having a tertiary amino group, and organic acid salts such as formate and acetate of the vinyl monomer having a tertiary amino group. Among them, dialkylaminoalkanes (meth) acrylates are preferred.
Examples of the vinyl monomer having a quaternary ammonium salt include: a vinyl monomer obtained by the reaction of the vinyl monomer having a tertiary amino group with a quaternizing agent, and a vinyl monomer having a quaternary ammonium salt such as diallyldimethylammonium chloride. Examples of the quaternary agent include: alkyl halides (alkyl halides) such as methyl chloride (methyl chloride) and methyl bromide (methyl bromide); halogenated aralkyl (arylalkylhalide) such as benzyl chloride (benzyl chloride) and benzyl bromide (benzyl bromide); dimethyl sulfate (dimethyl sulfate), diethyl sulfate (diethyl sulfate), epichlorohydrin (epichlorohydrin), 3-chloro-2-hydroxypropyltrimethylammonium chloride (3-chloro-2-hydroxypropyltrimethylammonium chloride), and glycidyl trialkylammonium chloride (glycidyl trialkylammonium chloride). These vinyl monomers having a tertiary amino group or a quaternary ammonium salt may be used alone in 1 kind or in combination of 2 or more kinds.
In the present invention, examples of the anionic vinyl monomer include: unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, 2- (meth) acrylamide-N-glycolic acid (2- (meth) acrylamide-N-glyconic acid), and N-acryloylglycine (N-acryloylglycine); unsaturated dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and citraconic acid; unsaturated tricarboxylic acids such as aconitic acid and 3-butene-1, 2, 3-tricarboxylic acid (3-butene-1, 2, 3-tricarboxylic acid); unsaturated tetracarboxylic acids such as 1-pentane-1, 1, 4, 4-tetracarboxylic acid (1-pentane-1, 1, 4, 4-tetracarboxylic acid), 4-pentane-1, 2, 3, 4-tetracarboxylic acid (4-pentane-1, 2, 3, 4-tetracarboxylic acid), and 3-hexane-1, 1, 6, 6-tetracarboxylic acid (3-hexane-1, 1, 6, 6-tetracarboxylic acid); unsaturated sulfonic acids such as vinyl sulfonic acid (vinylsulfonic acid), styrene sulfonic acid (styrene sulfonic acid), and 2-acrylamido-2-methylpropanesulfonic acid (2-acrylamide-2-methylpropanesulfonic acid); unsaturated phosphonic acids such as vinylphosphonic acid (vinylphosphonic acid) and α -phenylvinylphosphonic acid (α -phenylphosphonic acid); alkali metal salts such as sodium and potassium salts and ammonium salts of the anionic vinyl monomers. These anionic vinyl monomers may be used alone in 1 kind or in combination of 2 or more kinds.
Among the above anionic vinyl monomers, unsaturated monocarboxylic acids and unsaturated dicarboxylic acids are preferable in terms of the paper strength-enhancing effect, and specifically, acrylic acid, 2-acrylamido-N-glycolic acid, itaconic acid, and salts thereof are particularly preferable.
In the present invention, the monomer having a (meth) allyl group may be any monomer having a (meth) allyl group, and may be classified into monomers having a (meth) allyl group, other than the (meth) allyl group, even if the monomer has other functional groups such as an anionic group and a cationic group. Specific examples thereof include: (meth) acrylic sulfonic acid or a salt thereof, (meth) allyl alcohol, (meth) allyl amine, allyl ammonium salt, and the like. Among them, preferred are (meth) acrylic sulfonic acid or a salt thereof, and dimethylhydroxyethylmethylammonium chloride (dimethylhydroxymethy methylammonium chloride).
In the present invention, as the monomer in the amphoteric polyacrylamide copolymer (a), other monomers may be used within a range not impairing the effects of the present invention. Here, the range not to impair the effect of the present invention is preferably as follows: the amphoteric polyacrylamide copolymer (a) contains 100 mol% of (meth) acrylamide, cationic vinyl monomer, anionic vinyl monomer and (meth) allyl group-containing monomer, and 0 to 3.0 mol% of other monomers.
Examples of the other monomer component include a nonionic vinyl monomer, a crosslinking agent, and a chain transfer agent. Examples of the nonionic vinyl monomer include (meth) acrylate, (meth) acrylonitrile, styrene derivatives, vinyl acetate, vinyl propionate, and vinyl methyl ether. These may be used alone in 1 kind or in combination of 2 or more kinds.
Examples of the crosslinking agent include: n-substituted (meth) acrylamides such as N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-dimethyl (meth) acrylamide, N-diethyl (meth) acrylamide, and N-isopropyl (meth) acrylamide; di (meth) acrylates such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, and the like; bis (meth) acrylamides such as N, N' -methylenebismethacrylamide, ethylenebis (meth) acrylamide, and hexamethylenebis (meth) acrylamide; examples of the polyfunctional monomer include tri-to tetrafunctional vinyl monomers such as 1, 3, 5-triacryloylhexahydro-1, 3, 5-triazine (triacrylformal), triallylisocyanurate, N-diallylacrylamide, N-diallylmethacrylamide, triallylamine, and tetramethylolmethane tetraacrylate. Examples of the compound include a water-soluble azacyclopropenyl (azidinyl) compound, a water-soluble polyfunctional epoxy compound, and a silicon compound. These may be used alone in 1 kind or in combination of 2 or more kinds. Among these, N-substituted (meth) acrylamides are preferred.
