CN101608047A - Water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and retention aid for paper making - Google Patents
Water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and retention aid for paper making Download PDFInfo
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Abstract
The invention provides the quality that particle diameter is even, storage stability well, does not influence gained paper and can keep water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and the retention aid for paper making of high paper strength.A kind of water-soluble polymer dispersion, it is that to be dispersed in salt concn be to obtain in the salt brine solution more than the 10 weight %, below the saturation concentration for the mode of 0.1～150 μ m with median size that its macromolecule dispersing agent (B) that has a branched structure by use makes water-soluble polymers (A), wherein, the content of water-soluble polymers (A) is 10～40 weight %, and the viscosity of dispersion liquid is 100～30000MPas in the time of 25 ℃.
Description
Technical field
The present invention relates to water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and retention aid for paper making.
Background technology
Paper receives publicity as resource capable of circulation, uses in various uses.According to the difference of purposes, to the intensity requirement to some extent of paper, have in the purposes of intensity sometimes, in order to improve the intensity of paper, many unusable papers toughener at needs.
As paper strengthening agent, be extensive use of the acrylamide family macromolecule, usually, the acrylamide family macromolecule obtains with other polymerizable monomer copolymerization by make acrylamide etc. in the aqueous solution, the applicant has also proposed various paper strengthening agents (for example, with reference to patent documentation 1 and 2 etc.).But, because paper is reclaimed and uses repeatedly, thereby exist as the staple fibreization and the deterioration of the paper pulp of paper material and constantly make progress, and the concentration of inorganics in the paper manufacturing systems and inclusion raising, intensity, drainability and retention rate are difficult to problems such as raising.
As the solution countermeasure that drainability, retention rate in the problems referred to above are reduced, proposed to use the method for the dispersion of the water-soluble polymer that dispersion polymerization forms in salt brine solution as retention aid, drainability rising agent (with reference to patent documentation 3 and 4).According to this method, though can access the dispersion liquid that drainability, retention rate are improved, but when using the dispersion liquid that obtains by this method, exist the raising of paper intensity insufficient, and owing to can't obtain the inadequate problem of quality of uniform dispersion liquid thereby gained paper.
Patent documentation 1: No. 3109194 communique of Japanese Patent
Patent documentation 2: No. 3487059 communique of Japanese Patent
Patent documentation 3: the special fair 3-74682 communique of Japan
Patent documentation 4: the special fair 6-72170 communique of Japan
Summary of the invention
The objective of the invention is to, the quality that particle diameter is even, storage stability well, does not influence gained paper is provided and can keeps water-soluble polymer dispersion, paper strengthening agent, paper grade (stock) drainability rising agent and the retention aid for paper making of high paper strength.
In order to address the above problem, the inventor furthers investigate, found that, by the water-soluble polymer dispersion that use to utilize macromolecule dispersing agent, water-soluble polymers be dispersed in specified particle diameter form in the salt brine solution of high density with particular viscosity with branched structure as paper strengthening agent, can make the quality of gained paper good, particularly find by using dispersion copolymerization method, can easily obtain the even and stable water-soluble polymer dispersion of particle diameter, thereby finish the present invention.
Promptly, the present invention relates to water-soluble polymer dispersion, the paper strengthening agent that contains this water-soluble polymer dispersion, contain the paper grade (stock) drainability rising agent of this water-soluble polymer dispersion and contain the retention aid for paper making of this water-soluble polymer dispersion, it is that to be dispersed in salt concn be more than the 10 weight % for the mode of 0.1～150 μ m with median size that the macromolecule dispersing agent (B) that described water-soluble polymer dispersion has a branched structure by use makes water-soluble polymers (A), in the following salt brine solution of saturation concentration and obtain, wherein, the content of water-soluble polymers (A) is 10～40 weight %, and the viscosity of dispersion liquid is 100～30000mPas.
The invention effect
The water-soluble polymer dispersion of the application of the invention is as paper strengthening agent, can not influence quality and gives paper strength to paper.In addition, by adding water-soluble polymer dispersion of the present invention, therefore mineral filler and as the retention raising of the pulp of the raw material of paper also can be used as retention aid for paper making and uses.In addition, by adding water-soluble polymer dispersion of the present invention, the drainability when copying paper improves, and therefore also can be used as paper grade (stock) drainability rising agent and uses.
Embodiment
Water-soluble polymer dispersion of the present invention, it is that to be dispersed in salt concn be to obtain in the salt brine solution more than the 10 weight %, below the saturation concentration for the mode of about 0.1 μ m～about 150 μ m with median size that the macromolecule dispersing agent (B) (hereinafter referred to as (B) composition) that has a branched structure by use makes water-soluble polymers (A) (hereinafter referred to as (A) composition), it is characterized in that, the content of water-soluble polymers (A) is about 10 weight %～about 40 weight %, and the viscosity of dispersion liquid is about 100mPas～about 30000mPas in the time of 25 ℃.Median size is during less than 0.1 μ m, because the influence of particle diameter, viscosity has the tendency that increases, and in addition, when particle diameter was too small, surface-area increased, and may cause the problem on the storage stability such as particle coacervation, thereby not preferred; When median size surpasses 150 μ m, produce particle and problem on the storage stability such as easily precipitate, thus not preferred.In addition, when viscosity is lower than 100mPas, produces particle and problem on the storage stability such as easily precipitate, thus not preferred; When viscosity surpasses 30000mPas, produce operational problem such as lose flowability, thus not preferred.
(A) composition that uses among the present invention can be by for example obtaining radical polymerization composition (a) (hereinafter referred to as (a) composition) polymerization with known method.As (a) composition, be not particularly limited, for example can enumerate: cationic free radical polymerization monomer (a1) (hereinafter referred to as (a1) composition), anionic free radical polymerization monomer (a2) (hereinafter referred to as (a2) composition), cross-linkable monomer (a3) (hereinafter referred to as (a3) composition) and (methyl) acrylamide (a4) (hereinafter referred to as (a4) composition) etc.
As (a1) composition,, can use known material so long as have at least one cationic functional group as amino or quaternary ammonium group and the material with a free-radical polymerised functional group then is not particularly limited.Specifically for example can enumerate: N, N-dimethylaminoethyl (methyl) acrylate, N, N-diethyl aminoethyl (methyl) acrylate, N, N-dimethyl aminopropyl (methyl) acrylamide, N, the salt of (methyl) acrylic monomer of tertiary-amino-containings such as N-diethyl amino propyl group (methyl) acrylamide, (methyl) acrylic monomer of this tertiary-amino-containing, (methyl) acrylic monomer of this tertiary-amino-containing and quaternizing agent reaction and (methyl) acrylic ester monomer that contains quaternary ammonium salt of obtaining etc.Salt can be inorganic acid salts such as hydrochloride, vitriol, also can be organic acid salts such as acetate.In addition, as quaternizing agent, can enumerate monochloro methane, Benzyl Chloride, methyl-sulfate, epoxy chloropropane etc.These (a1) compositions can be used alone or two or more mixing is used.Wherein, N, the quaternized thing of Benzyl Chloride of N-dimethylaminoethyl (methyl) acrylate are when forming polymkeric substance, from the hydrophobicity height, be difficult for being dissolved in the salts solution aspect and consider preferred.
