JP4593801B2 - Paper strength enhancement method - Google Patents

Paper strength enhancement method Download PDF

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JP4593801B2
JP4593801B2 JP2001021310A JP2001021310A JP4593801B2 JP 4593801 B2 JP4593801 B2 JP 4593801B2 JP 2001021310 A JP2001021310 A JP 2001021310A JP 2001021310 A JP2001021310 A JP 2001021310A JP 4593801 B2 JP4593801 B2 JP 4593801B2
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polymer
paper strength
cationic polymer
soluble
dispersant
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JP2002294593A (en
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勝利 田中
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ハイモ株式会社
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Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a paper strength enhancing method, and more specifically, produced by dispersion polymerization of a mixture of an anionic monomer and a nonionic monomer in an aqueous salt solution in the presence of a cationic water-soluble polymer. The present invention relates to a method for enhancing paper strength, which comprises dissolving an obtained polymer dispersion in water to form an ion complex and then adding it to a papermaking raw material before paper making.
[0002]
[Prior art]
Usually, anionicity and amphotericity are used as the paper strength enhancer. Of these, amphoteric paper strength enhancers are conventionally copolymers of acrylamide and N, N-dialkylamino (meth) acrylate or N, N-dialkylamino (meth) acrylamide and (meth) acrylic acid. Has been used. Further, N, N-methylenebisacrylamide or the like (JP-A-63-50597) is copolymerized as a cross-linking agent, and more recently, N, N-dimethylacrylamide is copolymerized to show a unique solution property. A paper strength enhancer made of a polymer has been developed (JP-A-5-140893, JP-A-5-287893, JP-A-5-272092, JP-A-7-97790, etc.).
[0003]
On the other hand, paper strength enhancers using “intermolecular amphotericity” are also being studied. This is an application of the same action as an amphoteric polymer by ionic interaction between an anionic polymer and a cationic polymer, and a stronger interaction can be expected than an intramolecular amphoteric polymer. For example, Japanese Patent Application Laid-Open No. 7-90797, Japanese Patent Application Laid-Open No. 10-131086, or Japanese Patent Application Laid-Open No. 10-131085 discloses a prescription.
[0004]
On the other hand, various patents are disclosed for a method for producing a dispersion composed of a cationic water-soluble polymer by coexisting an ionic polymer dispersant in an aqueous salt solution. For example, Japanese Patent Publication No. 2-38131 discloses that a cationic polymer soluble in an aqueous salt solution is used as a dispersant when a dispersion in which the polymer is soluble in the aqueous salt solution and the polymerized polymer is insoluble is produced. The method of making it coexist as is disclosed. Japanese Patent Publication No. 4-39481 discloses that when producing a dispersion composed of an anionic or cationic water-soluble polymer, a polyvalent such as ethylene glycol, propylene glycol, glycerin or polyethylene glycol. It is a method of coexisting. JP-A-10-212320 discloses a method for producing an anionic water-soluble polymer dispersion in an aqueous salt solution. The cationic polymer coexisting at the time of polymerization is 1 to 10% by weight with respect to the monomer.
[0005]
Since the paper strength enhancer is a necessary condition for being added to the papermaking raw material and quickly dissolved, the solution type dominates. However, since the intramolecular or intermolecular amphoteric polymer is a solution type, the concentration increases from 15% to 20%. A high-concentration solution type paper strength enhancer has also been studied, but the relationship between the molecular weight and the apparent viscosity related to the effect has not yet been overcome. Although a high concentration can be expected in the case of a dispersion, a polymer dispersion type paper strength enhancer has not yet appeared in the market, and its production formulation is not disclosed.
[0006]
[Problems to be solved by the invention]
An object of the present invention is to develop a formulation of a polymer fine particle dispersed paper strength enhancer that can be expected to have a high concentration.