Examples of the chain transfer agent include known chain transfer agents such as alkylmercaptans (alkyl mercaptanes) and 2, 4-diphenyl-4-methyl-1-pentene (2, 4-diphenyl-4-methyl-1-pentene). These may be used alone in 1 kind or in combination of 2 or more kinds.
Regarding the monomer ratio in the amphoteric polyacrylamide copolymer (a), in view of ion balance or subsequent reaction with an amide group dialdehyde compound, the preferable range is 74.0 to 99.7 mol% of (meth) acrylamide, 0.1 to 12.0 mol% of a cationic vinyl monomer, 0.1 to 10.0 mol% of an anionic vinyl monomer, 0.1 to 4.0 mol% of a (meth) allyl group-containing monomer, and more preferable ranges are 83.0 to 99.7 mol% of (meth) acrylamide, 0.1 to 8.0 mol% of a cationic vinyl monomer having a tertiary amino group, 0.1 to 7.0 mol% of an anionic vinyl monomer, and 0.1 to 2.0 mol% of a (meth) allyl group-containing monomer.
The amphoteric polyacrylamide copolymer (a) can be obtained by a known polymerization method without any particular limitation on the method for producing the copolymer. In order to improve the adhesion to pulp, the papermaking additive of the present invention is preferably prepared by stepwise or dropwise polymerization of the monomer component.
The number average molecular weight and molecular weight distribution of the amphoteric polyacrylamide copolymer (a) are not particularly limited, but the molecular weight increases upon reaction with the dialdehyde compound and exceeds the appropriate range of the number average molecular weight and molecular weight distribution, and therefore, the number average molecular weight is preferably 5 to 300 ten thousand, and the molecular weight distribution is preferably 2.0 to 7.0.
The method for producing the aldehyde-functionalized polyacrylamide (A) in the present invention is not particularly limited. For example, aldehyde-functional polyacrylamide (A') can be obtained by reacting a dialdehyde compound (b) with an amphoteric polyacrylamide copolymer (a) under the following conditions (1) to (5).
(1) The molar ratio of the dialdehyde compound (b) to the amide group of the amphoteric polyacrylamide copolymer (a) is 10-60%,
(2)pH7.5～12.5，
(3) the temperature is 1-60 ℃,
(4) the concentration of the amphoteric polyacrylamide copolymer (a) before reaction is 0.5 to 11.0 mass%,
(5) the time is 20 seconds to 4 hours.
The dialdehyde compound (b) reacted with the amphoteric polyacrylamide copolymer (a) may be selected from the group consisting of glyoxal, glutaraldehyde, 2,5-diformylfuran (2, 5-diformylfuran), 2-hydroxyhexanedialdehyde (2-hydroxyhexanedialdehyde), succinaldehyde (succinaldehyde), and combinations thereof. Glyoxal is most preferred from the viewpoint of reactivity or drainage effect.
The amount of the dialdehyde compound (b) to be reacted with the amphoteric polyacrylamide copolymer (a) is preferably mixed and reacted with the amphoteric polyacrylamide copolymer (a) in a molar ratio of 10 to 60% based on the amide groups in the copolymer (a) in the production method of the present invention from the viewpoints of reaction efficiency and effect (production condition 1). By performing such a reaction, the amide reaction rate, which is the ratio of the amide group of the aldehyde-functionalized polyacrylamide (A) to the amide group of the dialdehyde compound to the amide group of the aldehyde compound, is easily 3 to 20 mol%,
the step of reacting the amphoteric polyacrylamide copolymer (a) with the dialdehyde compound (b) is preferably carried out under production condition 2, since the reaction of the amphoteric polyacrylamide copolymer (a) with the dialdehyde compound (b) can be accelerated by adding an alkali if necessary and adjusting the pH of the reaction solution to 7.5 to 12.5.
When the temperature at which the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) are reacted is in the range of 1 to 60 ℃, the reaction of the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) is accelerated, and thus (production condition 3) is preferable.
When the concentration of the amphoteric polyacrylamide copolymer (a) before reaction is in the range of 0.5 to 11.0% by mass, the molecular weight, the intrinsic viscosity, and the aldehyde-functional amide content can be easily adjusted while suppressing thickening of the reaction solution, and thus the method is preferable (production condition 4).
The reaction time of the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) is preferably in the range of 20 seconds to 4 hours, because the reaction of the polyacrylamide and the dialdehyde compound can be accelerated (production condition 5).
The polyacrylamide-based papermaking additive containing the aldehyde-functional polyacrylamide (A) of the present invention satisfies all of the following conditions (1) to (3):
(1) the aldehyde-functionalized polyacrylamide (A) has an amide reaction rate of 3 to 20 mol% based on the ratio of the amide group of the dialdehyde compound to the amide group of the (meth) acrylamide constituent unit before the dialdehyde is added,
(2) the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) is 50 to 400 ten thousand,
(3) the aldehyde-functionalized polyacrylamide (A) has an isoelectric point with an ionization degree of 0meq/g at a pH value of 3.5-8.5.