As (a2) composition,, can use known material so long as the material that has at least one anionic functional group and have a free-radical polymerised functional group then is not particularly limited.Specifically for example can enumerate: (methyl) vinylformic acid, fumaric acid, toxilic acid, maleic anhydride, methylene-succinic acid, itaconic anhydride, citraconic acid, citraconic anhydride etc. contain carboxylic monomer, (methyl) allyl sulphonic acid etc. and contain phosphorous acidic group monomers such as sulfonic group monomer, 2-methylacryoyloxyethyl phosphoric acid ester, phosphoric acid vinyl acetate etc.In addition, these monomers also can form the salt of basic metal or amine etc.They can be used alone or two or more mixing is used.Wherein, methylene-succinic acid is owing to make coherency, the dewatering raising thereby preferred of water-soluble polymer dispersion.
As (a3) composition, then be not particularly limited so long as have the material of at least two free-radical polymerised functional groups, can use known material.Specifically for example can enumerate: multifunctional (methyl) acrylic amides such as methylene-bis (methyl) acrylamide, hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, TEG two (methyl) acrylate, six ethylene glycol bisthioglycolates (methyl) acrylate, tripropylene glycol two (methyl) acrylate, two (methyl) esters of acrylic acids such as two cyclopentanol two (methyl) acrylate, as the monomeric trimethylolpropane tris of the polyfunctional vinyl with three above vinyl (methyl) acrylate, tetramethylolmethane three (methyl) acrylate, 1,3,5-three (methyl) acryloyl-oxy six hydrogen-1,3, the 5-triazine, three (methyl) allyl group isocyanuric acid ester, three (methyl) allyl amine, tetramethylol methane four (methyl) acrylate etc., aromatic series polyvinyl compound such as Vinylstyrene etc.They can be used alone or two or more mixing is used.Wherein, consider preferred methylene-bis (methyl) acrylamide or 1,3,5-three acryloyl-oxies six hydrogen-1,3,5-triazines from the aspect that the copolymerization that becomes to grade with (a1)～(a4) is high.
In addition, (a) composition also can use the free radical polymerization monomer with a free-radical polymerised functional group (a5) (hereinafter referred to as (a5) composition) beyond the composition of (a1) composition～(a4).As (a5) composition, specifically for example can enumerate: N-substituted acrylamide class, aromatic vinyl monomer, alkyl (methyl) esters of acrylic acid, vinyl carboxylates class, (methyl) vinyl cyanide, vinyl alcohol etc.As N-substituted acrylamide class, can use known material with being not particularly limited.Specifically for example can enumerate: N, N-dimethyl (methyl) acrylamide, N, N-diethyl (methyl) acrylamide, N, simple function N-substituted acrylamide classes such as N-di-isopropyl (methyl) acrylamide, N-methyl (methyl) acrylamide, N-ethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, the N-tertiary butyl (methyl) acrylamide.As aromatic vinyl monomer, can enumerate the monofunctional monomer class that has aromatic ring in vinylbenzene, alpha-methyl styrene, the Vinyl toluene equimolecular.In addition, as (methyl) alkyl-acrylates, can enumerate: monofunctional monomer classes such as (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) ethyl acrylate, (methyl) cyclohexyl acrylate.As the vinyl carboxylates class, can enumerate vinyl acetate, propionate etc.They can be used alone or two or more mixing is used.Wherein, N,N-DMAA obtain water-soluble polymer dispersion and with the copolymerization height of used (methyl) acrylamide, thereby preferred.
Each composition as containing in (a) composition is not particularly limited, and preferably must use (a1) composition and (a4) composition, and use (a2) composition, (a3) composition as required.In addition, the consumption of each composition is not particularly limited, usually use the about 3 moles of % of (a1) composition～about 40 moles of %, about 0 mole of % of (a2) composition～about 40 moles of %, the about 0 mole of % of (a3) composition～about 1 mole of %, the about 20 moles of % of (a4) composition～about 97 moles of %, preferred 6～20 moles of % of (a1) composition, 3～20 moles of % of (a2) composition, 0.001～0.01 mole of % of (a3) composition, 20～90 moles of % of (a4) composition of using.In addition, when using (a5) composition, its consumption is generally below about 1 mole of %, is preferably 0.5 mole below the %.
(A) composition obtains by making (a) composition carry out radical polymerization.So operation obtains the weight-average molecular weight of (A) composition, be generally about 1,000,000～about 2,000 ten thousand, be preferably about 3,000,000～about 10,000,000.
In addition, be meant the weight-average molecular weight that the polyethylene oxide that recorded by GPC-LALLS method or GPC-RALLS method converted in this said weight-average molecular weight, be with 0.5 mole/L acetate buffer solution (0.5 mole/L acetic acid+0.5 mole %/L sodium acetate aqueous solution, pH about 4.2) be solvent (elutriant), in polymer concentration 0.0125 weight %, 5 ° or the 90 ° values of measuring down (40 ℃) in scattering of light angle.In addition, measuring used polymkeric substance uses to be adjusted to and adds caustic soda behind the 0.5 weight % to pH is 10～12, dipping obtained in 4 hours in the hot water bath more than 80 ℃ again sample.In addition, weight-average molecular weight in this specification sheets and number-average molecular weight are the values of measuring by this method.
(B) composition that uses among the present invention then can use known material so long as have the free radical polyalcohol of branched structure with being not particularly limited.It obtains by make radical polymerization composition (b) (hereinafter referred to as (b) composition) polymerization with known method.As (b) composition, be not particularly limited, for example can enumerate: cationic free radical polymerization monomer (b1) (hereinafter referred to as (b1) composition), anionic free radical polymerization monomer (b2) (hereinafter referred to as (b2) composition), cross-linkable monomer (b3) (hereinafter referred to as (b3) composition) and (methyl) acrylamide (b4) (hereinafter referred to as (b4) composition) etc.
As (b1) composition, can use the same monomer of (a1) composition that can use when preparing (A) composition.In addition, as (b1) composition, the aspect that easily the positively charged ion amount is adjusted to desirable value during from the formation polymkeric substance is considered, preferred (methyl) acrylyl oxy-ethyl-trimethyl salmiac that uses.
As (b2) composition, can use the same monomer of (a2) composition that can use when preparing (A) composition.In addition, as (b2) composition, from the copolymerization height of (methyl) acrylamide, the transfer (chain transfer) of free radical takes place easily, the aspect of regulating molecular weight and crosslinking structure easily considers preferred (methyl) allyl sulphonic acid that uses.
As (b3) composition, can use the same monomer of (a3) composition that can use when preparing (A) composition.In addition, as (b3) composition, from the aspect consideration high, preferred methylene-bis (methyl) acrylamide or 1,3,5-three (methyl) acryloyl-oxy six hydrogen-1,3,5-triazines with the copolymerization of (methyl) acrylamide.
In addition, (b) composition also can use free radical polymerization monomer (b5) (hereinafter referred to as (b5) composition) beyond the composition of (b1) composition～(b4).As (b5) composition, can use the same monomer of (a5) composition that can use when preparing (A) composition.They can be used alone or two or more mixing is used.Wherein, N, N-dimethyl (methyl) acrylamide is high thereby preferred with the copolymerization of (methyl) acrylamide.