[0007]
[Means for Solving the Problems]
As a result of intensive studies to solve the above problems, the inventors have reached the invention as described below. That is, the invention of claim 1 has a weight average molecular weight of 1,000,000 to 5,000,000 comprising fine polymer particles by a dispersion polymerization method in the presence of a dispersing agent comprising a cationic polymer soluble in the aqueous salt solution. The anionic water-soluble polymer is a dispersion obtained by polymerizing an anionic water-soluble polymer, and the anionic water-soluble polymer is 5 to 30 mol% of an anionic monomer represented by the following general formula (1): A polymer of a monomer mixture composed of 70 to 95 mol% of (meth) acrylamide and 0 to 20 mol% of another nonionic monomer that can be copolymerized, and the dispersant comprising the cationic polymer is the anion 0.5 to 3.0 times the ionic equivalent of the water-soluble water-soluble polymer and the weight ratio of monomer: cationic polymer = 1: 0.26 to 1: 0.43 Dissolve the produced dispersion in water and polyion After generating the Npurekussu a paper strength method characterized by adding to the papermaking raw material before papermaking.
[Chemical 1]
R 1 is hydrogen, methyl group or carboxymethyl group, R 2 is hydrogen or carboxyl group, A is SO 3 , C 6 H 4 SO 3 , CONHC (CH 3 ) 2 CH 2 SO 3 or COO, Y is hydrogen or positive Ion [0008]
The invention according to claim 2 is the paper strength enhancing method according to claim 1, wherein the dispersant comprising the cationic polymer is a polyacrylamide Hoffman reaction product.
[0009]
A third aspect of the present invention is the paper strength enhancing method according to the first aspect, wherein the dispersing agent comprising the cationic polymer is a vinylamine polymer.
[0010]
The invention according to claim 4 is the paper strength enhancing method according to claim 1, wherein the dispersing agent comprising the cationic polymer is a copolymer of a vinyl cationic monomer and acrylamide. .
[0011]
The invention according to claim 5 is characterized in that the cation equivalent of the dispersant composed of the cationic polymer soluble in the aqueous salt solution is 3.0 to 10.0 meq / g. This is a paper strength enhancement method.
[001 2 ]
The invention according to claim 6 is the paper strength enhancing method according to claim 1, wherein the anionic water-soluble polymer has a weight average molecular weight of 1,000,000 to 5,000,000.
[00 13 ]
The invention of claim 7, the salt constituting the aqueous salt solution is a method for producing an anionic water-soluble polymer dispersion according to claim 1, characterized in that it contains at least one polyvalent anion salt.
[00 14 ]
DETAILED DESCRIPTION OF THE INVENTION
The polymer dispersion used in the paper strength enhancing method of the present invention is 5 to 30 mol% of an anionic monomer represented by the general formula (1), 70 to 95 mol% of (meth) acrylamide and copolymerizable. Polymer fine particles obtained by dispersing a monomer mixture composed of 0 to 20 mol% of other nonionic monomers in a salt aqueous solution in the presence of a dispersant composed of a cationic polymer soluble in the salt aqueous solution. An anionic water-soluble polymer consisting of The dispersant composed of the cationic polymer is produced by coexisting 0.5 to 3.0 times the ion equivalent of the anionic water-soluble high component. The ion equivalent of the dispersing agent composed of the cationic polymer to be coexistent is 3.0 to 10.0 meq / g, preferably 4.0 to 10.0 meq / g. If this is expressed in terms of mol% of the cationic group in the cationic polymer, it is about 25 mol% in the case of the Hoffman reactant hydrochloride or N-vinylformamide polymer hydrochloride hydrolyzate of polyacrylide. To about 80 mol%, preferably about 30 mol% to about 80 mol%. In the case of dimethylaminoethyl methacrylate sulfate / acrylamide copolymer, it is about 30 mol% or more, preferably about 50 mol% or more. Alternatively, in the case of dimethyldiallylammonium chloride / acrylamide copolymer, it is about 30 mol% or more, preferably about 40 mol% or more.