In the aldehyde-functionalized polyacrylamide (a), the ratio of the amide group to which the dialdehyde compound is added to the amide group of the amide-functionalized polyacrylamide (a), i.e., the amide reaction rate, must be 3 to 20 mol% (see condition 1 for polyacrylamide (a)), and more preferably 3 to 15 mol%. The said amide reaction rate is obtained by13Measured by C-NMR, from 179 to 181ppm (peak of aldehyde-functional amide) by 182 to 185ppm (peak of amide group)The ratio of the ratio is obtained. When the amide reaction rate is less than 3%, the amount of aldehyde groups in the polymer is insufficient, and when it is more than 20%, the reaction proceeds excessively, so that the cross-linking reaction between the polymers occurs via the dialdehyde compound, and finally the amount of aldehyde groups in the polymer is insufficient. Therefore, covalent bonds between celluloses based on aldehyde groups cannot be formed, which is disadvantageous in the paper strength-improving effect or drainage.
The number average molecular weight of the aldehyde-functionalized polyacrylamide (A) must be in the range of 50 to 400 million (polyacrylamide (A) condition 2), more preferably 50 to 300 million. If the number average molecular weight is less than 50 ten thousand, the adhesion effect is poor because the proportion of the low molecular weight polymer component contained therein, which contributes little to the adhesion to the pulp, is large. When the amount exceeds 400 ten thousand, the pulp is coagulated to deteriorate the paper, and the paper strength-enhancing effect is not good. The number average molecular weight in the present invention refers to a value obtained by a GPC-MALS method in which a multi-angle light scattering detector is connected to GPC.
The aldehyde-functionalized polyacrylamide (A) must have an isoelectric point of 0meq/g of ionization at a pH of 3.5 to 8.5 (polyacrylamide (A) condition 3). When the isoelectric point is in the range of pH3.5 to 8.5, the polymers in the papermaking system form a complex (complex) by the ionic interaction of cations and anions, and the effect of adhesion to pulp is enhanced, so that the paper strength enhancing effect and drainage are advantageous. The isoelectric point as referred to herein means a value measured by a PCD potentiometer, but is not limited to this device as long as it can be measured by the same principle.
The molecular weight distribution of the aldehyde-functionalized polyacrylamide (A) is preferably 2.0 to 8.0, more preferably 2.0 to 7.0. The molecular weight distribution is the ratio (Mw/Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn), and excessive coagulation of pulp is likely to occur when the molecular weight distribution exceeds 8.0. The aldehyde-functional polyacrylamide (A) having an appropriate molecular weight distribution is less likely to cause deterioration of paper due to excessive coagulation of pulp, and is advantageous in paper strength-enhancing effect. In the present invention, the weight average molecular weight necessary for obtaining the molecular weight distribution is a value obtained by a GPC-MALS method in which a multi-angle light scattering detector is connected to GPC.
The polyacrylamide-based papermaking additive of the present invention contains the aldehyde-functional polyacrylamide (a) as a main component, and preferably has a proportion of 60 mass% or more, more preferably 80 mass% in terms of the total solid content. In addition, the polyacrylamide-based papermaking additive of the present invention may contain an unreacted dialdehyde compound. In this case, it is preferable to add an acid to adjust the pH to 2.5 to 4.5, and to use the resulting mixture as an additive for papermaking after the reaction with the dialdehyde compound is stopped. However, when the reaction is immediately carried out, the reaction solution may be directly added to the pulp slurry without lowering the pH. Examples of the base for adjusting pH include sodium hydroxide, potassium hydroxide, and ammonia, and examples of the acid include sulfuric acid, hydrochloric acid, and acetic acid. In addition, preservatives, defoaming agents, and the like may also be contained.
It is preferable to add the polyacrylamide-based papermaking additive of the present invention to a pulp slurry (hereinafter, sometimes referred to simply as "internal addition").
The pulp slurry is obtained by diluting the pulp with water to form a slurry. Examples of the pulp include: bleached or unbleached chemical pulp such as kraft pulp and sulfite pulp; bleached or unbleached high retention pulp such as groundwood pulp, mechanical pulp, thermomechanical pulp and the like; old paper pulp such as old newspapers, old magazines, old corrugated paper, deinked old paper and the like.
The amount of the polyacrylamide-based papermaking additive to be added is usually 0.01 to 3.0% by mass, preferably 0.05 to 2.5% by mass, and more preferably 0.1 to 2.0% by mass, based on the solid content of the pulp. When an aluminum compound such as bauxite sulfate or polyaluminum chloride (PAC) is added, it is preferable to add 0.1 to 1.0% by mass based on the solid content of the pulp. Further, examples of a method for adding the polyacrylamide-based papermaking additive to the pulp slurry include: any method may be used, for example, a method of adding the polyacrylamide-based papermaking additive without using any aluminum compound, a method of adding the polyacrylamide-based papermaking additive after adding the polyacrylamide-based papermaking additive, a method of adding the aluminum compound and the polyacrylamide-based papermaking additive at the same time, and the like.
According to the present invention, when making paper, acidic pulp slurry using aluminum sulfate, or neutral pulp slurry using no or a small amount of aluminum sulfate may be used. In addition, the pulp slurry can be usedAn acidic rosin-based sizing agent, a neutral rosin-based sizing agent, an alkyl ketene dimer-based sizing agent, an olefin-based or alkyl succinic anhydride-based sizing agent, and the like are added. Examples of the method of adding these sizing agents include: a method of adding a sizing agent to a pulp slurry and then adding a polyacrylamide-based papermaking additive, a method of diluting a polyacrylamide-based papermaking additive, mixing the diluted polyacrylamide-based papermaking additive with a sizing agent in advance, and then adding the diluted polyacrylamide-based papermaking additive. Further, the pulp slurry may suitably contain: fillers such as clay, kaolin, calcium carbonate, barium sulfate, titanium dioxide, and the like; sizing agents other than the above-mentioned sizing agents, sizing adhesives, internal paper strength agents other than the present invention (dry paper strength agents, wet paper strength agents), antifoaming agents, pH adjusting agents, dyes, optical brighteners, retention aids, and the like. In addition, the manufactured paper usually has a grammage of 10 to 400g/m2Left and right.
