JP5366301B2 - Powdered ionic water-soluble polymer and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ionic water-soluble polymer having small transportation cost and an environmental load, to provide a method for production thereof, and to provide the ionic water-soluble polymer for flocculant uses, for further specifically, dehydrating treatment uses of sludge, dehydrating treatment uses of papermaking sludge, and exhibiting excellent functions in a method for adding it to a papermaking raw material, and carrying out papermaking. <P>SOLUTION: The ionic water-soluble polymer is a mixture of a water-soluble polymer and a powdery product etc., obtained by drying and granulating a dispersion obtained according to dispersion polymerization, or an aqueous gelled material. The water-soluble polymer comprises powder exhibiting a specific ionic character, and is obtained by carrying out emulsification and polymerization with a surfactant so as to provide a water-immiscible organic liquid as a continuous phase, and an aqueous solution of a monomer mixture containing a cationic monomer and multifunctional monomer as essential components as a dispersed phase, and then drying and granulating the resultant water-in-oil type emulsion-like liquid. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a powdered ionic water-soluble polymer, a method for producing the same, and a use thereof. More specifically, the present invention relates to a powder having a water-soluble polymer expressing a specific different ionicity and a use thereof. .

Conventionally, ionic water-soluble polymers are various such as water-dispersible slurry, aqueous solution thickener, dispersant, paper strength enhancer, sludge dewatering agent, yield improver for papermaking raw materials, and drainage improver for papermaking. There are various forms such as powders, pasty aqueous solutions, water-in-oil emulsions or aqueous dispersions.

In the field of sludge dewatering treatment, the amount of sludge generated is increasing and the difficulty of dewatering is advancing due to the deterioration of sludge properties, and there is a strong demand for improved sludge dewaterability and reduced moisture content of dewatered cakes. In the industrial field, there are demands for deterioration of raw material conditions due to an increase in the amount of used paper, and improvement in productivity due to an increase in papermaking speed.

In response to such demands, various improvements have been made to ionic water-soluble polymers.

Patent Document 1 exemplifies application of a crosslinked cationic polymerizable dispersion in oil to sludge.

Patent Document 2 exemplifies application as a sludge dewatering agent in which an ionic water-soluble polymer having a charge encapsulation rate of 35% or more and an ionic water-soluble polymer having a charge encapsulation rate of 5 or more and less than 35% are combined. .

Patent Document 3 exemplifies a method in which a water-in-oil emulsion of a crosslinked water-soluble cationic monomer polymer is applied to a papermaking process as a yield improver and a drainage improver.

All of the improved methods exemplified above are polymer liquids in the form of water-in-oil emulsions, which are characterized in that the polymer itself can be freely designed.

On the other hand, the powdered ionic water-soluble polymer usually undergoes a polymerization reaction at a high concentration. The polymer itself can be freely designed to prevent solidification and gelation of the polymer, and the three-dimensional structure can be obtained. It is difficult to control.

However, compared to ionic water-soluble polymers in the form of water-in-oil emulsions, they are characterized by fewer impurities such as hydrophobic solvents, water, and dispersants, and are advantageous in terms of transportation costs and environmental impact. There is a disadvantage that flexibility is small.

In order to overcome this drawback, Patent Document 4 describes a spray-dried product of a cationic water-soluble polymer, and Patent Document 5 describes a crosslinked cationic water-soluble polymer obtained by spray drying. Applications as molecules and flocculants are illustrated.

These powder water-soluble cationic water-soluble polymers are not described in terms of charge inclusion rate, and are clearly outside the scope of consideration.

In this way, ionic water-solubility that meets the demands of various ionic water-soluble polymers, and can meet the demands from the aspect of reducing the amount of use, reducing the environmental burden and cost of use. No polymer has ever been presented.
Japanese Patent Publication No. 08-164 JP 2005-144346 A Japanese Patent Laid-Open No. 10-140696 U.S. Pat. No. 4,035,317 JP-T-2001-516773

An object of the present invention is to provide an ionic water-soluble polymer composed of a powder that has low transportation cost and environmental load and can be used in a reduced amount, and a method for producing the same. An object of the present invention is to provide an ionic water-soluble polymer composed of a powder exhibiting an excellent function for a processing use, a papermaking sludge dehydration treatment application and a papermaking raw material addition method.

As a result of intensive studies, the present inventors have surprisingly reached the invention described in claim 1 below. That is, the invention of claim 1 emulsifies with a surfactant so that a water-immiscible organic liquid becomes a continuous phase, and an aqueous monomer mixture containing a cationic monomer and a polyfunctional monomer becomes a dispersed phase. The water-in-oil powder obtained by drying the water-in-oil emulsion liquid obtained after polymerization, and having a charge encapsulation rate of the ionic polymer of 35% or more and 90% or less ( A) and one or more selected from powders of water-soluble polymers having a charge inclusion rate of less than 35% and 3% or more having a cationic group other than the production method of drying and granulating the water-in-oil emulsion liquid A powdery ionic water-soluble polymer comprising a mixture of the water-soluble polymer powder (B) , wherein the powdered ionic water-soluble polymer is represented by the following general formula (1) and / or (2): Monomer 4.9999-100 mol A copolymer of 0 to 50 mol% of a monomer represented by the following general formula (3), 0 to 95 mol% of a water-soluble nonionic monomer and 0.0001 to 0.1 mol% of a polyfunctional monomer The water-soluble polymer powder (A), the water-soluble polymer powder (B ₁ ) having the structure represented by the following general formula (4) or general formula (5), the following general formula (1) or (2) A water-soluble high copolymer comprising a monomer represented by 5-95 mol% and a water-soluble nonionic monomer 0-90 mol% and a monomer 5-50 mol% represented by the following general formula (3) It is a powdered ionic water-soluble polymer that is a mixture of molecular powder (B ₂ ) and an acid .
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl group having 1 to ₃ carbon atoms, an alkoxyl group or a benzyl group, and R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A is O or NH, B is an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, _{X 1} ^- represents respectively an anion.
General formula (2)
R ₅ and R _{6 each} represent hydrogen or a methyl group, R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.
General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation.
General formula (4)
R _{12 and} R ₁₃ represent hydrogen or a methyl group, H ⁺ Z ⁻ represents an inorganic acid and / or an organic acid, and H ⁺ Z ⁻ = 0 when not neutralized.
General formula (5)
R _{12 and} R ₁₃ represent hydrogen or a methyl group, H ⁺ Z ⁻ represents an inorganic acid and / or an organic acid, and H ⁺ Z ⁻ = 0 when not neutralized.

In the invention of claim 2, the powdered ionic water-soluble polymer is represented by the following general formula (1) and / or (2): monomer 4.9999-100 mol%, the following general formula (3) Water-soluble polymer powder which is a copolymer of 0 to 50 mol% of represented monomers, 0 to 95 mol% of water-soluble nonionic monomers and 0.0001 to 0.1 mol% of polyfunctional monomers ( A), a water-soluble polymer powder which is a copolymer of 5 to 100 mol% of the monomer represented by the general formula (1) or (2) and 0 to 95 mol% of a water-soluble nonionic monomer ( B ₁ ), 5 to 95 mol% of a monomer represented by the following general formula (1) or (2), 5 to 50 mol% of a monomer represented by the following general formula (3), and a water-soluble nonionic monomer Water-soluble high content which is a copolymer of 0 to 90 mol% Powder (B ₂₎ and in powder form ionic water-soluble polymer is a mixture of acids.
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl group having 1 to ₃ carbon atoms, an alkoxyl group or a benzyl group, and R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A is O or NH, B is an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, _{X 1} ^- represents respectively an anion.
General formula (2)
R ₅ and R _{6 each} represent hydrogen or a methyl group, R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.
General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation.