[00 15 ]
The weight ratio between the monomer and the cationic polymer is as follows. In the case of acrylic acid / acrylamide = 12/88 (mol%), if Hoffman reactant hydrochloride of N-vinylformamide or hydrochloric acid hydrolyzate of N-vinylformamide polymer, cationization degree 60 mol% is used, When the cationic polymer is added so that the equivalent ratio is 0.5 to 3.0, the weight ratio becomes monomer: cationic polymer = 1: 0.2 to 1: 1.2.
[00 16 ]
The cationic polymer used in the present invention becomes a dispersing agent at the time of polymerization, dissolves the dispersion after production in water, and adds it to the papermaking raw material before papermaking. It also functions as a yield improver that forms a polymer and polyion complex. Therefore, it is preferable that the amount is larger than the equivalent with respect to the ion equivalent of the anionic water-soluble polymer. Usually 0.5 to 3.0 times coexist, but preferably 1.0 to 2.0 times.
[00 17 ]
Specific examples of the cationic polymer used in the present invention include the above-mentioned polyacrylidohoffman reaction product or N-vinylformamide polymer acid hydrolyzate, dimethylaminoethyl (meth) acrylate, ( Examples thereof include a copolymer of acrylamide with diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide or a quaternized product thereof, or dimethyldiallylammonium chloride. Generally, primary amino group-containing cationic polymers have a high aggregating action, so that when Hoffman reaction product of polyacrylide or N-vinylformamide polymer acid hydrolysis is used as a dispersant, the drainage of papermaking raw material increases. preferable. However, when the papermaking pH is increased to 6.5 to 8 and the like, these cationic polymers have low dissociation and do not increase freeness. In such a case, a cationic polymer obtained by copolymerizing a tertiary or quaternary ammonium base-containing acrylic or diallylammonium salt monomer is used.
[00 18 ]
Examples of anionic monomers copolymerized with (meth) acrylamide include acrylic acid, methacrylic acid, itaconic acid, maleic acid, vinyl sulfonic acid, vinyl benzene sulfonic acid or 2-acrylamido 2-methylpropane sulfonic acid. is there.
[00 19 ]
Further, the paper strength enhancer comprising this polymer dispersion can be copolymerized with other nonionic monomers. For example, (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide Etc.
[00 20 ]
The copolymerization molar ratio of these monomers used for polymerization is 5 to 30 mol% of anionic monomer, 70 to 95 mol% of acrylamide and 0 to 20 mol% of other nonionic monomer capable of copolymerization. Preferably, it is anionic monomer mol%, acrylamide 78-95 mol% and other copolymerizable nonionic monomers 0-10 mol%.
[00 21 ]
The weight average molecular weight of the cationic polymer used as the dispersant is 100,000 to 3,000,000, preferably 500,000 to 3,000,000. As described above, since the cationic polymer functions as a dispersant and a yield improver, the higher the molecular weight, the better the drainage. However, if the molecular weight is too high, it affects the texture and is not preferable. Further, the function as a dispersant tends to decrease even if the molecular weight is too high, and falls within the above range. One anionic water-soluble polymer has a weight average molecular weight of 1,000,000 to 5,000,000, preferably 2,000 to 3,000,000. Usually, the molecular weight of a commercially available amphoteric paper strength enhancer is about 2 million to 5 million, but in the case of the present invention, since a cationic polymer and a polyion complex are formed, the apparent molecular weight increases, The molecular weight of the polymer is preferably not too high, and falls within the above range.
[00 22 ]
The polymerization concentration is in the range of about 20 to 40% by weight, preferably 20 to 30% by weight. However, the polymerization concentration here also means the concentration when the supply of all the monomers is completed by adopting a method of adding the monomer dividedly. The higher the polymerization concentration, the better the productivity and transportability. However, when the polymerization concentration is too high, a stable dispersion cannot be obtained and the above range is obtained. The monomer concentration at the start is 15 to 25%, and a method in which the monomer is additionally supplied to increase the concentration and finally 20 to 40% by weight can be employed.