Each composition as containing in (b) composition is not particularly limited, and preferably must use (b1) composition and (b3) composition, and use (b2) composition, (b4) composition as required.In addition, the consumption of each composition is not particularly limited, usually use the about 30 moles of % of (b1) composition～about 99.999 moles of %, about 0 mole of % of (b2) composition～about 5 moles of %, the about 0.001 mole of % of (b3) composition～about 1 mole of %, the about 0 mole of % of (b4) composition～about 70 moles of %, preferred 50～99 moles of % of (b1) composition, 0.1～1 mole of % of (b2) composition, 0.001～0.1 mole of % of (b3) composition, 0.5～50 mole of % of (b4) composition of using.In addition, when using (b5) composition, its consumption is generally below about 5 moles of %, is preferably 1 mole below the %.
(B) composition obtains by make (b) composition carry out radical polymerization with known method.Be not particularly limited as radical polymerization.So operation obtain the common weight-average molecular weight of (B) composition be about 10,000～about 2,000,000, when nonvolatile component is adjusted to 20 weight %, be about 100mPas～about 30000mPas 25 ℃ viscosity.
(A) composition and (B) consumption of composition be not particularly limited, usually preferably with respect to (A) composition 100 weight parts, use about 1 weight part of (B) composition～about 10 weight parts.By with (A) composition and (B) consumption of composition be set in the described scope, can access dispersion liquid with polymerisate that more high dispersion stability and paper strength strengthen the property.
As using (A) composition, (B) composition, and make it be dispersed in method in the salt brine solution that salt concn 10 weight % are above, saturation concentration is following, for example (A) composition can be mixed known dispersing method such as employing mechanical dispersion with (B) composition.In addition, the salt that uses during as the preparation salt brine solution as long as not dissolving (A) composition then is not particularly limited, can use inorganic salt, usually as vitriol, phosphoric acid salt etc.Particularly, for example can use: ammonium sulfate, sodium sulfate, sal epsom, Tai-Ace S 150, ammonium hydrogen phosphate, sodium hydrogen phosphate, potassium hydrogen phosphate etc.
In addition, by make in the salt brine solution of (a) composition more than salt concn 10 weight %, below the saturation concentration, dispersion polymerization in the presence of (B) composition, the particle diameter of water-soluble polymer dispersion of the present invention becomes evenly, and it is narrower that molecular weight distribution becomes, thereby preferred especially.The effect of macromolecule dispersing agent in dispersion polymerization fully understood as yet, but thinks that it works when the separating out of polymerisate, and prevents adhesion, the cohesion of the particle that generates.Think that (B) of the present invention composition prevents the excellent property of polymerisate adhesion, cohesion.In addition, dispersion polymerization can be adopted known method, adds radical polymerization initiator usually in the presence of (B) composition, salt, (a) composition, carries out radical polymerization and get final product.Polymerization temperature is different because of the kind of polymerization starter, so long as the temperature that polymerization starter can work gets final product.Add the salt that uses can be divided into that polymerization is added midway, mix after the polymerization etc.The viscosity increased of salt concn reaction solution during less than 10 weight, thus not preferred.In addition, by with (A) composition and (B) ratio (Mw/Mn) of the weight-average molecular weight of mixture of ingredients (Mw) and number-average molecular weight (Mn) be set at about 1.0～about 3.0, can under the state of keeping high paper strength reinforced effects, further reduce influence to quality, thus preferred.In addition, with (A) composition and (B) ratio (Mw/Mn) of the weight-average molecular weight of mixture of ingredients (Mw) and number-average molecular weight (Mn) be set at 1.0～2.0 and can significantly improve the paper strength reinforced effects, thereby preferred especially.
When water-soluble polymer dispersion of the present invention uses as paper strengthening agent, usually preferably will (A) composition be set in more than 3,000,000 with (B) weight-average molecular weight of mixture of ingredients, in addition, to dilute until solid component concentration be about 0.01 weight %～about 1 weight % for preferred water etc.
When water-soluble polymer dispersion of the present invention uses as the drainability rising agent, usually preferably will (A) composition be set in more than 3,000,000 with (B) weight-average molecular weight of mixture of ingredients, in addition, to dilute until solid component concentration be about 0.01 weight %～about 1 weight % for preferred water etc.
When water-soluble polymer dispersion of the present invention uses as retention aid, usually preferably will (A) composition be set in more than 3,000,000 with (B) weight-average molecular weight of mixture of ingredients, in addition, to dilute until solid component concentration be about 0.01 weight %～about 1 weight % for preferred water etc.
Embodiment
Below, enumerate embodiment and comparative example and further specifically describe the present invention, but the invention is not restricted to these embodiment.
(Production Example 1) macromolecule dispersing agent manufacture method
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 80% aqueous solution, 249.99 grams (standard analysis 199.99 grams of the acrylyl oxy-ethyl-trimethyl salmiac of packing into (hereinafter referred to as DMAEA-Q); 99.995 mole %), methylene-bisacrylamide (hereinafter referred to as MBAA) 0.008 restrains (0.005 mole of %), ion exchanged water 529.4 restrains, and carries out nitrogen replacement when being heated to 65 ℃.To wherein adding 2,3% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization as polymerization starter under stirring.Because self heat release elevates the temperature, and 80 ℃ of polymerizations 1 hour, obtains having the macromolecule dispersing agent of branched structure.The viscosity of gained macromolecule dispersing agent is adjusted to 25 ℃, uses rotary viscosimeter instrument (sesame pumping system Co., Ltd. system) to measure (below, viscosity is the value that uses the same method and measure).
(Production Example 2) macromolecule dispersing agent manufacture method
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 80% aqueous solution, 250 grams (standard analysis 200 grams) of the DMAEA-Q that packs into, ion exchanged water 530 grams carry out nitrogen replacement when being heated to 65 ℃.To wherein adding 2,3% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization as polymerization starter under stirring.Because self heat release elevates the temperature, and 80 ℃ of polymerizations 1 hour, is not had the macromolecule dispersing agent of branched structure.
(Production Example 3) macromolecule dispersing agent manufacture method
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the N that packs into, 75% aqueous solution, 249.2 grams (standard analysis 186.9 grams of the quaternized thing of Benzyl Chloride (hereinafter referred to as DMAEA-BQ) of N-dimethylaminoethyl acrylate; 79.49 mole %), 1,3,5-three acryloyl-oxy six hydrogen-1,3,5-triazine (hereinafter referred to as TAF) 0.0217 gram (0.01 mole of %), sodium methallyl sulfonate 0.69 gram (0.5 mole of %), acrylamide 12.4 grams (20 moles of %), ion exchanged water 517.3 grams carry out nitrogen replacement when being heated to 65 ℃.To wherein adding 2,3% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization as polymerization starter under stirring.Because self heat release elevates the temperature, and 80 ℃ of polymerizations 1 hour, obtains having the macromolecule dispersing agent of branched structure.