Further, if necessary, starch, surface paper strength enhancers such as polyvinyl alcohol and acrylamide polymers, surface sizing agents, dyes, paints, and anti-slip agents may be applied by a size sprayer, a horizontal roll coater (gate roll coater), a Bill blade coater (calender), a calender (calender), or the like.
When the above-mentioned polyacrylamide-based additive for papermaking of the present invention is added to a pulp slurry, the papermaking pH of the pulp slurry containing other additives added as needed is preferably 3.5 to 8.5, more preferably 6.5 to 8.5, from the viewpoint of the paper strength-enhancing effect. In the present invention, the paper pH refers to the pH of the pulp slurry before paper machine dewatering, and the pH of the pulp slurry before paper machine dewatering corresponds to the pH of the headbox in terms of general practice.
Examples of the paper produced by using the polyacrylamide-based papermaking additive of the present invention include: such as PPC paper, light-sensitive paper base paper, hot paper base paper, art paper, polishing coating paper, high-grade coating paper, such as toilet paper, such as fruit bag base paper, washing label base paper, decorative board base paper, wallpaper base paper, printing paper, laminated board base paper, food container base paper, heavy bag double-layer kraft paper, single-side kraft paper, electrical insulation paper, lining, middle core, paper tube base paper, gypsum board base paper, newspaper paper, paperboard, etc. No matter what paper making process, the practical paper strength enhancing effect can be provided for the paper tape made by paper making. Among them, it is particularly preferable to use the paper requiring paper strength or the paper restricted to use of alumina sulfate (information paper, coating base paper, paperboard). In addition, the paper of the present invention also includes paperboard.
Examples
The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples. In each example, unless otherwise specified, parts and% are by mass. The physical property values of the respective examples were measured by the following methods.
The number average molecular weight, weight average molecular weight and molecular weight distribution were obtained by GPC-MALS method in which a multi-angle light scattering detector was connected to GPC under the following measurement conditions.
HPLC: agilent1100 series
Column (column): SHODEX SB806MHQ manufactured by SHOWA DENKO K.K
Leacheate: phosphate buffer containing sodium nitrate (pH3)
Flow rate: 1.0 ml/min
The detector 1: multi-angle light scatter detector DAWN manufactured by American Huanya stunt technology corporation
The detector 2: difference refractive index detector RI-101 manufactured by Showa Denko K.K
(production of amphoteric Polyacrylamide copolymer (a))
Production example 1
Into a 1 liter four-necked flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen gas introducing tube were charged 260.00g of water, 126.81g of a 50% acrylamide aqueous solution as a monomer (1), 0.10g of dimethylacrylamide, 15.60g of a 30% sulfuric acid aqueous solution, 15.72g of dimethylaminoethyl methacrylate and 1.27g of sodium methallylsulfonate. Subsequently, the temperature was raised to 60 ℃ under a nitrogen atmosphere, 0.24g of ammonium persulfate was added as a polymerization initiator to start polymerization, and the reaction temperature was raised to 90 ℃. Thereafter, 180.00g of water was added, 132.49g of a 50% acrylamide aqueous solution as the monomer (2), 0.10g of dimethylacrylamide, 5.40g of acrylic acid, 1.27g of sodium methallylsulfonate, and 0.48g of ammonium persulfate were further added, and when the viscosity was estimated to be 3000 mPas at 25 ℃, water 290.00 was immediately added to obtain an amphoteric polyacrylamide copolymer (a-1) having a solid content of 15.0%. The measurement results of the proportion (mol%), the number average molecular weight, the weight average molecular weight, and the molecular weight distribution of the monomer units constituting the amphoteric polyacrylamide copolymer (a-1) are given in table 1.
Production examples 2 to 14 and comparative production examples 1 to 6
Amphoteric polyacrylamide copolymers (a-2) to (a-14) and (ra-1) to (ra-6) having a solid content of 15.0% were obtained in the same manner as in production example 1, except that the compositions of the monomers (1) and (2) were changed as shown in Table 1. The measurement results of the proportions (mol%), number average molecular weights, weight average molecular weights, and molecular weight distributions of the monomer units constituting the amphoteric polyacrylamide copolymers (a-2) to (a-14) and (ra-1) to (ra-6) are shown in Table 1.