[00 23 ]
The polymerization conditions are usually appropriately determined according to the monomer used and copolymerization mol%, and the temperature is in the range of 0 to 100 ° C., preferably 20 to 80 ° C. For the initiation of polymerization, a radical polymerization initiator is used. These initiators may be either oil-soluble or water-soluble, and can be polymerized by any of azo, peroxide, and redox systems. Examples of oil-soluble azo initiators are 2,2′-azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (2-methylpropionate), 4,4-azobis (4-methoxy-2,4dimethyl) valeronitrile and the like are mentioned and dissolved in a water-miscible solvent and added.
[00 24 ]
Examples of water-soluble azo initiators include 2,2′-azobis (amidinopropane) dichloride, 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] And dihydrochloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of redox systems include a combination of ammonium peroxodisulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine, and the like. Examples of peroxides include ammonium or potassium peroxodisulfate, hydrogen peroxide, benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, succinic peroxide, t-butylperoxy 2-ethylhexanoate, etc. I can give you. The most preferred among these initiators is a redox initiator, which is a combination of ammonium peroxodisulfate or potassium peroxodisulfate with sodium sulfite or sodium bisulfite.
[00 25 ]
Also, polyfunctional monomers such as N, N-methylenebisacrylamide and ethylene glycol (meth) acrylate, or N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide It is also possible to synthesize and modify a crosslinked or branched polymer by copolymerizing a thermally crosslinkable monomer.
[00 26 ]
The inorganic salt constituting the aqueous salt solution is preferably a polyvalent anion salt such as sulfate or phosphate rather than a monovalent anion salt such as an alkali metal halide. Examples of the salt used include ammonium sulfate, sodium sulfate, potassium sulfate, sodium monohydrogen phosphate, sodium dihydrogen phosphate and the like. In addition, the monovalent anion salt such as the alkali metal halide is effective when used in combination with the polyvalent anion salt. The concentration of these inorganic salts in the polymerization system is in the range of 5% by weight to the saturated concentration.
[00 27 ]
The polymer dispersion of the present invention is added as follows. First, the dispersion is dissolved in water and then added to the papermaking raw material before papermaking. Wet-end machine chests and seed boxes are assumed to be added. The amount added is 0.05 to 2%, preferably 0.1 to 0.5%, for the papermaking raw material. Examples of the papermaking raw material include high-quality paper or paperboard raw material, and the type of pulp is chemical pulp, mechanical pulp, or waste paper.
[00 28 ]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated in more detail with an Example and a comparative example, this invention is not restrict | limited to a following example, unless the summary is exceeded.
[00 29 ]
(Synthesis Example 1) Deionized water: 85.0 g, sodium chloride 90.0 g, 60% acrylic acid: 25.3 g in a four-neck 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube , 220.1 g of 50% acrylamide was added to obtain a homogeneous mixed solution, and as a dispersant, hydrochloric acid hydrolyzate of 25% aqueous solution poly-N-vinylformamide (weight average molecular weight 680,000, ion equivalent 7.88 meq / g) 75 0.0 g (0.7 times the ion equivalent of acrylic acid) and 0.75 g of 10% isopropyl alcohol (0.05% by weight of monomer) as a polymerization degree regulator were added and completely dissolved. . The solution pH at this time was 3.05. Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 30 ± 2 ° C. using a constant temperature water bath. 30 minutes after introduction of nitrogen, 2.5 g of 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (based on monomer, 200 ppm) was added. Then, polymerization was started. After 8 hours from the start of polymerization, 0.6 g of the initiator was added, and the polymerization was further continued for 15 hours to complete the reaction. Let this prototype be prototype-1. The composition of this trial production-1 was a single amount to a concentration of 25%, acrylic acid / acrylamide = 12/88 (mol%), and the dispersion viscosity was 1630 mPa · s. The weight average molecular weight was measured with a molecular weight measuring instrument (DLS-7000, manufactured by Otsuka Electronics Co., Ltd.) by a static light scattering method. The results are shown in Table 1.