(Production Example 4) macromolecule dispersing agent manufacture method
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 75% aqueous solution, 143.84 grams (standard analysis 107.9 grams of the DMAEA-BQ that packs into; 39.9 80% aqueous solution, 96.83 grams (standard analysis 77.46 grams of DMAEA-Q mole %); 39.9 mole %), MBAA 0.3091 gram (0.2 mole of %), sodium methallyl sulfonate 0.16 gram (0.1 mole of %), acrylamide 14.18 restrain (19.9 moles of %), ion exchanged water 524.3 restrains, and carries out nitrogen replacement when being heated to 65 ℃.To wherein adding 2,3% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization as polymerization starter under stirring.Because self heat release elevates the temperature, and 80 ℃ of polymerizations 1 hour, obtains having the macromolecule dispersing agent of branched structure.
Table 1
| ? ??(b1) | ? ??(b2) | ? ??(b3) | ? ??(b4) | Nonvolatile component (%) | Viscosity (mPas) | |
| Production Example 1 | ??DMAEA-Q ??99.995 | ??- | ??MBAA ??0.005 | ??- | ??20 | ??1500 |
| Production Example 2 | ??DMAEA-Q ??100 | ??- | ??- | ??- | ??20 | ??1500 |
| Production Example 3 | ??DMAEA-BQ ??79.49 | ??SMAS ??0.5 | ??TAF ??0.01 | ??AM ??20 | ??20 | ??500 |
| Production Example 4 | ??DMAEA-Q/DMAEA-BQ ??39.9/39.9 | ??SMAS ??0.1 | ??MBAA ??0.2 | ??AM ??19.9 | ??20 | ??11000 |
In the table, numeral mole % (b1)～(b4), viscosity is represented the measured value under 25 ℃, following compound is represented in the record that each compound (monomer etc.) is called for short.
DMAEA-Q: acrylyl oxy-ethyl-trimethyl salmiac
DMAEA-BQ:N, the quaternized thing of Benzyl Chloride of N-dimethylaminoethyl acrylate
SMAS: sodium methallyl sulfonate
TAF:1,3,5-three acryloyl-oxies six hydrogen-1,3,5-triazines
IA: methylene-succinic acid
MBAA: methylene-bisacrylamide
AM: acrylamide
The manufacture method of (embodiment 1) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 939.8 grams.To wherein adding acrylamide 182.96 gram (74.995 moles of %), N, 60% aqueous solution, 324.49 grams (standard analysis 194.69 grams of the quaternized thing of Benzyl Chloride (hereinafter referred to as DML) of N-dimethylaminoethyl Methacrylamide; 20 moles of %), methylene-succinic acid 22.32 restrains (5 moles of %), methylene-bisacrylamide (hereinafter referred to as MBAA) 0.0265 restrains (0.005 mole of %), carries out nitrogen replacement when being heated to 45 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 2) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 3 is obtained are dissolved in ion exchanged water 939.8 grams.To 60% aqueous solution, 324.49 grams (standard analysis 194.69 grams that wherein add acrylamide 182.96 grams (74.995 moles of %), DML; 20 moles of %), methylene-succinic acid 22.32 restrains (5 moles of %), MBAA 0.0265 restrains (0.005 mole of %), carries out nitrogen replacement when being heated to 45 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (embodiment 3) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 998.6 grams.To wherein adding acrylamide 257.52 gram (79.99 moles of %), N, N-dimethylaminoethyl Methacrylamide (hereinafter referred to as DM) 142.36 grams (20 moles of %), TAF 0.1129 gram (0.01 mole of %), behind sulfuric acid adjusting pH to 3, when being heated to 45 ℃, carry out nitrogen replacement.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (embodiment 4) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 3 is obtained are dissolved in ion exchanged water 998.6 grams.After wherein add acrylamide 257.52 grams (79.99 moles of %), DM 142.36 grams (20 moles of %), TAF 0.1129 gram (0.01 mole of %), regulating pH to 3, when being heated to 45 ℃, carry out nitrogen replacement with sulfuric acid.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (embodiment 5) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 160 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 954.12 grams.To 60% aqueous solution, 110.97 grams (standard analysis 66.582 grams that wherein add acrylamide 214.12 grams (76.995 moles of %), DML; 6 moles of %), 75% aqueous solution, 84.39 grams (standard analysis 63.292 grams of DMAEA-BQ; 6 moles of %), methylene-succinic acid 55.98 restrains (11 moles of %), MBAA 0.0302 restrains (0.005 mole of %), carries out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 6) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 50 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 1059.68 grams.To 60% aqueous solution, 118.48 grams (standard analysis 71.088 grams that wherein add acrylamide 261.29 grams (87.995 moles of %), DML; 6 moles of %), 75% aqueous solution, 90.11 grams (standard analysis 67.582 grams of DMAEA-BQ; 6 moles of %), MBAA 0.0322 gram (0.005 mole of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 7) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 1018.38 grams.To 75% aqueous solution, 204.87 grams (standard analysis 153.65 grams that wherein add acrylamide 209.29 grams (77.5 moles of %), DMAEA-BQ; 15 moles of %), methylene-succinic acid 37.06 gram (7.5 moles of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 8) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 1016.14 grams.To 75% aqueous solution, 213.86 grams (standard analysis 160.4 grams that wherein add acrylamide 239.61 grams (85 moles of %), DMAEA-BQ; 15 moles of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 9) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 1049.29 grams.To wherein adding acrylamide 338.92 grams (91.99 moles of %), DM 40.73 grams (5 moles of %), methylene-succinic acid 20.22 grams (3 moles of %), TAF 0.1292 gram (0.01 mole of %), behind sulfuric acid adjusting pH to 3, when being heated to 40 ℃, carry out nitrogen replacement.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (embodiment 10) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 1 is obtained are dissolved in ion exchanged water 1048.81 grams.After wherein add acrylamide 358.18 grams (94.99 moles of %), DM 41.68 grams (5 moles of %), TAF 0.1322 gram (0.01 mole of %), regulating pH to 3, when being heated to 40 ℃, carry out nitrogen replacement with sulfuric acid.