The invention of claim 3, wherein the water-soluble polymer powder (A) is powdered ionic water according to claim 1 or 2, characterized in that the water-emulsion form liquid oil is obtained by spray-drying Functional polymer.

The invention of claim 4, wherein the water-soluble polymer powder (A) is a water-emulsion liquid form in the oil in a dryer according to claim 1, characterized in that is obtained by drying directly in a emulsion form liquid Alternatively , the powdered ionic water-soluble polymer described in 2 .

The invention according to claim 5 is the water-soluble polymer powder having a cationic group obtained by drying the dispersion obtained by dispersing and dispersing the water-soluble polymer powder (B) in salt water or water-immiscible organic liquid. The powdered ionic water-soluble polymer according to claim 1 , wherein the powdered ionic water-soluble polymer is one or more selected from the group consisting of:

In the invention of claim 6, the water-soluble polymer powder (B) is selected from a powder of a water-soluble polymer having a cationic group obtained by drying a viscous liquid obtained by aqueous solution polymerization or an aqueous gel-like material having no fluidity. The powdered ionic water-soluble polymer according to claim 1 , wherein the powdered ionic water-soluble polymer is one or more.

The invention according to claim 7 is the powdered ionic water-soluble polymer according to claim 1 or 2 , wherein the water-in-oil emulsion liquid does not contain a surfactant having an HLB value of 10 or more. is there.

The invention of claim 8 is characterized in that the powdered ionic water-soluble polymer according to any one of claims 1 to 7 is dissolved in water, then added to the sludge, agglomerated and dehydrated by a dehydrator. This is a dehydration method.

The invention of claim 9 is characterized in that the powdered ionic water-soluble polymer according to any one of claims 1 to 7 is dissolved in water and then added to the papermaking raw material before papermaking and used. Is the method.

The invention according to claim 10 is the paper manufacturing method according to claim 9 , which is used in combination with an organic anionic substance.

The invention of claim 11 is characterized in that the anionic substance is a polymer of 3 to 100 mol% of a monomer represented by the following general formula (3) and a water-soluble nonionic monomer. The paper manufacturing method according to claim 9 .

General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation.

The ionic water-soluble polymer comprising the powder of the present invention is a combination of an ionic water-soluble polymer having a charge encapsulation rate of 35% or more and 90% or less and an ionic water-soluble polymer of less than 35% and 3% or more. Because it is an ionic water-soluble polymer, it exhibits a particularly excellent function for flocculant applications, specifically sludge dewatering treatment, paper sludge dewatering treatment and papermaking raw materials. Not only can the amount of addition be reduced, but it is a powdery water-soluble polymer with few impurities, so transportation costs, carbon dioxide emissions from transportation, and water-in-oil emulsion The amount of hydrophobic dispersion media and surfactants discharged into the environment can be reduced compared to hydrophilic polymers.

The ionic water-soluble polymer of the present invention includes an ionic water-soluble polymer having a charge encapsulation rate of 35% or more and 90% or less, and an ionic water-soluble polymer having a charge encapsulation rate of less than 35% and 5% or more. It is an ionic water-soluble polymer formed by combining molecules.

Here, a cationic water-soluble polymer obtained by copolymerizing a monomer aqueous solution containing a cationic monomer and a polyfunctional monomer, and an amphoteric, cationic monomer and anionic monomer In an ionic water-soluble polymer having a positive difference in molar concentration, the charge inclusion rate is calculated as follows.
Charge inclusion rate [%] = (1−α / β) × 100
α is a 0.01% aqueous solution of a cationic water-soluble polymer adjusted to pH 4.0 with acetic acid.
The titer was determined by titration with PCD 03, Muetek PCD-Two Titortor Version 2) by titrating with a dropping solution: 1 / 1000N aqueous polyvinyl polyvinyl sulfonate solution, dropping rate: 0.05 ml / 10 seconds, end point determination: 0 mv. β is 1 / 400N in 0.01% aqueous solution of cationic water-soluble polymer adjusted to pH 4.0 with acetic acid.
A sufficient amount of potassium polyvinyl sulfonate aqueous solution was added to neutralize the charge, and stirred sufficiently. Similarly, using a PCD titrator, dropping solution: 1 / 1000N diallyldimethylammonium chloride aqueous solution, dropping rate: 0.05 ml / 10 Second, end point determination: titration at 0 mv, the difference between the blank value and this titration amount. The blank value is the 1/400 N adjusted to pH 4.0 with acetic acid.
The same amount of potassium polyvinyl sulfonate aqueous solution as the amount of potassium polyvinyl sulfonate aqueous solution was similarly dropped with a PCD titrator: 1/1000 N diallyldimethylammonium chloride aqueous solution, dropping speed: 0.05 ml / 10 seconds, end point determination: 0 mv The titration amount obtained by titration.

In the present invention, there is a difference in the molar concentration of amphoteric and cationic monomers and anionic monomers obtained by copolymerizing an aqueous monomer solution containing a cationic monomer and a polyfunctional monomer. For an ionic water-soluble polymer that is negative, the charge encapsulation rate is calculated as follows.
Charge inclusion rate [%] = (1−α / β) × 100
α is a 0.01% aqueous solution of a crosslinkable water-soluble ionic polymer adjusted to pH 10.0 with ammonia.
PCD 03, Muetek PCD-Two Titortor Version 2), dropping solution: 1 / 1000N
This is a titration amount obtained by titration with diallyldimethylammonium chloride aqueous solution, dropping rate: 0.05 ml / 10 sec, end point determination: 0 mV. β is 1 / 400N in 0.01% aqueous solution of a crosslinkable water-soluble ionic polymer adjusted to pH 10.0 with ammonia.
Add a sufficient amount of diallyldimethylammonium chloride aqueous solution to neutralize the charge, and stir well. Similarly, using a PCD titrator, drop solution: 1 / 1000N
Titrate with potassium polyvinyl sulfonate aqueous solution, dropping speed: 0.05 ml / 10 sec, end point determination: 0 mV, and this titration value is subtracted from the blank value. The blank value is an aqueous diallyldimethylammonium chloride solution having the same concentration as that of the above sample adjusted to pH 10.0 with ammonia.
A titration amount obtained by titrating at a polyvinyl polyvinyl sulfonate aqueous solution, dropping speed: 0.05 ml / 10 sec, end point determination: 0 mV.

The charge inclusion rate of the ionic water-soluble polymer in the present invention is a parameter related to the ionic expression efficiency, and a large difference between the forward titration and the back titration of the cationic substance is caused by sludge, paper sludge and papermaking. When added alone to the raw material, there is a clear correlation with the effect.

When an ionic water-soluble polymer with a charge inclusion rate of less than 35% and 3% or more is added to agglomerated substances such as sludge, papermaking sludge or papermaking raw material, it is agglomerated with a low addition amount and the water content is reduced. The coagulable substance is re-dispersed with the increase in viscosity and becomes viscous, and the moisture content of sludge increases.

When a charge inclusion rate of 35% or more and 90% or less is added, a large and strong floc is formed with an increase in addition over a wide range of addition amount, and the water content of the cohesive substance is significantly reduced.

In addition, when a substance having a charge inclusion rate of more than 90% is added, it hardly contributes to the aggregation behavior of the aggregating substance unless a chemical more than several times that of the other substances is added.