[ Table 1]
The abbreviations in table 1 have the following meanings:
AAm: acrylamide
DM: dimethylaminoethyl methacrylate
DMC: 2- (methacryloyloxy) -N, N, N-trimethylethanaminium chloride
(2-(methacryloyloxy)-N,N,N-trimethylethanammonium chlorid)
DPA: n- (2-dimethylaminoethyl) acrylamide (N- [2- (dimethylamino) ethyl ] acrylamide)
DADMAC: diallyl dimethyl ammonium chloride
IA: itaconic acid
AGA: 2-acrylamido-N-glycolic acid
AAc: acrylic acid
SMAS: sodium methallyl sulfonate
HEMAC: dimethyl hydroxyethyl methyl ammonium chloride
MET: mercaptoethanol
MBAAm: methylene bisacrylamide
DMAAm: dimethylacrylamide
Mn: number average molecular weight
Mw: weight average molecular weight
Mw/Mn: molecular weight distribution
(reaction of amphoteric Polyacrylamide copolymer (a) with dialdehyde Compound (b))
Example 1
12.69g of a 15% aqueous solution of the amphoteric polyacrylamide copolymer (a-1) prepared in production example 1, 163.00g of ion-exchanged water, and 1.16g of a 40% aqueous solution of glyoxal as the dialdehyde compound (b) (35 mol% based on the amide group of the copolymer (a)) were added to a 200mL beaker, and the temperature was raised to 35 ℃ while stirring at 180 rpm. The pH at this point was 3.8. Subsequently, 2.66g of a 5.0% aqueous sodium hydroxide solution was added and the pH was adjusted to 10.0, thereby starting the reaction. After stirring for 30 minutes, 0.67g of a 30% aqueous solution of sulfuric acid was added to adjust the pH to 3.0, thereby stopping the reaction. The reaction conditions of the amphoteric polyacrylamide copolymer (a) and the dialdehyde compound (b) are shown in Table 2. The measurement results of the number average molecular weight, weight average molecular weight, molecular weight distribution and amide reaction rate of the resulting polyacrylamide-based additive for papermaking (a-1) are shown in table 3. Note that the amide reaction rate was determined by using INVOA (400MHz) manufactured by VARIAN13C-NMR measurement.
The ionization degree of the polyacrylamide-based additive for papermaking (a-1) was measured by adjusting the polymer concentration to 0.1 wt% with a PCD potentiometer PCD02 (manufactured by MUTEC corporation) and measuring an aqueous solution adjusted in pH with an acid or alkali component. As a result, the isoelectric point was 0meq/g, which was pH4.4, and it was confirmed that the isoelectric point existed in the range of pH3.5 to 8.5. The results are given in table 3.
Examples 2 to 16 and comparative examples 1 to 10
Polyacrylamide papermaking additives containing aldehyde-functionalized polyacrylamides (A-2) to (A-16) and (RA-1) to (RA-10) were obtained in the same manner as in example 1, except that the kind, reaction temperature, pH, concentration, time and amount of glyoxal (mol% is based on the amide group in the copolymer (a)) of the amphoteric polyacrylamide copolymer (a) were changed as shown in Table 2. The number average molecular weight, molecular weight distribution, amide reaction rate, and isoelectric point of the obtained aldehyde-functionalized polyacrylamide were measured in the same manner as in example 1, and the measurement results are shown in Table 3.
[ Table 2]
[ Table 3]
< production and evaluation of paperboard using low-conductivity old paper pulp slurry and alumina sulfate >
Application example 1
Bauxite sulfate was added to an old corrugated paper pulp slurry having a concentration of 2.4%, a freeness (canadian standard freeness) of 350 and a conductivity of 200mS/m, and the amount of the added bauxite sulfate was 0.5% by mass based on the solid content of the pulp. Then, the polyacrylamide-based papermaking additive obtained in example 1 was added in an amount of 0.3 mass% in terms of solid content relative to the solid content of pulp. After The pulp slurry was stirred, The pulp concentration was diluted to 0.8% with water having a pH of 7.0, and then The Noble was used&The paper was made by a paper machine manufactured by Wood company, and dried at 100 ℃ for 120 seconds by a drum dryer after extrusion to obtain a grammage of 80g/m2The paper of (1). The resulting paper was evaluated for the fracture coefficient and internal bond (internal bond) described below, and the results are shown in table 4. Further, the pulp slurry was adjusted as described above until the pulp concentration became 0.8%, and then the drainability evaluation (DDT) was performed, and the results are shown in table 4.
Fracture coefficient: the measurement was carried out in accordance with JIS P8112.
Internal combination: it was prepared according to JAPAN TAPPI 18-2.
DDT: the diluted pulp slurry (concentration: 0.8%) was poured into a 7.5cm diameter drainage apparatus in 500mL using a device similar to the "dynamic drainage Jar" described in Tappi volume 56, No. 10 (1973) page 46, and filtered through a 100 mesh wire gauze by opening a lower valve while stirring at 600rpm, and the time taken to reach a certain amount of filtrate was measured, and the amount of filtrate was used to evaluate the drainability. The time until the amount of the filtrate reached 100g was measured. A smaller number indicates better drainage.
Application examples 2 to 32 and application comparative examples 1 to 24
The same operation as in application example 1 was carried out except that the kinds and mass% of the polyacrylamide-based papermaking additives in application example 1 were changed as shown in Table 4, to obtain a grammage of 80g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 4. The drainability evaluation (DDT) was also performed as in application example 1, and the results are shown in table 4.
[ Table 4]
< production and evaluation of a paperboard with a low conductivity old paper pulp slurry but without bauxite sulfate >
Application example 33
The polyacrylamide-based additive for papermaking obtained in example 1 was added to a used corrugated paper pulp slurry having a concentration of 2.4%, a freeness (canadian standard freeness) of 350 and a conductivity of 200mS/m, and the amount of the addition was 0.3% by mass in terms of solid content relative to the solid content of the pulp. After The pulp slurry was stirred, The pulp concentration was diluted to 0.8% with water having a pH of 7.0, and then The Noble was used&The paper was made by a paper machine manufactured by Wood company, and dried at 100 ℃ for 120 seconds by a drum dryer after extrusion to obtain a grammage of 80g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 5. The drainability evaluation (DDT) was also performed as in application example 1, and the results are shown in table 5.