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (embodiment 11) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 4 is obtained are dissolved in ion exchanged water 999.68 grams.To 60% aqueous solution, 118.48 grams (standard analysis 71.088 grams that wherein add acrylamide 261.29 grams (87.995 moles of %), DML; 6 moles of %), 75% aqueous solution, 90.11 grams (standard analysis 67.582 grams of DMAEA-BQ; 6 moles of %), MBAA 0.0322 gram (0.005 mole of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 12) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 4 is obtained are dissolved in ion exchanged water 1018.38 grams.To 75% aqueous solution, 204.87 grams (standard analysis 153.65 grams that wherein add acrylamide 209.29 grams (77.5 moles of %), DMAEA-BQ; 15 moles of %), methylene-succinic acid 37.06 gram (7.5 moles of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (embodiment 13) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, 110 grams of the dispersion agent with branched structure, ammonium sulfate 400 grams that Production Example 4 is obtained are dissolved in ion exchanged water 1049.29 grams.To wherein adding acrylamide 338.92 grams (91.99 moles of %), DM 40.73 grams (5 moles of %), methylene-succinic acid 20.22 grams (3 moles of %), TAF 0.1292 gram (0.01 mole of %), behind sulfuric acid adjusting pH to 3, when being heated to 40 ℃, carry out nitrogen replacement.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (comparative example 1) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 939.8 grams.To 60% aqueous solution, 324.49 grams (standard analysis 194.69 grams that wherein add acrylamide 182.96 grams (74.995 moles of %), DML; 20 moles of %), methylene-succinic acid 22.32 restrains (5 moles of %), MBAA 0.0265 restrains (0.005 mole of %), carries out nitrogen replacement when being heated to 45 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (comparative example 2) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 998.6 grams.After wherein add acrylamide 257.52 grams (79.99 moles of %), DM 142.36 grams (20 moles of %), TAF 0.1129 gram (0.01 mole of %), regulating pH to 3, when being heated to 45 ℃, carry out nitrogen replacement with sulfuric acid.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (comparative example 3) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 160 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 954.12 grams.To 60% aqueous solution, 110.97 grams (standard analysis 66.582 grams that wherein add acrylamide 214.12 grams (76.995 moles of %), DML; 6 moles of %), 75% aqueous solution, 84.39 grams (standard analysis 63.292 grams of DMAEA-BQ; 6 moles of %), methylene-succinic acid 55.98 restrains (11 moles of %), MBAA 0.0302 restrains (0.005 mole of %), carries out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (comparative example 4) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 50 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 1059.68 grams.To 60% aqueous solution, 118.48 grams (standard analysis 71.088 grams that wherein add acrylamide 261.29 grams (87.995 moles of %), DML; 6 moles of %), 75% aqueous solution, 90.11 grams (standard analysis 67.582 grams of DMAEA-BQ; 6 moles of %), MBAA 0.0322 gram (0.005 mole of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (comparative example 5) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 1018.38 grams.To 75% aqueous solution, 204.87 grams (standard analysis 153.65 grams that wherein add acrylamide 209.29 grams (77.5 moles of %), DMAEA-BQ; 15 moles of %), methylene-succinic acid 37.06 gram (7.5 moles of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (comparative example 6) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 1016.14 grams.To 75% aqueous solution, 213.86 grams (standard analysis 160.4 grams that wherein add acrylamide 239.61 grams (85 moles of %), DMAEA-BQ; 15 moles of %), carry out nitrogen replacement when being heated to 40 ℃.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain water-soluble polymer dispersion.
The manufacture method of (comparative example 7) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 1049.29 grams.To wherein adding acrylamide 338.92 grams (91.99 moles of %), DM 40.73 grams (5 moles of %), methylene-succinic acid 20.22 grams (3 moles of %), TAF 0.1292 gram (0.01 mole of %), behind sulfuric acid adjusting pH to 3, when being heated to 40 ℃, carry out nitrogen replacement.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
The manufacture method of (comparative example 8) water-soluble polymer dispersion
In 2 liters of five mouthfuls of removable flasks that possess agitator, thermometer, reflux condensing tube, nitrogen ingress pipe, the dispersion agent that does not have branched structure 110 grams, ammonium sulfate 400 grams that Production Example 2 is obtained are dissolved in ion exchanged water 1048.81 grams.After wherein add acrylamide 358.18 grams (94.99 moles of %), DM 41.68 grams (5 moles of %), TAF 0.1322 gram (0.01 mole of %), regulating pH to 3, when being heated to 40 ℃, carry out nitrogen replacement with sulfuric acid.To wherein adding 2,2% aqueous solution, 20 grams of 2 '-azo diisobutyl amidine hydrochloride carry out polymerization in 12 hours as polymerization starter under stirring, and obtain the polymkeric substance of dispersed microparticles in salt brine solution.
To the dispersion that embodiment and comparative example obtain, measure median size, molecular weight distribution, in addition, observe the particle outward appearance.It the results are shown in table 2.In addition, median size and particle outward appearance are by carrying out with observation by light microscope.The particle outward appearance is even according to particle, many these 3 stages of the micro-existence of oversize particle, oversize particle estimate.Molecular weight distribution is the value of being measured by weight-average molecular weight that obtains with the polyethylene oxide scaled value that records by gel permeation chromatography and number-average molecular weight.
Gel permeation chromatography is measured under following condition determination.
GPC main body: TOSOH Co., Ltd's system
Post: one of system guard column PWXL of TOSOH Co., Ltd and two of GMPWXL (40 ℃ of temperature)
Elutriant: 0.5 mole/L acetate buffer solution (0.5 mole/L acetic acid (Wako Pure Chemical Industries, Ltd.'s system)+0.5 mole/L sodium-acetate (the キ シ ダ KCC system) aqueous solution, pH about 4.2)
Flow velocity: 0.8ml/ minute
Detector: TOSOH Co., Ltd system concentration detector (RI-8010) and light scattering detector (LS-8000) (room temperature) LALLS method, PVC ス コ テ Star Network corporate system TDA MODEL301 (concentration detector, 90 ° of light scattering detectors and viscosity detector (40 ℃ of temperature)) RALLS method
Measure sample: be adjusted to that to add caustic soda behind the 0.5 weight % be 10～12 until pH, dipping was diluted to 0.0125 weight % with elutriant and measures after 4 hours in the hot water bath more than 80 ℃.