A powdered ionic water-soluble polymer obtained by mixing an ionic water-soluble polymer having a charge inclusion ratio of less than 35% and 3% or more and an ionic water-soluble polymer having a charge inclusion ratio of 35% or more and 90% or less is agglomerated. When added to the coagulant substance, it not only aggregates and lowers the water content with a low addition amount, but also forms a huge and strong floc with an increase in the amount added, significantly reducing the water content of the coagulant substance.

The powdered ionic water-soluble polymer in the present invention is blended with powders produced by two different production methods. That is, the water-soluble polymer powder (A) is surface active so that an organic liquid immiscible with water becomes a continuous phase and an aqueous monomer mixture containing a cationic monomer and a polyfunctional monomer becomes a dispersed phase. An ionic polymer powder obtained by emulsifying and polymerizing with an agent and then drying and granulating the resulting water-in-oil emulsion liquid, wherein the charge inclusion rate of the ionic polymer is 35% or more and 90% or less. . As a specific drying method, there is a method of spraying and drying a water-in-oil emulsion liquid in a spray dryer. This is simple and easy to operate, but the particle size becomes fine and further processing for adjusting the particle size is necessary. There is also a method in which a water-in-oil emulsion liquid is directly put into a dryer and dried for a certain period of time to crush the lump. In this method, it is necessary to pay attention to the management of the drying temperature and the drying time.

On the other hand, the water-soluble polymer powder (B) is obtained by drying a dispersion obtained by dispersion polymerization in salt water or a water-immiscible organic liquid, a viscous liquid obtained by aqueous solution polymerization, or a non-flowable aqueous gel. It is at least one selected from powders of water-soluble polymer having a granulated cationic group-containing charge inclusion ratio of less than 35% and 5% or more. That is, in the case of a dispersion polymerized by dispersion in salt water, there is a method in which the dispersion is directly put into a drier and dried for a certain time to crush the lump. In the case of a dispersion obtained by dispersion polymerization in water in an immiscible organic liquid, the immiscible organic liquid is separated, and wet polymer particles are dried in a dryer to form a powder. The viscous liquid produced by the aqueous solution polymerization precipitates a polymer with a water-miscible organic liquid, which is dried and pulverized. In the case of a non-flowable aqueous gel-like product obtained by polymerizing a monomer at a high concentration in water, the gel-like product is minced with a meat chopper, dried, pulverized and powdered. As described above, the water-soluble polymer powder (A) and the water-soluble polymer powder (B) are mixed to produce an ionic water-soluble polymer comprising the powder of the present invention.

The mixing ratio of the water-soluble polymer powder (A) having a charge inclusion rate of 35% to 90% and the water-soluble polymer powder (B) having a charge inclusion rate of less than 35% and 3% or more is not particularly limited. The ionic water-soluble polymer having a charge inclusion rate of 35% or more and 90% or less is 30% of the total ionic water-soluble polymer, depending on the intended aggregation property and the properties of the target aggregation material. The ionic polymer having a charge inclusion ratio of less than 35% and 5% or more is in the range of 5 to 70% by mass, preferably the ionic water-soluble polymer is a total ionic water solution. An ionic polymer having a charge inclusion rate of less than 35% is in a range of 5 to 50% by mass, and the charge inclusion rate is less than 35%. % Of ionic polymer in the range of 10-50% by mass It is also preferable to combine the ionic water-soluble polymer having the structure.

A specific mixing example is represented by the water-soluble polymer powder (A) having a charge inclusion ratio of 35% or more and 90% or less according to claim 1 and the general formula (4) and / or the general formula (5). water-soluble polymer having the structure, i.e. polyamidine water-soluble polymer or a mixture of polyvinyl amine based water-soluble polymer with a so-called (meth) acrylic amphoteric water-soluble polymer and an acid, there have electrodeposition load encapsulation efficiency 35 % And 90% or less of the water-soluble polymer powder (A), (meth) acrylic cationic water-soluble polymer, (meth) acrylic amphoteric water-soluble polymer and acid mixture.

The amount of the polyfunctional monomer added when polymerizing the water-soluble polymer powder (A) having a charge inclusion rate of 35% or more and 90% or less is 0.0001 to 0.1 mol of the total monomers. %, Preferably 0.0005 to 0.005 mol% is added. For this reason, if it is less than 0.0001 mol%, the performance of the crosslinkable polymer is hardly exhibited, and if it is higher than 0.1 mol%, the crosslinking proceeds excessively and the performance deteriorates. As an example of the polyfunctional monomer, a monomer having a plurality of vinyl groups is preferable. That is, N, N-methylenebis (meth) acrylamide, triallylamine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, dimethacrylic acid-1,3-butylene glycol, Examples thereof include polyethylene glycol di (meth) acrylate, N-vinyl (meth) acrylamide, N-methylallylacrylamide, glycidyl acrylate, and polyethylene glycol diglycidyl ether.

Examples of the cationic monomer represented by the general formula (1) in the powdered ionic water-soluble polymer of the present invention include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl, and the like. (Meth) acrylamide, diethylaminopropyl (meth) acrylamide and their neutralized salts with hydrogen halide, sulfuric acid, nitric acid, organic acid, etc., quaternized products with alkyl halide, benzyl halide, dimethyl sulfate, diethyl sulfate, etc., general formula Examples of the cationic monomer represented by (2) include dimethyldi (meth) allylammonium chloride, di (meth) allylmethylbenzylammonium chloride, and the like. It is also possible to use it. The amount of the cationic monomer is not particularly limited as long as the water-soluble polymer after polymerization has a cationic property, but is cationic with respect to all monomers except the polyfunctional monomer. The amount of the monomer is preferably in the range of 5 to 95 mol%.

The polyfunctional monomer is not particularly limited as long as it has a plurality of unsaturated double bonds, but N, N′-methylenebis (meth) acrylamide, triallylamine, ethylene glycol di (meth) acrylate, Examples include polyethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, and N-vinyl (meth) acrylamide. As a quantity of a polyfunctional monomer, it is preferable that it is the range of 1-100 mass% with respect to the total monomer mass except a polyfunctional monomer, More preferably, it is 5-50 mass%. It is a range.

The monomer mixture aqueous solution in the present invention may contain a copolymerizable anionic monomer and / or a water-soluble nonionic monomer in addition to the above monomer. Examples of the anionic monomer represented by the general formula (3) include vinyl sulfonic acid, vinyl benzene sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, methacrylic acid, acrylic acid, itaconic acid, maleic acid or p-carboxystyrene etc. are mentioned. The amount of the anionic monomer is preferably in the range of 0 to 50 mol% with respect to all monomers excluding the polyfunctional monomer.

Examples of water-soluble nonionic monomers include (meth) acrylamide, N, N-dimethylacrylamide, vinyl acetate, acrylonitrile, methyl acrylate, 2-hydroxyethyl (meth) acrylate, diacetone acrylamide, N -Vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, acryloylmorpholine, acryloylpiperazine, etc. are mentioned, and the amount thereof is in the range of 0 to 95 mol% with respect to all monomers except the polyfunctional monomer. It is preferable that

The monomer aqueous solution mixture may contain a compound having chain transferability in addition to the monomer. Examples of compounds having chain transferability include 2-ppanol, 2-mercaptoethanol, sodium methallyl sulfonate, sodium formate and the like, which are appropriately added depending on the composition, polymerization rate and molecular weight of the target polymer. To do.