Application examples 34 to 64 and application comparative examples 25 to 48
The same procedures as in application example 33 were carried out except that the kinds and mass% of the polyacrylamide-based papermaking additives in application example 33 were changed as shown in Table 5, to obtain a grammage of 80g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 5. The drainability evaluation (DDT) was also performed as in application example 1, and the results are shown in table 5.
[ Table 5]
< production and evaluation of a paperboard using a high-conductivity old paper pulp slurry and alumina sulfate >
Application example 65
Bauxite sulfate was added to an old corrugated paper pulp slurry having a concentration of 2.4%, a freeness (canadian standard freeness) of 350 and a conductivity of 800mS/m, and the amount of the added bauxite sulfate was 0.5% by mass based on the solid content of the pulp. Then, the polyacrylamide-based papermaking additive obtained in example 1 was added in an amount of 0.3 mass% in terms of solid content relative to the solid content of pulp. After The pulp slurry was stirred, The pulp concentration was diluted to 0.8% with water having a pH of 7.0, and then The Noble was used&The paper was made by a paper machine manufactured by Wood company, and dried at 100 ℃ for 120 seconds by a drum dryer after extrusion to obtain a grammage of 80g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 6. The drainability evaluation (DDT) was also carried out in the same manner as in application example 1, and the results are shown in Table 6.
Application examples 66 to 85 and comparative application examples 49 to 60
The same procedures as in application example 65 were carried out except that the kinds of the polyacrylamide-based papermaking additives in application example 65 were changed as shown in Table 6, to obtain a grammage of 80g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 6. The drainability evaluation (DDT) was also carried out in the same manner as in application example 1, and the results are shown in Table 6.
[ Table 6]
< production and evaluation of paper Using BKP >
Application example 81
To a mixed pulp slurry of broadleaf bleached kraft pulp (LBKP)/cb (coat broke) 8/2 having a concentration of 2.4%, a freeness (canadian standard freeness) of 410 and a conductivity of 100mS/m, 0.1 mass% of bauxite sulfate was added in terms of alumina relative to the solid content of the pulp, and then 0.3 mass% of the polyacrylamide internal strength agent obtained in example 1 was added in terms of solid content. The pulp slurry was stirred, and then The pulp concentration was diluted to 0.8% with water having a pH of 7.5, and further 10% of calcium carbonate (TP 121, product of Orthomson industries, Ltd.) was added with stirring, and The Noble was used&The paper was made by a paper machine manufactured by Wood company, and dried at 100 ℃ for 100 seconds by a drum dryer after extrusion to obtain a grammage of 60g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 1, and the results are shown in Table 7. The drainability evaluation (DDT) was also carried out in the same manner as in application example 1, and the results are shown in Table 7.
Application examples 82 to 112 and application comparative examples 61 to 84
The same procedures as in application example 81 were carried out except that the mass% of alumina sulfate and the type of the polyacrylamide type internal paper strength additive in application example 81 were changed as shown in Table 7 to obtain a grammage of 60g/m2The paper of (1). The paper thus obtained was evaluated in the same manner as in application example 81, and the results are shown in Table 7. Further, the drainability evaluation (DDT) was carried out in the same manner as in application example 81, and the results are shown in Table 7.
[ Table 7]
< evaluation of improvement of Water repellency of paperboard >
Application example 113 and application comparative example 85
0.5 mass% of bauxite sulfate was added to an old pulp slurry of corrugated paper having a concentration of 2.4%, a freeness (Canadian Standard freeness) of 350 and a conductivity of 200mS/m, based on the solid content of the pulp. Then, the polyacrylamide-based papermaking additive obtained in example 1 was added in an amount of 0.3% by mass in terms of solid content relative to the solid content of pulp. After stirring the pulp slurry, the pulp concentration was diluted to 0.8% with water of ph 7.0. Then, the sheet was dewatered in vacuum (degree of vacuum 30kpa, 60 seconds) with a paper machine (pulse sheet former) to obtain a sheet with a grammage of 400 g. A sponge and a filter paper were stacked on the paper sheet, and pressed with a flat press at 4.2kgf-1 for 1 second. The wet moisture content of the squeezed paper web was calculated from the weight of the squeezed paper web and the weight of the paper web dried at 110 ℃ for 2 hours, and the results are shown in Table 8.
[ Table 8]
As is apparent from tables 4 to 7, the polyacrylamide-based papermaking additives of the present invention described in the examples are excellent in adhesion to pulp, regardless of the pulp conductivity and the presence or absence of bauxite sulfate, and are rated excellent at a level satisfying both paper strength and drainage properties, as compared with the polyacrylamide-based papermaking additives of the comparative examples which do not satisfy the structure and condition of the present invention in item 1.
From the results of the application examples using the polyacrylamide-based papermaking additives of examples 1, 6 and 7, it is understood that the polyacrylamide-based papermaking additives having a molecular weight distribution within a more preferable range of 2.0 to 8.0 are superior in paper strength-enhancing effect to those having a molecular weight distribution outside the range.
From the results of the application examples using the polyacrylamide-based papermaking additive of examples 1, 9, 10, 11 and 12, it is understood that the paper strength-enhancing effect is more excellent if the proportion of the monomer unit constituting the amphoteric acrylamide copolymer (a) is within a more preferable range.