[00 30 ]
(Synthesis example 2) When the hydrochloric acid hydrolyzate of poly-N-vinylformamide of Example 1 is added in the same manner as in Example 1 and added as a 1.4-fold dispersant with respect to the ion equivalent of acrylic acid An anionic water-soluble dispersion was synthesized. Let this prototype be prototype-2. The composition of the trial production-2 was a single amount to a concentration of 25%, acrylic acid / acrylamide = 12/88 (mol%), and the dispersion viscosity was 1270 mPa · s. Similarly, the weight average molecular weight was measured. The results are shown in Table 1.
[00 31 ]
(Synthesis Example 3) When the hydrochloric acid hydrolyzate of poly-N-vinylformamide of Example 1 was added as a dispersant 2.0 times the ion equivalent of acrylic acid by the same operation as in Example 1. An anionic water-soluble dispersion was synthesized. Let this prototype be prototype-3. The composition of trial production-3 was a single amount to a concentration of 22%, acrylic acid / acrylamide = 12/88 (mol%), and the dispersion viscosity was 1060 mPa · s. Similarly, the weight average molecular weight was measured. The results are shown in Table 1.
[00 32 ]
(Synthesis Example 4) Deionized water: 20.0 g, ammonium sulfate 90.0 g, 60% acrylic acid: 25.3 g in a four-neck 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube 220.1 g of 50% acrylamide was added to obtain a uniform mixed solution, and 30% aqueous solution poly-N, N dimethylaminoethyl acrylate sulfate (weight average molecular weight 1.15 million, ion equivalent 6.99 meq / g) as a dispersant. Add 140.0 g (1.4 times the ion equivalent of acrylic acid) and 0.75 g of 10% isopropyl alcohol (0.05% by weight of monomer) as a polymerization degree regulator, and dissolve completely. It was. The solution pH at this time was 3.12. Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 30 ± 2 ° C. using a constant temperature water bath. 30 minutes after introduction of nitrogen, 2.5 g of 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (based on monomer, 200 ppm) was added. Then, polymerization was started. After 8 hours from the start of polymerization, 0.6 g of the initiator was added, and the polymerization was further continued for 15 hours to complete the reaction. This prototype is designated Prototype-4. The composition of trial production 4 was a single amount to a concentration of 25%, acrylic acid / acrylamide = 12/88 (mol%), and the dispersion viscosity was 985 mPa · s. Similarly, the weight average molecular weight was measured. The results are shown in Table 1.
[00 33 ]
(Synthesis Example 5) 90.0 g of sodium chloride, 25.3 g of 60% acrylic acid: 220.1 g of 50% acrylamide was added to a four-necked 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. In addition, as a uniform mixed solution, 162.7 g (weight average molecular weight 1,450,000, ion equivalent 9.10 meq / g) 162.7 g (1.4 times the ion equivalent of acrylic acid) as a dispersant. ) And 0.75 g of 10% isopropyl alcohol (0.05% by weight of monomer) as a polymerization degree adjusting agent were added and completely dissolved. The solution pH at this time was 3.01. Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 30 ± 2 ° C. using a constant temperature water bath. 30 minutes after introduction of nitrogen, 2.5 g of 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (based on monomer, 200 ppm) was added. Then, polymerization was started. After 8 hours from the start of polymerization, 0.6 g of the initiator was added, and the polymerization was further continued for 15 hours to complete the reaction. This prototype is designated Prototype-5. The composition of the trial product-5 was a single amount to a concentration of 25%, acrylic acid / acrylamide = 12/88 (mol%), and the dispersion viscosity was 2170 mPa · s. Similarly, the weight average molecular weight was measured. The results are shown in Table 1.
[00 34 ]
(Synthesis Example 6) Deionized water: 44.3 g, sodium chloride 90.0 g, 60% acrylic acid: 25.3 g in a four-necked 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube , 179.4 g of 50% acrylamide and 21.1 g of 2-hydroxyethyl methacrylate were added to obtain a uniform mixed solution, and a hydrochloric acid hydrolyzate of 25% aqueous solution poly-N-vinylformamide (weight average molecular weight) as a dispersant. 680,000, ion equivalent 7.88 meq / g) 137.5 g (1.4 times the ion equivalent of acrylic acid) and 0.75 g of 10% isopropyl alcohol as a polymerization degree regulator (0.05 monomer) % By weight) was added and completely dissolved. The solution pH at this time was 3.05. Thereafter, nitrogen is introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature is adjusted to 30 ± 2 ° C. using a constant temperature water bath. 30 minutes after introduction of nitrogen, 2.5 g of 1% aqueous solution of 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride (based on monomer, 200 ppm) was added. Then, polymerization was started. After 8 hours from the start of polymerization, 0.6 g of the initiator was added, and the polymerization was further continued for 15 hours to complete the reaction. This prototype is designated Prototype-6. The composition of this trial product-6 was a single amount to a concentration of 25%, acrylic acid / acrylamide / 2-hydroxyethyl methacrylate = 12/78/10 (mol%), and the dispersion viscosity was 850 mPa · s. It was. Similarly, the weight average molecular weight was measured. The results are shown in Table 1.
[00 35 ]
(Preparation of Comparative Product) An anionic water-soluble polymer composed of acrylic acid / acrylamide = 12/88 (mol%) was polymerized by an aqueous solution polymerization method at a monomer concentration of 20% by weight. When the molecular weight was measured by the same method, it was 2.43 million. This anionic water-soluble polymer and the cationic water-soluble polymer used as a dispersant in the examples were mixed at 0.7 and 1.4 in terms of ionic equivalent, and the pH was adjusted to 3.0 to 3.2. Then, an aqueous solution type paper strength enhancer consisting of 15% pure polymer was prepared. These samples are subjected to comparison-1 to comparison-5. Table 2 shows the water-soluble polymer used and the mixing ratio.
[00 36 ]
Examples 1-6
A papermaking test of a paper strength enhancer comprising the dispersion of the present invention was performed using a liner raw material (SS content 2.54%, pH 5.52 and ash content 0.20%). After making this papermaking raw material 0.8% concentration, add commercially available emulsion sizing agent to pulp 0.10%, aluminum sulfate (8.0% as Al 2 O 3 minutes) vs. pulp 1.5%. After adjusting the pH to 5.85, each of trial production-1 to trial production-6 of Synthesis Examples 1 to 6 was diluted with water to obtain 0.5% polyion complex. The pH of each dilution was adjusted to 6.5-7.0. Thereafter, 0.3% is added to the papermaking raw material, and after stirring for 20 seconds, papermaking is performed with a Tappi standard sheet machine to a basis weight of 100 g / m 2, and the obtained wet paper is pressed at 5 kg / cm 2 for 2 minutes The paper was dried for 3 minutes with a 105 ° C. rotary dryer to obtain a hand-made paper. This handmade paper was conditioned for 24 hours under the conditions of 20 ° C. and 65% HR, and then the specific burst strength according to JIS P 8112, J.P. TAPPI
The specific compressive strength was measured according to JIS P 8126. The results are shown in Table 3.
[00 37 ]
[Comparative Examples 1-5]
The tests for Comparative-1 to Comparative-5 were performed in the same manner as in Examples 1-6. The results are shown in Table 3.
[00 38 ]
Examples 7 to 12
A papermaking test of a paper strength enhancer comprising the dispersion of the present invention was performed using a liner raw material (SS content 2.54%, pH 5.52 and ash content 0.20%). This time, the sulfuric acid band and the emulsion size were not added, and the case where only each of Samples 1 to 6 of Synthesis Examples 1 to 6 was added was performed. After diluting to 0.5% to make polyion complex, adding 0.3%, stirring for 20 seconds, papermaking to a basis weight of 100 g / m2 with a tappi standard sheet machine, and the resulting wet paper Was pressed at 5 kg / cm 2 for 2 minutes and then dried with a rotary dryer at 105 ° C. for 3 minutes to obtain hand-made paper. This handmade paper was conditioned for 24 hours under the conditions of 20 ° C. and 65% HR, and then the specific burst strength according to JIS P 8112, J.P. TAPPI
The specific compressive strength was measured according to JIS P8126. The results are shown in Table 4.
[00 39 ]
[Comparative Examples 6 to 10]
Tests were performed on Comparative-1 to Comparative-5 by the same operations as in Examples 7-12. The results are shown in Table 4.
[00 40 ]
[Table 1]
PVAM: poly-N-vinylformamide hydrochloride hydrolyzate PDMA: poly-N, N-dimethylaminoethyl acrylate sulfate PAMH: polyacrylamide Hoffman reactant hydrochloride AAC: acrylic acid, AAM: acrylamide, HEMA: 2-Hydroxyethyl methacrylate dispersion viscosity: mPa · s, molecular weight: 10,000, weight ratio: dispersant to monomer (%)
[00 41 ]
[Table 2]
PVAM: poly-N-vinylformamide hydrochloride hydrolyzate PDMA: poly-N, N-dimethylaminoethyl acrylate sulfate PAMH: polyacrylamide Hoffman reactant hydrochloride equivalent ratio: (cationic polymer ion equivalent) / (Anionic polymer ion equivalent)
Mixture viscosity (15% concentration): mPa · s
[00 42 ]
[Table 3]
Specific rupture degree: Dimensionless ratio Ring crush: Dimensionless [00 43 ]
[Table 4]
Specific burst rate: dimensionless ratio ring crush: dimensionless

Claims (7)

  1. An anionic water-soluble polymer having a weight average molecular weight of 1,000,000 to 5,000,000 consisting of polymer fine particles by a dispersion polymerization method in the presence of a dispersant comprising a cationic polymer soluble in the salt solution in a salt solution. A dispersion obtained by polymerization, wherein the anionic water-soluble polymer is an anionic monomer represented by the following general formula (1) 5 to 30 mol%, (meth) acrylamide 70 to 95 mol% and It is a polymer of a monomer mixture composed of 0 to 20 mol% of other nonionic monomers that can be copolymerized, and the dispersant composed of the cationic polymer is changed to an ionic equivalent of the anionic water-soluble polymer. Dispersion prepared by coexisting so as to be 0.5 to 3.0 times the weight ratio of monomer: cationic polymer = 1: 0.26 to 1: 0.43 was dissolved in water. After generating polyion complex Paper strength enhancing method is characterized by adding to the papermaking raw material before papermaking.
    R 1 is hydrogen, methyl group or carboxymethyl group, R 2 is hydrogen or carboxyl group, A is SO 3 , C 6 H 4 SO 3 , CONHC (CH 3 ) 2 CH 2 SO 3 or COO, Y is hydrogen or positive ion
  2.  2. The paper strength enhancing method according to claim 1, wherein the dispersing agent comprising the cationic polymer is a polyacrylamide Hoffman reaction product.
  3.  The paper strength enhancing method according to claim 1, wherein the dispersant made of the cationic polymer is a vinylamine polymer.
  4.  2. The paper strength enhancing method according to claim 1, wherein the dispersing agent comprising the cationic polymer is a copolymer of a vinyl cationic monomer and acrylamide.
  5.  5. The paper strength enhancing method according to claim 1, wherein a cation equivalent of a dispersant comprising a cationic polymer soluble in the aqueous salt solution is 3.0 to 10.0 meq / g.
  6.  The paper strength enhancing method according to any one of claims 1 to 5, wherein the dispersant comprising a cationic polymer soluble in the salt aqueous solution has a weight average molecular weight of 100,000 to 3,000,000.
  7. The method for enhancing paper strength according to claim 1, wherein the salt constituting the aqueous salt solution contains at least one kind of polyvalent anion salt.
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JPH10212320A (en) * 1997-01-29 1998-08-11 Hymo Corp Production of anionic water-soluble polymer dispersion, anionic water-soluble polymer dispersion, and its use
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