The copolymerization rate of the monomer represented by the following general formula (1) and / or (2) of the water-soluble polymer powder (A) is 4.9999 to 100 mol%, preferably 9.9999 to 100 mol%. More preferably, it is 19.9999-100 mol%. The copolymerization rate of the monomer represented by the following general formula (3) is 0 to 50 mol%, preferably 0 to 30 mol%, more preferably 0 to 20 mol%. In other ranges, sludge dewatering performance and the like are lowered when the cationicity is low, or in the case of amphoteric, the anionic property is too high and adversely affects the mud dewatering performance and the like. Moreover, it is 0.0001-0.1 mol% of polyfunctional monomers, Preferably it is 0.0005-0.01 mol%, More preferably, it is 0.001-0.01 mol%. In other ranges, the agglomeration performance is reduced with respect to sludge having a small fiber content, such as digested sludge, and if it is too much, the water-soluble polymer may become insoluble in water, which is not preferable.

The copolymerization rate of the monomer represented by the following general formula (1) and / or (2) of the water-soluble polymer powder (B) is 5 to 100 mol%, preferably 10 to 100 mol%, Preferably it is 20-100 mol%. The copolymerization rates of the monomer represented by the following general formula (3) and the water-soluble nonionic monomer are 0 to 50 mol% and 0 to 50 mol%, respectively, preferably 0 to 30 mol% and 0 It is -70 mol%, More preferably, it is 0-20 mol% and 0-80 mol%. In other ranges, sludge dewatering performance and the like are lowered when the cationicity is low, or in the case of amphoteric, the anionic property is too high and adversely affects the mud dewatering performance and the like.

The water-immiscible organic liquid that forms a continuous phase is not particularly limited as long as it is an organic liquid that causes phase separation when mixed with water and can be emulsified with a surfactant, but paraffins, kerosene, light oil, Examples thereof include mineral oils such as medium oils, hydrocarbon synthetic oils having characteristics such as boiling point and viscosity in substantially the same range as these, and mixtures thereof. As content, it is preferable that it is the range of 20 mass%-50 mass% with respect to the water-in-oil type emulsion whole quantity.

Examples of surfactants required for emulsification include non-ionic surfactants of HLB 3-10 as examples of at least one surfactant having an amount effective to form a water-in-oil emulsion and HLB. Specific examples thereof include sorbitan monooleate, sorbitan dioleate, sorbitan trioleate, sorbitan monostearate, sorbitan distearate, sorbitan monolaurate, sorbitan dilaurate, Sorbitan monopalmitate, sorbitan dipalmitate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan monostearate, polyoxyethylene stearyl ether, polyoxyethylene lauryl ether Tellurium, polyoxyethylene cetyl ether, poly Polyoxyethylene tridecyl et - ether, polyoxyethylene oleyl et - ether, and high molecular nonionic surfactants and the like. The addition amount of these surfactants is 0.5 to 10% by mass, preferably 1 to 5% by mass, based on the total amount of the water-in-oil emulsion.

The polymerization conditions are usually appropriately determined according to the monomer used and the copolymerization mol%, and the temperature is in the range of 0 to 100 ° C. In particular, when the water-in-oil emulsion polymerization method is applied, it is carried out in the range of 20 to 80 ° C, preferably 20 to 60 ° 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.

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 polymerization concentration of the monomer is in the range of 20 to 50% by mass, preferably in the range of 25 to 40% by mass with respect to the mass of the emulsion, and the monomer composition, polymerization method, and selection of the initiator The polymerization concentration and temperature are set as appropriate. The molecular weight of the water-soluble polymer obtained by polymerizing these monomers is preferably in the range of 3 million to 20 million.

When using a water-in-oil emulsion of a general cationic water-soluble polymer dissolved in water for use as a flocculant, add a highly hydrophilic amphiphilic copolymer or hydrophilic surfactant. Then, the emulsion particles covered with the oil film are treated with water so that the water-soluble polymer therein is easily dissolved, diluted with water and used for each application. The water-in-oil emulsion of the present invention can also contain an amphiphilic copolymer and a hydrophilic surfactant, but the powder obtained by spray-drying contains impurities and is sprayed. When the powder obtained after drying is dissolved in water and used, especially when it contains a hydrophilic surfactant having an HLB value of 10 or more, the reason is not clear, but the surfactant and the cationic polymer are probably combined. Since a dissolution rate becomes slow in order to form a body, the thing which does not contain is more preferable.

In the present invention, the water-soluble polymer powder (B) having a charge encapsulation rate of the ionic polymer having a cationic group of less than 35% and 5% or more is obtained from an ionic water-soluble polymer having a vinylamine structural unit or an amidine structure. It can also be used.

An ionic water-soluble polymer having a vinylamine structural unit can also be used as the water-soluble polymer powder (B) comprising a powder having a charge inclusion ratio of less than 35% and 3% or more.

Examples of the ionic water-soluble polymer having a vinylamine structural unit include a hydrolyzate of N-vinylformamide and N-vinylacetamide, and a Hoffman modified product of polyacrylamide.

An ionic water-soluble polymer having an amidine structure can be used as the water-soluble polymer powder (B) having a charge inclusion ratio of less than 35% and 3% or more.

The ionic water-soluble polymer having an amidine structure is obtained by modifying a hydrolyzate of N-vinylformamide or N-vinylacetamide and acrylonitrile copolymer, or a copolymer of (meth) acrylamide and (meth) acrylonitrile. It can be obtained by modification after Hofmann decomposition.

Further, the water-soluble polymer powder (B) having a charge encapsulation rate of less than 35% and 3% or more can be used in combination.

The sludge dewatering method of the present invention is a method in which the powdered ionic water-soluble polymer according to any one of claims 1 to 7 is dissolved in water and then added to the sludge to be aggregated and dehydrated by a dehydrator. There are no particular restrictions on the type of sludge, such as surplus sludge generated during biological treatment such as papermaking wastewater, chemical industrial wastewater, and food industry wastewater, or raw sludge, mixed raw sludge, surplus sludge, digested sludge, etc. Can be used for organic sludge.

The powdered ionic water-soluble polymer of the present invention is a method in which it is dissolved in water and then added to sludge dewatering and paper sludge to be agglomerated and dehydrated by a dehydrator. There are no particular restrictions on the type of dehydrator used for sludge dewatering and paper sludge dewatering. Pressure dehydration devices such as belt presses, screw presses, rotary presses, filter presses, etc., or centrifugal separators, vacuum filters, etc. Is given as an example.

In the sludge dewatering method and paper sludge dewatering method of the present invention, as a dehydrator that can be particularly preferably used, the charge inclusion rate of the powdered ionic water-soluble polymer according to claim 1 and the behavior of the dewatering effect When the charge inclusion ratio is in the range of 35% or more and 90% or less, there is a feature that a huge and strong floc is formed with an increase in the amount of addition, and the initial drainage amount of dehydration increases accordingly. And screw press dehydrators and rotary press dehydrators that require high flock and initial dewatering performance.

The sludge dewatering method and paper sludge dewatering method of the present invention can use an organic or inorganic coagulant in addition to the powdered ionic water-soluble polymer according to claims 1 to 7. Examples of organic coagulants include cationic polymers, such as (meth) acryloyloxyethyltrimethylammonium chloride, diallylamine compounds such as (meth) acryloyloxyalkyltrialkylammonium halides and diallyldimethylammonium chloride. Examples of inorganic coagulants include metal salts such as polyaluminum chloride, ferric chloride, and ferric sulfate.

The papermaking method of the present invention is a method in which the powdered ionic water-soluble polymer according to claims 1 to 7 is dissolved in water and then added to a papermaking raw material before papermaking. There are no particular restrictions on the type of papermaking raw material, and pulp such as kraft pulp, BKP, TMP, and DIP can be used. For ionic water-soluble polymers having a charge inclusion rate of 35% to 90%, DIP and the like It is particularly suitable when using a pulp containing a large amount of short fibers, a pulp containing a large amount of an anionic substance such as TMP, or a raw material containing a large amount of filler in addition to the pulp.