From the results of the application examples using the polyacrylamide-based papermaking additives of examples 1, 8, 15 and 16, it is understood that the paper strength-enhancing effect and the drainability are more excellent if the cationic vinyl monomer unit constituting the amphoteric polyacrylamide copolymer is a more preferable tertiary amine.
From table 8, it is apparent from the results of the application examples using the polyacrylamide-based papermaking additives of example 1 and comparative example 1 that the polyacrylamide-based papermaking additive of the present invention has a low wet paper moisture percentage, excellent paper strength enhancing effect, water drainability, and water squeeze ability enhancing effect even if the monomer composition and the number average molecular weight are about the same by introducing an aldehyde group into the polymer structure.
Claims (9)
1. A polyacrylamide-based papermaking additive containing an aldehyde-functionalized polyacrylamide (A), which is a dialdehyde compound adduct of an amphoteric polyacrylamide copolymer (a) having, as polymer constituent units, (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer and a (meth) allyl group-containing monomer, and which satisfies all of the following conditions (1) to (3):
(1) the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the dialdehyde compound, in the aldehyde-functionalized polyacrylamide (A) is 3 to 20 mol%,
(2) the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) is 50 to 400 ten thousand,
(3) the aldehyde-functionalized polyacrylamide (A) has an isoelectric point with an ionization degree of 0meq/g at a pH value of 3.5-8.5.
2. The polyacrylamide-based papermaking additive as defined in claim 1, wherein the molecular weight distribution of the aldehyde-functional polyacrylamide (A) is 2.0 to 8.0.
3. The polyacrylamide-based papermaking additive as defined in claim 1 or 2, wherein the proportions of the polymer constituent units are: 74.0 to 99.7 mol% of (meth) acrylamide, 0.1 to 12.0 mol% of a cationic vinyl monomer, 0.1 to 10.0 mol% of an anionic vinyl monomer, and 0.1 to 4.0 mol% of a (meth) allyl group-containing monomer.
4. The polyacrylamide-based papermaking additive as defined in claim 1 or 2, wherein the cationic vinyl monomer as a constituent unit of the polymer has a tertiary amino group.
5. The polyacrylamide-based papermaking additive as defined in claim 3 wherein the cationic vinyl monomer as a constituent unit of the polymer has a tertiary amino group.
6. A process for producing an aldehyde-functionalized polyacrylamide (A) -containing polyacrylamide-based papermaking additive, which comprises reacting an amphoteric polyacrylamide copolymer (a) obtained by polymerizing (meth) acrylamide, a cationic vinyl monomer, an anionic vinyl monomer and a (meth) allyl group-containing monomer with a dialdehyde compound (b) to obtain an aldehyde-functionalized polyacrylamide (A), wherein the following conditions (1) to (3) are all satisfied:
(1) the amide reaction rate, which is the ratio of the amide group added with the dialdehyde compound to the amide group added with the dialdehyde compound, in the aldehyde-functionalized polyacrylamide (A) is 3 to 20 mol%,
(2) the number average molecular weight of the aldehyde-functionalized polyacrylamide (A) is 50 to 400 ten thousand,
(3) the aldehyde-functionalized polyacrylamide (A) has an isoelectric point with an ionization degree of 0meq/g at a pH value of 3.5-8.5.
7. The process for producing the polyacrylamide-based papermaking additive according to claim 6, wherein the dialdehyde compound (b) is reacted with the amphoteric polyacrylamide copolymer (a) so as to satisfy the following conditions (1) to (5):
(1) the molar ratio of the dialdehyde compound (b) to the amide group of the amphoteric polyacrylamide copolymer (a) is 10-60%,
(2)pH7.5～12.5，
(3) the temperature is 1-60 ℃,
(4) the concentration of the amphoteric polyacrylamide copolymer (a) before reaction is 0.5 to 11.0 mass%,
(5) the time is 20 seconds to 4 hours.
8. The process for producing the polyacrylamide-based papermaking additive as defined in claim 6, wherein the dialdehyde compound (b) is glyoxal.