Table 2
| Dispersion | Dispersion agent | ? ??(a1) | ? ??(a2) | ? ??(a3) | ? ??(a4) | Viscosity (mPas) | Median size (μ m) | The particle outward appearance | Molecular weight distribution mw/mn |
| Embodiment 1 | Production Example 1 | ??DML20 | ??IA ??5 | ??MBAA ??0.005 | ??AM ??74.995 | ??3000 | ??30 | Evenly | ??1.8 |
| Embodiment 2 | Production Example 3 | ??DML20 | ??IA ??5 | ??MBAA ??0.005 | ??AM ??74.995 | ??3500 | ??30 | Evenly | ??1.6 |
| Embodiment 3 | Production Example 1 | ??DM20 | ??- | ??TAF ??0.01 | ??AM ??79.99 | ??4000 | ??30 | Evenly | ??1.7 |
| Embodiment 4 | Production Example 3 | ??DM20 | ??- | ??TAF ??0.01 | ??AM ??79.99 | ??4500 | ??20 | Evenly | ??1.5 |
| Embodiment 5 | Production Example 1 | ??DML/DMAEA-BQ ??6/6 | ??IA ??11 | ??MBAA ??0.005 | ??AM ??76.995 | ??15000 | ??20 | Evenly | ??1.4 |
| Embodiment 6 | Production Example 1 | ??DML/DMAEA-BQ ??6/6 | ??- | ??MBAA ??0.005 | ??AM ??87.995 | ??400 | ??30 | Evenly | ??1.5 |
| Embodiment 7 | Production Example 1 | ??DMAEA-BQ ??15 | ??IA ??7.5 | ??- | ??AM ??77.5 | ??4500 | ??20 | Evenly | ??1.8 |
| Embodiment 8 | Production Example 1 | ??DMAEA-BQ ??15 | ??- | ??- | ??AM ??85 | ??4000 | ??30 | Evenly | ??1.5 |
| Embodiment 9 | Production Example 1 | ??DM ??5 | ??IA ??3 | ??TAF ??0.01 | ??AM ??91.99 | ? ??3500 | ? ??40 | The oversize particle trace | ? ??2.6 |
| Embodiment 10 | Production Example 1 | ??DM ??5 | ??- | ??TAF ??0.01 | ??AM ??94.99 | ? ??800 | ? ??50 | The oversize particle trace | ? ??2.7 |
| Embodiment 11 | Production Example 4 | ??DML/DMAEA-BQ ??6/6 | ??- | ??MBAA ??0.005 | ??AM ??87.995 | ??1400 | ??20 | Evenly | ??1.5 |
| Embodiment 12 | Production Example 4 | ??DMAEA-BQ ??15 | ??IA ??7.5 | ??- | ??AM ??77.5 | ??8500 | ??20 | Evenly | ??1.7 |
| Embodiment 13 | Production Example 4 | ??DM ??5 | ??IA ??3 | ??TAF ??0.01 | ??AM ??91.99 | ? ??6500 | ? ??40 | The oversize particle trace | ? ??2.2 |
| Comparative example 1 | Production Example 2 | ??DML ??20 | ??IA ??5 | ??MBAA ??0.005 | ??AM ??74.995 | ? ??6000 | ? ??30 | Oversize particle is many | ? ??3.1 |
| Comparative example 2 | Production Example 2 | ??DM ??20 | ??- | ??TAF ??0.005 | ??AM ??79.99 | ? ??5500 | ? ??30 | Oversize particle is many | ? ??3.3 |
| Comparative example 3 | Production Example 2 | ??DML/DMAEA-BQ ??6/6 | ??IA ??11 | ??MBAA ??0.005 | ??AM ??76.995 | ? ??15500 | ? ??20 | Oversize particle is many | ? ??3.2 |
| Comparative example 4 | Production Example 2 | ??DML/DMAEA-BQ ??6/6 | ??- | ??MBAA ??0.005 | ??AM ??87.995 | ? ??500 | ? ??30 | Oversize particle is many | ? ??3.3 |
| Comparative example 5 | Production Example 2 | ? ??DMAEA-BQ ??15 | ? ??IA ??7.5 | ? ??- | ? ??AM ??77.5 | ? ??5000 | ? ??30 | Oversize particle is many | ? ??3.3 |
| Comparative example 6 | Production Example 2 | ??DMAEA-BQ ??15 | ??- | ??- | ??AM ??85 | ? ??3500 | ? ??30 | Oversize particle is many | ? ??3.3 |
| Comparative example 7 | Production Example 2 | ??DM ??5 | ??IA ??3 | ??TAF ??0.01 | ??AM ??91.99 | ? ??4000 | ? ??40 | The oversize particle trace | ? ??3.1 |
| Comparative example 8 | Production Example 2 | ??DM ??5 | ??- | ??TAF ??0.01 | ??AM ??94.99 | ? ??1000 | ? ??50 | The oversize particle trace | ? ??3.2 |
Numeral mole % in the table.Viscosity is the measured value under 25 ℃.
In addition, following compound is represented in the record that each compound (monomer etc.) is called for short in the table 2.
DML:N, the quaternized thing of Benzyl Chloride of N-dimethylaminoethyl Methacrylamide
DMAEA-BQ:N, the quaternized thing of Benzyl Chloride of N-dimethylaminoethyl acrylate
DM:N, N-dimethylaminoethyl Methacrylamide
SMAS: sodium methallyl sulfonate
MBAA: methylene-bisacrylamide
TAF:1,3,5-three acryloyl-oxies six hydrogen-1,3,5-triazines
AM: acrylamide
Evaluation method 1: at cardboard
(evaluation Example 1～26 and comparative evaluation example 1～10)
Old fluting board is pulled an oar with Niagara formula hollander, and adding with respect to paper stock solids component amount in the 350ml paper stock that is adjusted to Canadian Standard Freeness (C.S.F) is the Tai-Ace S 150 of 1.0 weight %, regulates pH to 6.5.When this paper stock slurry is copied paper, paper stock concentration is set at 1.5%, the water-soluble polymer dispersion that embodiment 1 to 13 and comparative example 1 to 8 are obtained is 0.05 weight % with the solid component concentration that tap water is diluted to polymkeric substance ((A)+(B)), add 0.05 weight % or 0.1 weight % with respect to paper stock solids component amount, with bonding/copy sheet machine (tapping/sheetmachine) dehydration, and with 5 kilograms/cm
2Pressing 2 minutes is so that grammes per square metre is 150 gram/m
2Mode copy paper.Then with rotary-type moisture eliminator 105 ℃ of dryings 4 minutes, and damping 24 hours under 23 ℃, the condition of 50%R.H. is measured then than rupture strength and quality variation factor.Simultaneously, pulp 500ml behind the above-mentioned interpolation medicine is poured in the Britt dynamic drainage instrument (40 order net), use agitator to stir (2000rpm) on one side with turbine blade, gather drainage 100ml from following hole on one side, behind No.2 filter paper suction filtration, drying is 60 minutes under 110 ℃, measures dried quality, obtains total retention rate (OPR) thus.In addition, the drainage amount of the pulp behind the above-mentioned interpolation medicine of also independent mensuration.
In addition, the drainage amount is measured according to JIS P8121, measure according to JIS P8131 than rupture strength, the quality variation factor by will through among the light (brightness) of the gained paper input Computerized image processing system Hyper-700 (OBS system), Luminance Distribution carried out statistical study measure.In addition, the internal intensity of evaluation Example 27～52 and comparative evaluation example 11～20 (internal bond) is measured according to J.TAPPI No18-2.
The water-soluble polymer dispersion solids component is shown in table 3 with respect to the adding rate of paper stock solids component and the measurement result of projects in each evaluation Example.
Table 3
| Dispersion | Adding rate (%) | Drainage amount (mL) | Than rupture strength (kPam 2/g) | Quality variation factor (%) | ??OPR ??(％) | |
| Evaluation Example 1 | Embodiment 1 | ??0.1 | ??468 | ??2.36 | ??21.7 | ??74.0 |
| Evaluation Example 2 | Embodiment 2 | ??0.1 | ??472 | ??2.38 | ??21.4 | ??74.2 |
| Evaluation Example 3 | Embodiment 3 | ??0.1 | ??42 | ??2.41 | ??22.0 | ??74.8 |
| Evaluation Example 4 | Embodiment 4 | ??0.1 | ??465 | ??2.44 | ??21.2 | ??75.0 |
| Evaluation Example 5 | Embodiment 5 | ??0.1 | ??464 | ??2.45 | ??21.2 | ??74.8 |
| Evaluation Example 6 | Embodiment 6 | ??0.1 | ??463 | ??2.41 | ??21.3 | ??74.6 |
| Evaluation Example 7 | Embodiment 7 | ??0.1 | ??467 | ??2.43 | ??21.0 | ??74.2 |
| Evaluation Example 8 | Embodiment 8 | ??0.1 | ??469 | ??2.44 | ??21.4 | ??74.7 |
| Evaluation Example 9 | Embodiment 9 | ??0.1 | ??463 | ??2.30 | ??23.3 | ??74.0 |
| Evaluation Example 10 | Embodiment 10 | ??0.1 | ??469 | ??2.25 | ??23.1 | ??73.4 |
| Evaluation Example 11 | Embodiment 11 | ??0.1 | ??462 | ??2.45 | ??21.2 | ??74.8 |
| Evaluation Example 12 | Embodiment 12 | ??0.1 | ??466 | ??2.46 | ??21.1 | ??74.3 |
| Evaluation Example 13 | Embodiment 13 | ??0.1 | ??465 | ??2.35 | ??22.8 | ??73.6 |
| Evaluation Example 14 | Embodiment 1 | ??0.05 | ??366 | ??2.28 | ??20.6 | ??72.1 |
| Evaluation Example 15 | Embodiment 2 | ??0.05 | ??362 | ??2.32 | ??20.3 | ??72.5 |
| Evaluation Example 16 | Embodiment 3 | ??0.05 | ??372 | ??2.32 | ??21.1 | ??72.4 |
| Evaluation Example 17 | Embodiment 4 | ??0.05 | ??362 | ??2.36 | ??21.0 | ??72.7 |
| Evaluation Example 18 | Embodiment 5 | ??0.05 | ??364 | ??2.3 | ??20.2 | ??72.1 |
| Evaluation Example 19 | Embodiment 6 | ??0.05 | ??363 | ??2.35 | ??21.0 | ??72.1 |
| Evaluation Example 20 | Embodiment 7 | ??0.05 | ??369 | ??2.33 | ??20.2 | ??72.0 |
| Evaluation Example 21 | Embodiment 8 | ??0.05 | ??370 | ??2.34 | ??20.5 | ??72.4 |
| Evaluation Example 22 | Embodiment 9 | ??0.05 | ??363 | ??2.21 | ??22.3 | ??72.0 |
| Evaluation Example 23 | Embodiment 10 | ??0.05 | ??369 | ??2.20 | ??22.1 | ??71.8 |
| Evaluation Example 24 | Embodiment 11 | ??0.05 | ??362 | ??2.35 | ??21.2 | ??72.8 |
| Evaluation Example 25 | Embodiment 12 | ??0.05 | ??366 | ??2.36 | ??21.1 | ??73.5 |
| Evaluation Example 26 | Embodiment 13 | ??0.05 | ??367 | ??2.28 | ??22.9 | ??72.2 |
| Comparative evaluation example 1 | Comparative example 1 | ??0.1 | ??460 | ??2.22 | ??23.6 | ??73.1 |
| Comparative evaluation example 2 | Comparative example 2 | ??0.1 | ??470 | ??2.31 | ??23.9 | ??73.3 |
| Comparative evaluation example 3 | Comparative example 3 | ??0.1 | ??465 | ??2.11 | ??23.8 | ??72.8 |
| Comparative evaluation example 4 | Comparative example 4 | ??0.1 | ??468 | ??2.13 | ??24.2 | ??72.9 |
| Comparative evaluation example 5 | Comparative example 5 | ??0.1 | ??461 | ??2.10 | ??24.2 | ??73.0 |
| Comparative evaluation example 6 | Comparative example 6 | ??0.1 | ??460 | ??2.15 | ??24.1 | ??72.8 |
| Comparative evaluation example 7 | Comparative example 7 | ??0.1 | ??468 | ??2.18 | ??24.5 | ??73.1 |
| Comparative evaluation example 8 | Comparative example 8 | ??0.1 | ??459 | ??2.17 | ??24.2 | ??72.4 |
| Comparative evaluation example 9 | Comparative example 1 | ??0.05 | ??370 | ??2.14 | ??22.8 | ??71.1 |
| Comparative evaluation example 10 | Comparative example 2 | ??0.05 | ??369 | ??2.11 | ??23.1 | ??71.0 |
The quality that quality variation factor numerical value is little is good.
Evaluation method 2: at external paper
(evaluation Example 27～52 and comparative evaluation example 11～20)
L-BKP is pulled an oar with Niagara formula hollander, adding with respect to paper stock solids component amount in the 400ml paper stock that is adjusted to Canadian Standard Freeness (C.S.F) is the Tai-Ace S 150 of 1.0 weight %, and interpolation is light calcium carbonate (Okutama Kogyo Co., Ltd.'s system, the trade(brand)name: マ パ one Le TP-121) as filler, regulate pH to 7.0 of 10 weight % with respect to paper stock solids component amount.When this paper stock slurry is copied paper, paper stock concentration is set at 1.0%, the aqueous solutions of polymers that embodiment 1 to 13 and comparative example 1 to 8 are obtained is 0.05 weight % with the solid component concentration that tap water is diluted to polymkeric substance ((A)+(B)), add 0.025 weight % or 0.05 weight % with respect to paper stock solids component amount, with bonding/copy sheet machine (tapping/sheet machine) dehydration, and with 5 kilograms/cm
2Pressing 2 minutes is so that grammes per square metre is 60 gram/m
2Mode copy paper.Then with rotary-type moisture eliminator 105 ℃ of dryings 4 minutes, internal intensity is measured in and damping 24 hours under 23 ℃, the condition of 50%R.H. then.In addition, drainage amount, quality variation factor and total retention rate are used with the same method of evaluation method 1 and are measured.
The water-soluble polymer dispersion solids component is shown in table 4 with respect to the adding rate of paper stock solids component and the measurement result of projects in each evaluation Example.
Table 4
| Dispersion | Adding rate (%) | Drainage amount (mL) | Internal intensity (N/m) | Quality variation factor (%) | ??OPR ??(％) | |
| Evaluation Example 27 | Embodiment 1 | ??0.025 | ??435 | ??251 | ??12.2 | ??88.0 |
| Evaluation Example 28 | Embodiment 2 | ??0.025 | ??448 | ??256 | ??12.1 | ??88.7 |
| Evaluation Example 29 | Embodiment 3 | ??0.025 | ??440 | ??248 | ??12.7 | ??88.2 |
| Evaluation Example 30 | Embodiment 4 | ??0.025 | ??449 | ??250 | ??12.5 | ??89.0 |
| Evaluation Example 31 | Embodiment 5 | ??0.025 | ??450 | ??255 | ??12.1 | ??88.1 |
| Evaluation Example 32 | Embodiment 6 | ??0.025 | ??444 | ??251 | ??12.4 | ??88.5 |
| Evaluation Example 33 | Embodiment 7 | ??0.025 | ??442 | ??253 | ??12.1 | ??88.9 |
| Evaluation Example 34 | Embodiment 8 | ??0.025 | ??448 | ??253 | ??12.3 | ??88.1 |
| Evaluation Example 35 | Embodiment 9 | ??0.025 | ??428 | ??245 | ??12.9 | ??86.3 |
| Evaluation Example 36 | Embodiment 10 | ??0.025 | ??432 | ??239 | ??13.1 | ??86.2 |
| Evaluation Example 37 | Embodiment 11 | ??0.025 | ??441 | ??250 | ??12.1 | ??88.3 |
| Evaluation Example 38 | Embodiment 12 | ??0.025 | ??443 | ??254 | ??12.3 | ??88.8 |
| Evaluation Example 39 | Embodiment 13 | ??0.025 | ??430 | ??242 | ??13.0 | ??86.3 |
| Evaluation Example 40 | Embodiment 1 | ??0.05 | ??496 | ??269 | ??14.2 | ??89.4 |
| Evaluation Example 41 | Embodiment 2 | ??0.05 | ??492 | ??270 | ??13.8 | ??89.8 |
| Evaluation Example 42 | Embodiment 3 | ??0.05 | ??501 | ??270 | ??14.4 | ??89.4 |
| Evaluation Example 43 | Embodiment 4 | ??0.05 | ??502 | ??272 | ??13.9 | ??90.0 |
| Evaluation Example 44 | Embodiment 5 | ??0.05 | ??510 | ??281 | ??13.4 | ??90.1 |
| Evaluation Example 45 | Embodiment 6 | ??0.05 | ??508 | ??275 | ??13.8 | ??92.1 |
| Evaluation Example 46 | Embodiment 7 | ??0.05 | ??509 | ??274 | ??13.2 | ??91.1 |
| Evaluation Example 47 | Embodiment 8 | ??0.05 | ??504 | ??273 | ??13.4 | ??91.3 |
| Evaluation Example 48 | Embodiment 9 | ??0.05 | ??508 | ??265 | ??14.9 | ??88.3 |
| Evaluation Example 49 | Embodiment 10 | ??0.05 | ??492 | ??269 | ??14.1 | ??87.2 |
| Evaluation Example 50 | Embodiment 11 | ??0.05 | ??501 | ??270 | ??13.3 | ??90.3 |
| Evaluation Example 51 | Embodiment 12 | ??0.05 | ??503 | ??274 | ??13.5 | ??91.8 |
| Evaluation Example 52 | Embodiment 13 | ??0.05 | ??510 | ??260 | ??14.2 | ??89.3 |
| Comparative evaluation example 11 | Comparative example 1 | ??0.025 | ??440 | ??240 | ??13.8 | ??87.1 |
| Comparative evaluation example 12 | Comparative example 2 | ??0.025 | ??442 | ??239 | ??14.0 | ??86.9 |
| Comparative evaluation example 13 | Comparative example 3 | ??0.025 | ??441 | ??230 | ??14.1 | ??86.8 |
| Comparative evaluation example 14 | Comparative example 4 | ??0.025 | ??438 | ??232 | ??14.2 | ??87.0 |
| Comparative evaluation example 15 | Comparative example 5 | ??0.025 | ??440 | ??228 | ??15.0 | ??85.9 |
| Comparative evaluation example 16 | Comparative example 6 | ??0.025 | ??439 | ??234 | ??14.1 | ??86.4 |
| Comparative evaluation example 17 | Comparative example 7 | ??0.025 | ??430 | ??238 | ??13.9 | ??86.5 |
| Comparative evaluation example 18 | Comparative example 8 | ??0.025 | ??434 | ??228 | ??13.9 | ??86.7 |
| Comparative evaluation example 19 | Comparative example 1 | ??0.05 | ??498 | ??253 | ??16.1 | ??88.0 |
| Comparative evaluation example 20 | Comparative example 2 | ??0.05 | ??499 | ??258 | ??16.1 | ??88.2 |
The quality that quality variation factor numerical value is little is good.
Claims (12)
1. water-soluble polymer dispersion, it is that to be dispersed in salt concn be to obtain in the salt brine solution more than the 10 weight %, below the saturation concentration for the mode of 0.1～150 μ m with median size that its macromolecule dispersing agent (B) that has a branched structure by use makes water-soluble polymers (A), wherein, the content of water-soluble polymers (A) is 10～40 weight %, and the viscosity of dispersion liquid is 100～30000mPas in the time of 25 ℃.
2. water-soluble polymer dispersion as claimed in claim 1, its by have the macromolecule dispersing agent of branched structure (B) in the presence of, make that dispersion polymerization obtains in the salt brine solution of radical polymerization composition (a) more than salt concn is 10 weight %, below the saturation concentration.
3. water-soluble polymer dispersion as claimed in claim 1 or 2, wherein, the water-soluble polymers (A) and the ratio (Mw/Mn) of weight-average molecular weight (Mw) and number-average molecular weight (Mn) of mixture with macromolecule dispersing agent (B) of branched structure are 1.0～3.0.
4. as each described water-soluble polymer dispersion in the claim 1～3, wherein, the macromolecule dispersing agent (B) with branched structure comprises and makes radical polymerization composition (b) polymerization that contains 30 moles of cationic free radical polymerization monomers of % (b1) at least and the polymkeric substance that obtains.
5. as each described water-soluble polymer dispersion in the claim 1～4, wherein,, use 1～10 weight part to have the macromolecule dispersing agent (B) of branched structure with respect to water-soluble polymers (A) 100 weight parts.
6. as each described water-soluble polymer dispersion in the claim 1～5, wherein, the macromolecule dispersing agent (B) with branched structure is to make cationic free radical polymerization monomer (b1), cross-linkable monomer (b3) and the anionic free radical polymerization monomer (b2) that uses as required and (b4) copolymerization of (methyl) acrylamide and the multipolymer that obtains.
7. as each described water-soluble polymer dispersion in the claim 1～6, wherein, the macromolecule dispersing agent (B) with branched structure is to make 30～99.999 moles of cationic free radical polymerization monomers of % (b1), 0～5 mole of % anionic free radical polymerization monomer (b2), 0.001～1 mole of % cross-linkable monomer (b3) and 0～70 mole of % (methyl) acrylamide (b4) copolymerization and the multipolymer that obtains.
8. as each described water-soluble polymer dispersion in the claim 1～7, wherein, water-soluble polymers (A) is to make cationic free radical polymerization monomer (a1), (methyl) acrylamide (a4) and the anionic free radical polymerization monomer (a2) that uses as required and cross-linkable monomer (a3) copolymerization and the multipolymer that obtains.
9. as each described water-soluble polymer dispersion in the claim 1～8, wherein, water-soluble polymers (A) is to make 3～40 moles of cationic free radical polymerization monomers of % (a1), 0～40 mole of % anionic free radical polymerization monomer (a2), 0～1 mole of % cross-linkable monomer (a3) and 20～97 moles of % (methyl) acrylamide (a4) copolymerization and the multipolymer that obtains.
10. a paper strengthening agent contains each described water-soluble polymer dispersion in the claim 1～9.
11. a paper grade (stock) drainability rising agent contains each described water-soluble polymer dispersion in the claim 1～9.
12. a retention aid for paper making contains each described water-soluble polymer dispersion in the claim 1～9.
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| CN102206302A (en) * | 2010-03-31 | 2011-10-05 | 荒川化学工业株式会社 | Water-soluble polymer dispersion liquid, paper strength agent, papermaking filter aid and papermaking retention agent |
| CN104343052A (en) * | 2013-08-08 | 2015-02-11 | 荒川化学工业株式会社 | Paper strength improver and paper obtained by using the paper strength improver |
| CN105980428A (en) * | 2014-12-08 | 2016-09-28 | 播磨化成株式会社 | Acrylamide polymer, paper strength enhancing agent, and paper |
| CN113863049A (en) * | 2021-10-29 | 2021-12-31 | 杭州绿邦科技有限公司 | Paper strengthening agent |
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| JP2010024441A (en) | 2010-02-04 |
| CN101608047B (en) | 2014-10-29 |
| JP5445831B2 (en) | 2014-03-19 |
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