The type of filler is not particularly limited, and examples include calcium carbonate, talc, kaolin, and titanium oxide. Moreover, there is no restriction | limiting also in pH at the time of papermaking, and papermaking on acidic and neutral conditions is also possible. When the ionic water-soluble polymer of the present invention is used, it is preferably used for improving the filler yield rate under neutral papermaking conditions in which a large amount of calcium carbonate is used.

Paper can be produced by adding the powdered ionic water-soluble polymer aqueous solution of the present invention to a pulp slurry to produce paper, but the addition location is not particularly limited, but the seed box, machine chest, screen entrance or exit Etc. are assumed. It is preferable to use 10 to 500 ppm of ionic water-soluble polymer added to the pulp weight.

The papermaking method using the powdered ionic water-soluble polymer of the present invention can be used in combination with one or more selected from inorganic and organic anionic substances. Examples of inorganic anionic substances include colloidal silica and bentonite, and examples of organic anionic substances include 3 to 100 mol% of anionic monomer represented by the general formula (3) and a water-soluble nonionic substance. A monomer copolymer can be exemplified.

There is no particular limitation on the form of the copolymer of 3 to 100 mol% of the anionic monomer represented by the general formula (3) and a water-soluble nonionic monomer, and it is a paste-like aqueous solution or water-in-oil emulsion. And aqueous dispersion liquids, and any of them can be added as an aqueous solution dissolved in water. There are no particular restrictions on the location of the addition, and it can be added before, after or simultaneously with the addition of the ionic water-soluble polymer, or both aqueous solutions or dispersions can be mixed and used.

There are no particular restrictions on the place where the anionic substance is added, but examples include a seed box, a machine chest, and an inlet or outlet of the screen, and it can be added before, after or simultaneously with the addition of the cationic polymer.

The addition amount of the anionic substance is not particularly limited, but it is preferable to add it in the range of 10 to 10,000 ppm with respect to 10 pulp weight.

(Examples) Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist.

(Production Example 1 of Powdered Ionic Water-Soluble Polymer with Charge Inclusion Ratio of Less than 35%, 3% or More) Four equipped with a stirrer equipped with a cross stirring blade, a reflux condenser, a thermometer, a nitrogen introduction pipe and a cooling device Into the mouth separable flask was charged 29.74 g of a 50 wt% acrylamide aqueous solution, 12.66 g of 80 wt% acryloyloxyethyltrimethylammonium chloride aqueous solution and 206.85 g of ion-exchanged water, and the inside of the flask was sufficiently purged with nitrogen. 0.75 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was charged, and the reaction was carried out at 35 ° C. for 15 hours. This was coated on a polyethylene film having a thickness of 0.07 mm so that the thickness was 10 mm or less, and was left to dry for 20 hours in a blow dryer at 80 ° C. Then, the obtained sheet copolymer was obtained. Then, it was broken and pulverized to obtain a powdered ionic water-soluble polymer. This was designated as Production Example 1 and the physical properties are shown in Table 1.

(Production Example 2) 9.83 g of 50% by mass acrylamide aqueous solution, 25.11 g of 80% by weight acryloyloxyethyltrimethylammonium chloride aqueous solution, 213.56 g of ion-exchanged water, and 1% by mass 2,2′-azobis [2- (2- A powdery ionic water-soluble polymer was obtained in the same manner as in Production Example 1 except that 1.50 g of imidazolin-2-yl) propane] dihydrochloride aqueous solution was used. This was designated as Production Example 2 and the physical properties are shown in Table 1.

(Production Example 3) 4.20 g of 50% by mass acrylamide aqueous solution, 19.90 g of 80% by mass acryloyloxyethyltrimethylammonium chloride aqueous solution, 1.81 g of 60% by mass acrylic acid, 208.33 g of ion-exchanged water and 1% by mass 2,2 A powdered ionic water-soluble polymer was obtained in the same manner as in Production Example 1 except that 3.75 g of an aqueous solution of '-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was used. This was designated as Production Example 3 and the physical properties are shown in Table 1.

(Production Example 4) An aqueous mixture prepared by charging 49.4 g of a 92 mass% N-vinylformamide aqueous solution, 35.3 g of acrylonitrile (Kanto Chemical Co., Ltd., special grade reagent), and 179.3 g of ion-exchanged water was added to 4.00 g of sorbitan monooleate. A mixture consisting of 132.00 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. was added, and the mixture was vigorously stirred for 15 minutes with a monogenizer at a rotation speed of 1000 rpm to obtain a monomer emulsion. This was charged into a four-necked separable flask equipped with a stirrer equipped with a cross stirring blade, a reflux condenser, a thermometer, a nitrogen inlet tube and a cooling device, and replaced with nitrogen using a cross stirring blade under a stirring condition of 400 prm. It was. After completion of the nitrogen substitution, 0.40 g of 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) was added and polymerization was carried out by maintaining at 30 ° C. for 20 hours in a nitrogen atmosphere. A molecular water-in-oil emulsion was obtained. This water-in-oil emulsion was sprayed into a granulating / drying apparatus, and dried and granulated until the water content of the granulated powder became 5% by mass or less to obtain a powdered ionic water-soluble polymer. This was designated as Production Example 4 and the physical properties are shown in Table 1.

(Production Example 5) 80.1 g of 50 mass% acrylamide aqueous solution, acrylonitrile (Kanto Chemical Co., Ltd.) in a four-necked separable flask equipped with a stirrer equipped with a cross stirring blade, a reflux condenser, a thermometer, a nitrogen inlet tube and a cooling device 19.9 g of Co., Ltd., a special grade reagent) and 200.0 g of ion-exchanged water were charged, and nitrogen substitution was performed under a stirring condition of 120 prm with a cross stirring blade. After completion of the nitrogen substitution, 1.20 g of 10% by mass 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was added and maintained at 35 ° C. for 20 hours under a nitrogen atmosphere. went. 50.0 g of this was collected, 150 g of ion-exchanged water was added, and the mixture was cooled to 5 ° C. or lower. 79.3 g of sodium hypochlorite (effective chlorine 12%) and 20.0 g of 48 mass% sodium hydroxide aqueous solution The mixed solution was added, and Hofmann reaction was performed at 15 ° C. or lower for 1 hour. This was neutralized by adding 55.0 g of 35% by weight aqueous hydrochloric acid solution, and the separated precipitate was applied on a 0.07 mm thick polyethylene film so that the thickness was 10 mm or less, and was blown dry at 80 ° C. After standing and drying for 20 hours in the machine, the obtained sheet-like copolymer was broken and ground to obtain a powdery ionic water-soluble polymer. This was designated as Production Example 5 and the physical properties are shown in Table 1.

(Production example of ionic water-soluble polymer comprising powder having a charge inclusion rate of 35% or more and 90% or less) (Production Example 6) A stirrer, reflux condenser, thermometer, nitrogen introduction pipe and cooling device equipped with a cross stirring blade A four-necked separable flask equipped with 59.48 g of 50 wt% acrylamide aqueous solution, 25.32 g of 80 wt% acryloyloxyethyltrimethylammonium chloride aqueous solution, 1.388 g of 0.1% N, N′-methylenebisacrylamide aqueous solution, Add a mixture of 3.73 g of sorbitan monooleate, 35.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C. and 0.555 g of 2-propanol, and vigorously stir for 15 minutes with a monogenizer at 1000 rpm. Monomer emulsification A liquid was obtained. 0.50 g of a 1% by mass 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was charged, and the reaction was carried out at 35 ° C. for 15 hours. This water-in-oil emulsion was sprayed into a granulating / drying apparatus, and dried and granulated until the water content of the granulated powder became 5% by mass or less to obtain a powdered ionic water-soluble polymer. This is referred to as Production Example 6 and the physical properties are shown in Table 1.

(Production Example 7)
0.555 g of 2-propanol was added and 2.775 g of a 0.1% N, N′-methylenebisacrylamide aqueous solution was added, and a powdery ionic water-soluble polymer was obtained in the same manner as in Production Example 5. This was designated as Production Example 7, and the physical properties are shown in Table 1.

(Production Example 8) In a four-necked separable flask equipped with a stirrer equipped with a cross stirrer, a reflux condenser, a thermometer, a nitrogen inlet pipe and a cooling device, 19.66 g of a 50 wt% acrylamide aqueous solution and 80 wt% acryloyloxy 50.22 g of ethyltrimethylammonium chloride aqueous solution, 1.388 g of 0.1% N, N′-methylenebisacrylamide aqueous solution, 3.73 g of sorbitan monooleate, 35.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C., 2-propanol A mixture consisting of 0.555 g was added, and the mixture was vigorously stirred for 15 minutes at 1000 rpm with a monogenizer to obtain a monomer emulsion. 0.50 g of a 1% by mass 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was charged, and the reaction was carried out at 35 ° C. for 15 hours. This water-in-oil emulsion was poured into a shallow container to a thickness of 1 cm, dried until the water content was 5% by mass or less, and then pulverized and granulated to obtain a powdered ionic water-soluble polymer. . This was designated as Production Example 8, and the physical properties are shown in Table 1.

(Production Example 9)
A four-necked separable flask equipped with a stirrer equipped with a cross stirrer, a reflux condenser, a thermometer, a nitrogen inlet pipe and a cooling device, 19.66 g of a 50% by weight acrylamide aqueous solution, 80% by weight acryloyloxyethyltrimethylammonium chloride aqueous solution 50.22 g, 2.775 g of 0.1% N, N′-methylenebisacrylamide aqueous solution, 3.73 g of sorbitan monooleate, 35.0 g of isoparaffin having a boiling point of 190 ° C. to 230 ° C., and 0.555 g of 2-propanol The mixture was added and vigorously stirred for 15 minutes with a monogenizer at 1000 rpm to obtain a monomer emulsion. 0.50 g of a 1% by mass 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was charged, and the reaction was carried out at 35 ° C. for 15 hours. This water-in-oil emulsion is poured into a shallow container to a thickness of 1 cm, dried until the water content is 5% by mass or less, then pulverized and granulated to obtain a powdered ionic water-soluble polymer. It was. This was designated as Production Example 9, and the physical properties are shown in Table 1.

(Production Example 10)
In a four-necked separable flask equipped with a stirrer equipped with a cross stirrer, a reflux condenser, a thermometer, a nitrogen inlet pipe and a cooling device, 8.40 g of a 50 wt% acrylamide aqueous solution and an 80 wt% acryloyloxyethyltrimethylammonium chloride aqueous solution 39.8 g, 60 mass% acrylic acid 3.62 g, 0.1% N, N′-methylenebisacrylamide aqueous solution 2.775 g, sorbitan monooleate 3.73 g and isoparaffin having a boiling point of 190 ° C. to 230 ° C. 35.0 g, A mixture composed of 0.555 g of 2-propanol was added, and the mixture was vigorously stirred for 15 minutes with a monogenizer at a rotation speed of 1000 rpm to obtain a monomer emulsion. 0.50 g of a 1% by mass 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution was charged, and the reaction was carried out at 35 ° C. for 15 hours. The water-in-oil emulsion was poured into a shallow container to a thickness of 1 cm, dried until the water content was 5% by mass or less, and then pulverized and granulated to obtain a powdered ionic water-soluble polymer. This was designated as Production Example 10 and the physical properties are shown in Table 1.

(Comparative Production Example 1) In a four-necked separable flask equipped with a stirrer equipped with a cross stirrer, a reflux condenser, a thermometer, a nitrogen inlet pipe and a cooling device, 29.74 g of 50 wt% acrylamide aqueous solution and 80 wt% acryloyl 12.66 g of oxyethyltrimethylammonium chloride aqueous solution, 0.025 g of 0.1% by mass N, N′-methylenebisacrylamide aqueous solution and 206.83 g of ion-exchanged water were charged, and the inside of the flask was sufficiently purged with nitrogen. % 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride aqueous solution (0.75 g) was charged and reacted at 35 ° C. for 15 hours. This was coated on a polyethylene film having a thickness of 0.07 mm so that the thickness was 10 mm or less, and was left to dry for 20 hours in a blow dryer at 80 ° C. Then, the obtained sheet copolymer was obtained. Then, it was broken and pulverized to obtain a powdered ionic water-soluble polymer. This was designated as Comparative Production Example 1 and the physical properties are shown in Table 1.

(Comparative Production Example 2) Single amount in the same manner as in Comparative Production Example 1 except that 213.19 g of ion-exchanged water was added and 0.375 g of 0.1% by mass N, N′-methylenebisacrylamide aqueous solution was added. A body copolymer was obtained. This is referred to as Comparative Production Example 2, and the physical properties are shown in Table 1.

(Comparative Production Example 3) Single amount in the same manner as in Comparative Production Example 1 except that ion-exchanged water was 212.93 g and 0.1 mass% N, N′-methylenebisacrylamide aqueous solution was added in an amount of 0.500 g. A body copolymer was obtained. This was designated as Comparative Production Example 3, and the physical properties are shown in Table 1.

The intrinsic viscosities of the prototypes in Production Examples 1 to 10 and Comparative Production Examples 1 to 3 were measured in 1N saline (25 ° C.). The cation equivalent value is a titration value with 1 / 400N potassium polyvinyl sulfonate by a colloid titration method. The aqueous solution viscosity is a viscosity (25 ° C.) measured with a B-type viscometer under No. 2 rotor and 30 rpm after stirring for 60 minutes with a magnetic stirrer so that a 0.2 mass% aqueous solution is obtained.

(Table 1)

(Ionic water-soluble polymer (a) made of powder having a charge inclusion rate of less than 35%, or (c) in the case of three types, and ionicity formed by combining powder (b) having a charge inclusion rate of 35% to 90% Water-soluble polymer prototype)
(Production Example 11) The powdered ionic water-soluble polymer produced in Production Example 1 and Production Example 6 was mixed by mass ratio until Production Example 1: Production Example 6 = 2: 8 until uniform. This was designated as Production Example 11, and the results are shown in Table 2.

(Production Example 12) The powdered ionic water-soluble polymer produced in Production Example 2 and Production Example 7 was mixed in a mass ratio so that Production Example 2: Production Example 7 = 2: 8 until uniform. This was designated as Production Example 12. The results are shown in Table 2.

(Production Example 13) Powdery powder was produced in the same manner as in Production Example 12 except that Production Example 3 and Production Example 8 were made, and 6.5% by mass of sulfamic acid was added to these ionic water-soluble polymers. An ionic water-soluble polymer was obtained. This was designated as Production Example 13, and the results are shown in Table 2.

(Production Example 14) The ionic water-soluble polymer composed of the powder produced in Production Example 4 and Production Example 7 is mixed by weight ratio until Production Example 4: Production Example 7 = 2: 8 until uniform. An ionic water-soluble polymer composed of powder was produced. This was designated as Production Example 14, and the results are shown in Table 2.

(Production Example 15) The ionic water-soluble polymer composed of the powder produced in Production Example 5 and Production Example 7 is mixed until it becomes uniform so that Production Example 5: Production Example 7 = 2: 8 by mass ratio, An ionic water-soluble polymer composed of powder was produced. This was designated as Production Example 15, and the results are shown in Table 2.

(Production Example 16) The ionic water-soluble polymer composed of the powder produced in Production Example 2 and Production Example 10 is produced in a mass ratio such that Production Example 2: Production Example 10 = 2: 8, and these ionic water-soluble polymers are highly soluble. 6.5% by mass of sulfamic acid was added to the molecules, mixed until uniform, and mixed until uniform to produce an ionic water-soluble polymer consisting of powder. This was designated as Production Example 16, and the results are shown in Table 2.

(Production Example 17) The ionic water-soluble polymer composed of the powder produced in Production Example 3 and Production Example 9 is mass-produced such that Production Example 9: Production Example 3 = 2: 8, and these ionic water-soluble polymers are highly soluble. 6.5% by mass of sulfamic acid was added to the molecule and mixed until uniform to produce an ionic water-soluble polymer consisting of powder. This was designated as Production Example 17, and the results are shown in Table 2.

(Production Example 18) The ionic water-soluble polymer composed of the powder produced in Production Example 3 and Production Example 10 is mass-produced such that Production Example 3: Production Example 10 = 2: 8, and these ionic water-soluble polymers are highly soluble. 6.5% by mass of sulfamic acid was added to the molecule and mixed until uniform to produce an ionic water-soluble polymer consisting of powder. This was designated as Production Example 18, and the results are shown in Table 2.

(Production Example 19) The ionic water-soluble polymer composed of the powder produced in Production Example 4 and Production Example 9 is mixed in a mass ratio so that Production Example 4: Production Example 9 = 2: 8 until uniform. An ionic water-soluble polymer composed of powder was produced. This was designated as Production Example 19, and the results are shown in Table 2.

Production Example 20 Production Example 3: Production Example 9: Production Example 4: = 2: 5: 3 by weight ratio of the ionic water-soluble polymer comprising the powder produced in Production Example 3, Production Example 4 and Production Example 9. In addition, 6.5% by mass of sulfamic acid was added to these ionic water-soluble polymers and mixed until uniform to produce an ionic water-soluble polymer consisting of powder. This was designated as Production Example 20, and the results are shown in Table 2.

(Production Example 21) The ionic water-soluble polymer comprising the powder produced in Production Example 3, Production Example 9 and Production Example 2 was produced in a mass ratio of Production Example 3: Production Example 9: Production Example 2 = 2: 5: 3, And 6.5 mass% sulfamic acid was added with respect to these ionic water-soluble polymers, and it mixed until it became uniform, and manufactured the ionic water-soluble polymer which consists of powder. This was designated as Production Example 21, and the results are shown in Table 2.

(Production Example 22) The ionic water-soluble polymer composed of the powder produced in Production Example 1 and Production Example 9 is mixed by mass ratio until Production Example 1: Production Example 9 = 2: 8 until uniform. An ionic water-soluble polymer composed of powder was produced. This was designated as Production Example 22, and the results are shown in Table 2.

(Production Example 23) The ionic water-soluble polymer composed of the powder produced in Production Example 2 and Production Example 8 is mixed in a mass ratio so that Production Example 2: Production Example 8 = 2: 8 until uniform. An ionic water-soluble polymer composed of powder was produced. This was designated as Production Example 23, and the results are shown in Table 2.

(Table 2)

(Sludge dewatering test 1) The ionic water-soluble polymer made of the powder produced in Production Examples 20 and 21 was dissolved in water to prepare a 0.2 wt% aqueous solution, and the sludge dewatering test was conducted. Human waste surplus sludge (pH 7.06, total ss content 46,250 mg / L) was collected in a 200 mL poly beaker, and 370 ppm, 400 ppm and 430 ppm of ionic water-soluble polymer solution consisting of the above powder was added to the sludge weight. Each sample was transferred to a beaker and stirred 20 times, then filtered through a T-1178L nylon filter cloth, and the amount of filtrate after 45 seconds was measured. Moreover, after observing the cake supportability (hardness of the dehydrated cake) of the filtered sludge, it was dehydrated at a press pressure of 2 kg / m ² for 1 minute to confirm the filter cloth peelability, and the moisture content of the cake (105 ° C., dried for 20 hours) Was measured. The results are shown in Table 3.

(Comparative sludge dewatering test 1) A sludge dewatering test was conducted in the same manner as in the sludge dewatering test 1 except that the powdered ionic water-soluble polymer was Production Examples 2, 3, 4, 5 and 7, respectively. . The results are shown in Table 3.

( Table 3 )
Regarding the cake supportability and filter cloth peelability, “◯” was given when the addition amount was 400 ppm in Production Example 10, “◎” when it was better, and “△” when it was inferior.

In the results of Table 3, ionic water-soluble polymers composed of powders having a charge inclusion rate of less than 35% and 35% or more and 90% or less are evident in terms of cake support and filter cloth peelability as a result of dehydration tests. It is clear that the initial drainage is improved and the water content of the dehydrated cake is decreased with the increase in the filtrate amount.

(Papermaking test 1 ) Anionic polymer (sodium acrylate 20 mol% -acrylamide 80 mol% copolymer, 0.5 wt% saline solution viscosity 120.0 (mPa · s) adjusted to 0.2 wt% with ion-exchanged water ) (Salt concentration 4 wt%, B-type viscometer No. 2 rotor, 60 rpm, 25 ° C. measurement)) and ionic water-soluble polymer composed of the powder synthesized in Production Example 21 dissolved in water to 0.2 wt% A papermaking test and a yield test using a Brit dynamic jar tester were performed using LBKP beaten to 400 ml of Canadian Standard Freeness. After adjusting LBKP to a concentration of 1.0%, commercially available calcium carbonate is added to the pulp weight by 20%, and aluminum sulfate (8.0% as Al ₂ O ₃ minutes) is added to the pulp weight by 1.2%. To pH 7.5. The anionic polymer aqueous solution was added to the papermaking raw material so that the anionic polymer was 100 ppm based on the weight of the pulp, followed by stirring for 15 seconds, and then an ionic water-soluble polymer solution comprising the powder of Production Example 21 Was added so that the weight of the polymer was 100 ppm and 200 ppm, respectively, with respect to the pulp weight, and further stirred at 2000 rpm for 30 seconds. After that, paper is made with a Tappi standard sheet machine so that the basis weight is 80 g / m ² , the obtained wet paper is pressed at 4 kg / cm ² for 5 minutes, and then dried with a 105 ° C. rotary dryer for 3 minutes, and handmade paper. Got. This handmade paper is 20 ° C, 65%
After humidity conditioning for 24 hours under HR conditions, the texture of the finished paper, opacity and ISO whiteness were evaluated. The results are shown in Table 4 .

After adjusting LBKP to a concentration of 0.5%, commercially available calcium carbonate is added to the pulp weight by 20%, aluminum sulfate (8.0% as Al2O3) is added to the pulp weight by 1.2%, and the pH is adjusted to 7. with sulfuric acid. Adjusted to 5. This papermaking raw material was put into a Brit type dynamic jar tester, and the anionic polymer solution was added so that the anionic polymer was 100 ppm by weight with respect to the pulp weight, followed by stirring at 2000 rpm for 15 seconds, The ionic water-soluble polymer solution composed of the powder of Production Example 21 was added so that the polymer weight was 100 ppm and 200 ppm, respectively, with respect to the pulp weight. Next, after stirring at 2000 rpm for 30 seconds, the stirring rotation speed was reduced to 800 rpm, white water was discharged for 10 seconds, and then white water was collected for 30 seconds. From the SS concentration of the collected white water and the amount of ash obtained by ashing at 525 ° C. for 2 hours, the total yield and the ash yield of the papermaking raw material were determined. The results are shown in Table 4 .

(Comparative Papermaking Test 1 ) With respect to Production Examples 2, 3 and 9, a papermaking test and a yield test were conducted in the same manner as in Example 4, and the appearance of the paper, the opacity, the ISO whiteness, and the total papermaking raw material The yield and ash yield were determined. The results are shown in Table 4 .

(Table 4 )
Formation evaluation: base bentonite / Production Example 7 of cationic polymer = 1000/100 compared to those bad and is △, that there is no difference ○
Measuring method of opacity of paper: JIS-P1849: 2000
ISO whiteness measurement method for paper: JIS-P1848: 2001

As shown in Table 4 , by using an anionic polymer, the total yield rate, the ash content yield rate, the opacity and the ISO whiteness are improved, while the texture of the finished paper is improved. Can be confirmed.

Claims (11)

Oil obtained by emulsifying and polymerizing a water-immiscible organic liquid with a surfactant to form a continuous phase and a monomer aqueous solution mixture containing a cationic monomer and a polyfunctional monomer to form a dispersed phase. An ionic polymer powder obtained by drying a water-in-oil emulsion liquid, wherein the water-soluble polymer powder (A) has a charge encapsulation rate of the ionic polymer of 35% to 90%, and the water-in-oil droplets. One or more water-soluble polymer powders selected from powders of water-soluble polymers having a charge inclusion rate of less than 35% and 3% or more, other than the production method of drying and granulating a mold emulsion liquid (B ), Which is a powdered ionic water-soluble polymer, wherein the powdered ionic water-soluble polymer is a monomer represented by the following general formula (1) and / or (2): 4.9999 to 100 mol %, The following general formula (3) The water-soluble polymer powder, which is a copolymer of 0 to 50 mol% of monomer, 0 to 95 mol% of water-soluble nonionic monomer and 0.0001 to 0.1 mol% of polyfunctional monomer (A), water-soluble polymer powder (B ₁ ) having a structure represented by the following general formula (4) or general formula (5), monomer 5 represented by the following general formula (1) or (2) Water-soluble polymer powder (B ₂ ) and acid comprising a copolymer of 95 mol% and a water-soluble nonionic monomer 0 to 90 mol% and a monomer 5 to 50 mol% represented by the following general formula (3) Powdered ionic water-soluble polymer which is a mixture of
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl group having 1 to ₃ carbon atoms, an alkoxyl group or a benzyl group, and R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A is O or NH, B is an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, _{X 1} ^- represents respectively an anion.
General formula (2)
R ₅ and R _{6 each} represent hydrogen or a methyl group, R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.
General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation.
General formula (4)
R _{12 and} R ₁₃ represent hydrogen or a methyl group, H ⁺ Z ⁻ represents an inorganic acid and / or an organic acid, and H ⁺ Z ⁻ = 0 when not neutralized.
General formula (5)
R _{12 and} R ₁₃ represent hydrogen or a methyl group, H ⁺ Z ⁻ represents an inorganic acid and / or an organic acid, and H ⁺ Z ⁻ = 0 when not neutralized. Oil obtained by emulsifying and polymerizing a water-immiscible organic liquid with a surfactant to form a continuous phase and a monomer aqueous solution mixture containing a cationic monomer and a polyfunctional monomer to form a dispersed phase. An ionic polymer powder obtained by drying a water-in-oil emulsion liquid, wherein the water-soluble polymer powder (A) has a charge encapsulation rate of the ionic polymer of 35% to 90%, and the water-in-oil droplets. One or more water-soluble polymer powders selected from powders of water-soluble polymers having a charge inclusion rate of less than 35% and 3% or more, other than the production method of drying and granulating a mold emulsion liquid (B ), Which is a powdered ionic water-soluble polymer, wherein the powdered ionic water-soluble polymer is a monomer represented by the following general formula (1) and / or (2): 4.9999 to 100 mol %, The following general formula (3) Water-soluble polymer powder comprising a copolymer of 0 to 50 mol% of a monomer, 0 to 95 mol% of a water-soluble nonionic monomer and 0.0001 to 0.1 mol% of a polyfunctional monomer ( A), a water-soluble polymer powder which is a copolymer of 5 to 100 mol% of a monomer represented by the following general formula (1) or (2) and 0 to 95 mol% of a water-soluble nonionic monomer ( B ₁ ), 5 to 95 mol% of a monomer represented by the following general formula (1) or (2), 5 to 50 mol% of a monomer represented by the following general formula (3), and a water-soluble nonionic monomer A powdery ionic water-soluble polymer which is a mixture of a water-soluble polymer powder (B ₂ ) which is a copolymer of 0 to 90 mol% of a body and an acid.
General formula (1)
R ₁ is hydrogen or a methyl group, R ₂ and R ₃ are an alkyl group having 1 to ₃ carbon atoms, an alkoxyl group or a benzyl group, and R ₄ is hydrogen, an alkyl group having 1 to 3 carbon atoms, an alkoxyl group or a benzyl group. , Same or different. A is O or NH, B is an alkylene group or an alkoxylene group having 2 to 4 carbon atoms, _{X 1} ^- represents respectively an anion.
General formula (2)
R ₅ and R _{6 each} represent hydrogen or a methyl group, R ₇ and R ₈ each represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group or a benzyl group, and X ₂ ⁻ represents an anion.
General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation. The powdered ionic water-soluble polymer according to claim 1 or 2 , wherein the water-soluble polymer powder (A) is obtained by spray-drying a water-in-oil emulsion liquid. The powder form according to claim 1 or 2 , wherein the water-soluble polymer powder (A) is obtained by directly drying a water-in-oil emulsion liquid in a drier with the emulsion liquid. Ionic water-soluble polymer. The water-soluble polymer powder (B) is at least one selected from powders of a water-soluble polymer having a cationic group obtained by drying a dispersion obtained by dispersion polymerization in salt water or water-immiscible organic liquid. The powdered ionic water-soluble polymer according to claim 1 or 2 , wherein The water-soluble polymer powder (B) is one or more selected from a powder of a water-soluble polymer having a cationic group obtained by drying a viscous liquid obtained by aqueous solution polymerization or an aqueous gel-like material having no fluidity. The powdered ionic water-soluble polymer according to claim 1 or 2 . The powdery ionic water-soluble polymer according to claim 1 or 2 , wherein the water-in-oil emulsion liquid does not contain a surfactant having an HLB value of 10 or more. A method for dewatering sludge, comprising dissolving the powdered ionic water-soluble polymer according to any one of claims 1 to 7 in water, adding to the sludge, agglomerating and dehydrating with a dehydrator. A papermaking method, wherein the powdered ionic water-soluble polymer according to any one of claims 1 to 7 is dissolved in water and then added to a papermaking raw material before papermaking. The papermaking method according to claim 9 , wherein the papermaking method is used in combination with an organic anionic substance. The papermaking according to claim 9 , wherein the anionic substance is a polymer of 3 to 100 mol% of a monomer represented by the following general formula (3) and a water-soluble nonionic monomer. Method.
General formula (3)
R ₉ is hydrogen or CH ₂ COOY ₂ , R ₁₀ is hydrogen, methyl group or COOY ₂ , Q is SO ₃ ⁻ , C ₆ H ₄ SO ₃ ⁻ , CONHC (CH ₃ ) ₂ CH ₂ SO ₃ ⁻ , C ₆ H ₄ COO ⁻ or COO ⁻ , and Y ₁ and Y ₂ each represent hydrogen or a cation.