9. A method for producing paper, characterized by adding the polyacrylamide-based papermaking additive according to any one of claims 1 to 5 to a pulp slurry in an amount of 0.01 to 3 mass% relative to the solid content of the pulp.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2015254997 | 2015-12-25 | ||
| JP2015-254997 | 2015-12-25 | ||
| PCT/JP2016/088084 WO2017110868A1 (en) | 2015-12-25 | 2016-12-21 | Polyacrylamide-based papermaking additive, method for producing same, and method for producing paper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108026699A CN108026699A (en) | 2018-05-11 |
| CN108026699B true CN108026699B (en) | 2020-10-16 |
Family
ID=59090776
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680049404.7A Active CN108026699B (en) | 2015-12-25 | 2016-12-21 | Polyacrylamide-based additive for papermaking, method for producing same, and method for producing paper |
Country Status (4)
| Country | Link |
|---|---|
| JP (1) | JP6593455B2 (en) |
| KR (1) | KR102063409B1 (en) |
| CN (1) | CN108026699B (en) |
| WO (1) | WO2017110868A1 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220341095A1 (en) * | 2019-09-26 | 2022-10-27 | Arakawa Chemical Industries, Ltd. | Paper-strengthening agent, paper, and method of producing paper |
| KR102463839B1 (en) * | 2020-12-08 | 2022-11-18 | 주식회사 지엔텍 | Shocking absorber for packing having low dust and static electricity |
| CN115652683A (en) * | 2022-11-21 | 2023-01-31 | 江苏富淼科技股份有限公司 | Papermaking method and papermaking system |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS54116411A (en) * | 1979-02-15 | 1979-09-10 | Japan Carlit Co Ltd | Paper strength enhancing agent not affected by ph |
| JPS57149593A (en) * | 1981-03-05 | 1982-09-16 | Kawasaki Heavy Ind Ltd | Treatment of pulp waste liquid |
| JPS57149595A (en) * | 1981-03-09 | 1982-09-16 | Rei Tech Inc | Improvement of paper quality in order to enhance wet paper strength |
| JPH06184985A (en) * | 1992-12-14 | 1994-07-05 | Sumitomo Chem Co Ltd | Production of paper of paperboard having temporary wet paper strength |
| JPH07189177A (en) * | 1993-12-24 | 1995-07-25 | Mitsubishi Oil Co Ltd | Amphoteric paper-strengthening agent and its production |
| AU5489999A (en) | 1998-08-19 | 2000-03-14 | Hercules Incorporated | Dialdehyde-modified anionic and amphoteric polyacrylamides for improving strength of paper |
| EP1399623B1 (en) * | 2001-06-11 | 2015-01-07 | Basf Se | Wet-strength finishing agents for paper |
| US7641766B2 (en) | 2004-01-26 | 2010-01-05 | Nalco Company | Method of using aldehyde-functionalized polymers to enhance paper machine dewatering |
| JP2005336646A (en) * | 2004-05-26 | 2005-12-08 | Mitsui Chemicals Inc | Additive for papermaking and paper obtained therefrom |
| MX2007000123A (en) * | 2004-07-08 | 2007-08-17 | Kemira Oyj | High-performance strength resins in papermaking industries. |
| EP1828480B1 (en) * | 2004-12-21 | 2014-05-21 | Hercules Incorporated | Reactive cationic resins for use as dry and wet strength agents in sulfite ion-containing papermaking systems |
| US7875676B2 (en) | 2006-09-07 | 2011-01-25 | Ciba Specialty Chemicals Corporation | Glyoxalation of vinylamide polymer |
| WO2008157321A2 (en) * | 2007-06-15 | 2008-12-24 | Buckman Laboratories International, Inc. | High solids glyoxalated polyacrylamide |
| US8709207B2 (en) * | 2010-11-02 | 2014-04-29 | Nalco Company | Method of using aldehyde-functionalized polymers to increase papermachine performance and enhance sizing |
| CN102050915B (en) * | 2010-11-30 | 2014-05-07 | 广州星业科技股份有限公司 | Method for preparing polymer for improving paper strength |
| US8636875B2 (en) * | 2011-01-20 | 2014-01-28 | Hercules Incorporated | Enhanced dry strength and drainage performance by combining glyoxalated acrylamide-containing polymers with cationic aqueous dispersion polymers |
| JP5618213B2 (en) * | 2011-05-31 | 2014-11-05 | 星光Pmc株式会社 | Polyacrylamide internal paper strength agent and paper manufacturing method |
-
2016
- 2016-12-21 CN CN201680049404.7A patent/CN108026699B/en active Active
- 2016-12-21 WO PCT/JP2016/088084 patent/WO2017110868A1/en active Application Filing
- 2016-12-21 KR KR1020187011847A patent/KR102063409B1/en active IP Right Grant
- 2016-12-21 JP JP2017558188A patent/JP6593455B2/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN108026699A (en) | 2018-05-11 |
| JP6593455B2 (en) | 2019-10-23 |
| KR102063409B1 (en) | 2020-01-07 |
| WO2017110868A1 (en) | 2017-06-29 |
| KR20180072706A (en) | 2018-06-29 |
| JPWO2017110868A1 (en) | 2018-07-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5832426B2 (en) | Paper, board and cardboard manufacturing methods | |
| US8349134B2 (en) | Method for producing high dry strength paper, paperboard or cardboard | |
| JP5618213B2 (en) | Polyacrylamide internal paper strength agent and paper manufacturing method | |
| JP5156650B2 (en) | Method for producing paper, board and cardboard with high dry strength | |
| EP2087172B1 (en) | A process for improving paper strength | |
| TWI575135B (en) | A coating composition and a process of using the same for making paper having improved dry strength | |
| CN107604755B (en) | Paper strength agent, method for producing paper strength agent, and method for producing paper and paper | |
| CN112601860B (en) | Additive for papermaking, paper and method for producing paper | |
| US9783933B2 (en) | Modified vinylamine-containing polymers and their use in papermaking | |
| CN108026699B (en) | Polyacrylamide-based additive for papermaking, method for producing same, and method for producing paper | |
| CN107849815B (en) | Method for manufacturing paper and board | |
| JP5640458B2 (en) | Method for producing paper-making paper strength enhancer | |
| JP3273534B2 (en) | Papermaking additive and papermaking method | |
| CN110318292B (en) | Surface paper strength enhancer, coating liquid, and method for producing paper | |
| CN113614307B (en) | Paper strength enhancer, paper and method for producing paper | |
| JP2001020198A (en) | Papermaking additive | |
| JP4352587B2 (en) | Paper making method | |
| AU2020202452B2 (en) | Novel additive based on water-soluble polymers and uses thereof | |
| JP2023161607A (en) | Papermaking method for improving yield and freeness | |
| WO2019002686A1 (en) | Methods to enhance alkenyl succinic anhydride sizing on paper | |
| JPH10121396A (en) | Production of paper or paper board |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |