JP3538822B2 - Aqueous dispersion composition of cationic polymer - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an aqueous dispersion composition of a cationic polymer. More specifically, the present invention maintains a low viscosity even at a high concentration by using a stable aqueous dispersion of a water-soluble cationic polymer used as a flocculant dewatering agent for sludge, an additive for paper, and the like. Excellent handling in terms of automation and labor saving, no oil like water-in-oil emulsion polymer, no dust like powder polymer, and excellent cationic property in terms of work environment improvement The present invention relates to an aqueous dispersion composition of a polymer.

[0002]

2. Description of the Related Art Polymers having vinylamine units obtained by hydrolyzing a polymer comprising N-vinylformamide or N-vinylacetamide as an essential monomer component (JP-A-58-23809, JP-A-59-3)
No. 9400) and a polymer having an amidine unit obtained by hydrolyzing a polymer containing N-vinylcarboxylic acid amide and acrylonitrile as essential components (JP-A-5-192513) include a coagulation dewatering agent for sludge and paper. Is known to exhibit good performance as an additive for use. In such a polymer flocculant, a polymer is cross-linked and adsorbed to two or more particles in water, and coagulation occurs. However, the larger the adsorbed layer thickness, the more advantageous the cross-linking coagulation is. Things are required. Furthermore, such a polymer flocculant is introduced into a dissociating group and is converted into an electrolyte, which causes electrostatic repulsion between ionized groups in water and greatly expands the polymer chain. However, it is not uncommon that the viscosity tends to be high, and the intrinsic viscosity measured using a 1N aqueous solution of sodium chloride as a solvent reaches 10 dl / g. When the viscosity of the aqueous solution increases, various difficulties arise in handling, and for example, pumping of a 5% by weight aqueous solution may not be possible. In order to improve the handleability of a polymer flocculant comprising a cationic polymer, it has been proposed to use a water-in-oil emulsion (JP-A-5-117).
313, JP-A-5-309208). By making the cationic polymer a water-in-oil emulsion,
Although the handleability is improved and labor saving is possible, the water-in-oil emulsion has a problem in terms of odor and safety in work because mineral oil is used as a dispersion medium, and from the viewpoint of global environmental protection. There is also a need for improvement.

[0003]

SUMMARY OF THE INVENTION The present invention provides a stable aqueous dispersion of a high molecular weight water-soluble cationic polymer which maintains a low viscosity even at a high concentration and has excellent handling properties in terms of automation and labor saving. The purpose is to provide a liquid.

[0004]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, by combining a polymer having an amine unit or an amidine unit with a specific salt, the polymer concentration is increased. in spite of,
Found that it can be made into an aqueous dispersion having good fluidity,
Based on this finding, the present invention has been completed. That is, the present invention provides: (1) (a) 10 to 30% by weight of a polymer having an amine unit of the general formula [1] or 10 to 30% by weight of a polymer having an amidine unit of the general formula [2] or [3]; 10 to 30% by weight of inorganic salt composed of nitrate alone or a combination of nitrate and another inorganic salt, (c) 0 to 10% by weight of nonionic or cationic water-soluble polymer, (d) Nonionic or cationic interface An aqueous dispersion composition of a flowable cationic polymer, characterized by containing 0 to 20% by weight of an activator and (e) water;

Embedded image (Wherein, R ¹ and R ² are hydrogen or a methyl group, and X ⁻ is a negative ion). Further, as a preferred embodiment of the present invention, (2) a polymer having an amine unit is hydrolyzed by using N-vinylformamide, N-vinylacetamide, N-isopropenylformamide or N-isopropenylacetamide as an essential monomer component (3) The aqueous dispersion composition of a cationic polymer according to item (1), wherein the polymer having an amidine unit is N-vinylformamide, N-vinylacetamide, N-isopropenylformamide or (4) Amine-based aqueous dispersion composition of a cationic polymer obtained by hydrolyzing and amidinating a polymer comprising N-isopropenylacetamide and (meth) acrylonitrile as essential monomer components; All structural units of polymer having units (1) wherein the proportion of amine units in the unit is 35 to 95 mol%
(5) The aqueous dispersion composition of the cationic polymer according to the item (2) or (2), wherein (5) the proportion of the amidine unit in the total structural units of the polymer having the amidine unit is 35 to 95 mol%.
(1) The aqueous dispersion composition of the cationic polymer according to the item (1) or (3), (6) the polymer having an amidine unit also has an amine unit, and the polymer having an amidine unit and an amine unit occupy in all the structural units. Item (1), wherein the ratio of the total amount is 35 to 95 mol%,
(3) The aqueous dispersion composition of the cationic polymer according to the above (3) or (5), (7) the first to sixth aspects wherein the nitrate is sodium nitrate.
(8) The aqueous dispersion composition of the cationic polymer according to the above (1) to (7), wherein the other inorganic salt is sodium chloride or sodium sulfate. Compositions.

The polymer having an amine unit used in the composition of the present invention comprises N-vinylformamide, N-vinylacetamide, N-isopropenylformamide or N-isopropenylacetamide represented by the general formula [4] as an essential monomer component. Can be obtained by hydrolysis of a polymer as Further, the polymer having an amidine unit used in the composition of the present invention is an N-polymer represented by the general formula [4].
A polymer comprising vinylformamide, N-vinylacetamide, N-isopropenylformamide or N-isopropenylacetamide and (meth) acrylonitrile represented by the general formula [5] as essential monomer components can be obtained by hydrolysis and amidination. it can.

Embedded image (Wherein, R ¹ , R ^2, and R ³ are hydrogen or a methyl group.) Further, the polymer subjected to the hydrolysis includes other copolymerizable vinyl monomer components and the like in addition to the essential monomer components. You may have. Examples of such copolymerizable vinyl monomers include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N
-Diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, vinyl acetate, styrene, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid, vinylsulfonic acid, styrenesulfonic acid, 2- (meth) ) Acrylamido-2-methylpropanesulfonic acid, N, N-dimethylaminoethyl (meth) acrylate, its tertiary salt, its quaternary ammonium salt, N, N-dimethylaminopropyl (meth) acrylamide, its tertiary salt, Examples thereof include, but are not limited to, quaternary ammonium salts, dimethyldiallylammonium chloride, and allylamine.

In the present invention, the polymerization method for obtaining the polymer to be subjected to the hydrolysis is not particularly limited, and may be solution polymerization, suspension polymerization, emulsification, or the like depending on the monomers used and the solubility of the produced polymer. Polymerization and the like can be selected. For example, if both the monomer used and the polymer to be produced are water-soluble, aqueous solution polymerization is possible.The monomer is dissolved in water, bubbling of an inert gas is carried out, and after raising the temperature to a predetermined temperature, the water-soluble polymerization initiator is added. A polymer can be obtained by the addition. The polymer obtained by the aqueous solution polymerization can be subjected to hydrolysis and amidination reaction as it is or after isolation. Also, when the solubility of the monomer used in water is small,
Suspension polymerization, emulsion polymerization and the like can be used. In emulsion polymerization, a polymer can be obtained by adding a monomer, an emulsifier, a water-soluble polymerization initiator, and the like to water and heating the mixture under stirring in an inert gas atmosphere. As the polymerization initiator, ammonium persulfate, potassium persulfate,
General initiators such as 2,2′-azobis (2-amidinopropane) dihydrochloride can be used, but azo compounds are particularly preferred. In the present invention, by heating an aqueous solution of the above polymer in the presence of an acid, an acid amide unit in the polymer is hydrolyzed to an amine unit represented by the general formula [1], and further, (meth) acrylonitrile and In the case of copolymerized copolymers, the reaction of an amine unit and an adjacent nitrile unit results in a general formula [2] or [3]
Is performed to produce an amidine unit represented by The hydrolysis and amidination reaction can be performed in two steps, but it is usually preferable to perform the reaction in one step. Reaction conditions can be selected according to the structure of the polymer and the desired hydrolysis and amidine conversion rates. Usually, the above-mentioned polymer is made into an aqueous solution or aqueous dispersion of 5 to 80% by weight, and an acid is added in an amount of 1 to 5 equivalents to an acid amide unit, and
By heating to 0 to 100 ° C., hydrolysis and amidination reaction can be performed. The acid used for the hydrolysis and amidination reaction is not particularly limited, and for example, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, acetic acid and the like can be used. The hydrolysis and amidification reaction of the aqueous solution of the polymer can be similarly carried out by heating in the presence of an alkali. In this case, the amine unit and the amidine unit are represented by the general formula [1],
It is not an ammonium salt type represented by [2] and [3], but an amine type. In the composition of the present invention, in the general formula [1], R ¹ is hydrogen or a methyl group, and all R ^{1 of} the polymer may be hydrogen or a methyl group, or a part of R ¹ of the polymer is hydrogen. And the balance may be a methyl group. In the composition of the present invention, in the general formulas [2] and [3], R ¹ and R ² are hydrogen or a methyl group, which may be the same or different from each other, and further, R ¹ or R ^{2 of the} polymer. R ² may be all hydrogen or methyl, or R ² of the polymer
Part of ¹ or R ² may be hydrogen and the remainder may be a methyl group. When R ¹ or R ² is an alkyl group having 2 or more carbon atoms, the polymer having the structure represented by the general formula [1], [2] or [3] may have insufficient hydrophilicity. In the composition of the present invention, the general formula [1], [2] or [3]
In the formula, X ⁻ is a negative ion, and examples of the negative ion include chloride ion, bromine ion, iodine ion, nitrate ion, and acetate ion.

In the composition of the present invention, the proportion of the amine unit in the total structural units of the polymer having an amine unit is 3 when the composition of the present invention is used as a polymer flocculant.
The content is preferably from 5 to 95 mol% from the viewpoint of performance. However, in terms of the aqueous dispersion as the composition of the present invention, the ratio of amine units to all structural units is not particularly limited, and regardless of the ratio. A stable aqueous dispersion can be obtained. In the composition of the present invention, the proportion of the amidine unit in the total structural units of the polymer having an amidine unit is preferably 35 to 95 mol% when the composition of the present invention is used as a polymer flocculant, in terms of performance, When the polymer having amidine units has amine units at the same time, the total amount of amidine units and amine units is 35
It is preferable in terms of performance that the content is about 95 mol%. However, in terms of the aqueous dispersion which is the composition of the present invention, the ratio of the total amount of the amidine unit or the amidine unit and the amine unit in the total structural units is not particularly limited, and is stable regardless of the ratio. It can be an aqueous dispersion. In the composition of the present invention, the polymer having an amine unit or an amidine unit is preferably of a high molecular weight when the composition of the present invention is used as a polymer flocculant. The intrinsic viscosity measured at 0 ° C. is preferably 1 dl / g or more, and more preferably 3 dl / g or more. In terms of the aqueous dispersion as the composition of the present invention, the intrinsic viscosity is not related to the intrinsic viscosity. And a stable aqueous dispersion can be obtained. In the composition of the present invention, the polymer having an amine unit or an amidine unit is added in an amount of 1 to the total amount of the aqueous dispersion composition.
It is blended so as to be 0 to 30% by weight. If the amount of the polymer having an amine unit or an amidine unit is less than 10% by weight based on the total amount of the aqueous dispersion composition, there is no particular problem in the production or performance of the aqueous dispersion composition. The object of the present invention of obtaining an aqueous dispersion composition of a cationic polymer having a viscosity is not sufficiently achieved. When the amount of the polymer having an amine unit or an amidine unit exceeds 30% by weight based on the total amount of the aqueous dispersion composition,
There is a possibility that the viscosity of the aqueous dispersion composition increases and gelation is likely to occur.

In the composition of the present invention, an inorganic salt composed of nitrate alone or a combination of nitrate and another inorganic salt is blended. Nitrate and other inorganic salts can be used without particular limitation as long as they are water-soluble. Examples of such a nitrate include sodium nitrate, potassium nitrate, magnesium nitrate, calcium nitrate, and ammonium nitrate. Also, as other inorganic salts,
For example, sodium chloride, potassium chloride, magnesium chloride, calcium chloride, ammonium chloride, sodium sulfate, potassium sulfate, magnesium sulfate, calcium sulfate, ammonium sulfate, sodium hydrogen sulfate, potassium hydrogen sulfate, ammonium hydrogen sulfate, sodium phosphate,
Examples thereof include potassium phosphate, ammonium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, dipotassium hydrogen phosphate, and potassium dihydrogen phosphate. By blending these inorganic salts with the aqueous dispersion composition, the fluidity of the polymer particles precipitated in water is improved. In the composition of the present invention, the inorganic salt composed of nitrate alone or a combination of nitrate and another inorganic salt is blended in an amount of 10 to 30% by weight based on the total amount of the aqueous dispersion composition. If the amount of the inorganic salt is less than 10% by weight based on the total amount of the aqueous dispersion composition, the polymer is hardly precipitated, and the viscosity of the aqueous dispersion composition may increase. The amount of the inorganic salt is 3 based on the total amount of the aqueous dispersion composition.
If it exceeds 0% by weight, the inorganic salt may be precipitated in the aqueous dispersion composition, and the polymer particles tend to adhere to each other. In the composition of the present invention, a nonionic or cationic water-soluble polymer can be blended if necessary. The nonionic or cationic water-soluble polymer to be blended is not particularly limited, for example, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, starch, guar gum, xanthan gum, ramzan gum, hydroxyethylcellulose, hydroxypropylcellulose, glucomannan, pullulan Polysaccharide, cationized starch, polyacrylamide, homopolymer of tertiary or quaternary ammonium salt of N, N-dimethylaminoethyl (meth) acrylate or copolymer with acrylamide, homopolymer of dimethyldiallylammonium chloride Alternatively, a copolymer with acrylamide, polyethyleneimine, and the like can be given, but the invention is not limited thereto. By adding a nonionic or cationic water-soluble polymer, the dispersion stability of the aqueous dispersion composition is improved. The amount of the nonionic or cationic water-soluble polymer is from 0 to 10% by weight based on the total amount of the aqueous dispersion composition.
When the amount of the water-soluble polymer is more than 10% by weight, the viscosity of the aqueous dispersion composition may increase, and the handling may be difficult.

The composition of the present invention may optionally contain a nonionic or cationic surfactant. The nonionic or cationic surfactant to be added is not particularly limited, and examples of the nonionic surfactant include alkyl polyoxyethylene ether and
Alkyl phenyl polyoxyethylene ether, polyethylene glycol fatty acid ester, polyhydric alcohol fatty acid ester, N, N-di (alkanol) alkaneamide and the like can be mentioned. Examples of the cationic surfactant include alkyltrimethylammonium salt ,
Alkyl pyridinium salts and the like can be mentioned. By compounding nonionic or cationic surfactant,
The dispersion stability of the aqueous dispersion composition is improved. The amount of the nonionic or cationic surfactant is from 0 to 20% by weight based on the total amount of the aqueous dispersion composition. Even if the amount of the surfactant exceeds 20% by weight, the amount of the surfactant increases. No improvement in the dispersion stability of the aqueous dispersion composition is obtained. There is no particular limitation on the method for producing the composition of the present invention,
(B) Inorganic salt, (c) water-soluble polymer and (d) surfactant can be blended at any stage of production. For example, when polymerizing (meth) acrylonitrile with N-vinylformamide or the like, or N-vinylformamide or the like, an inorganic salt, a water-soluble polymer and a surfactant are added, and after polymerization, hydrolysis or hydrolysis and amidine are added. Then, the aqueous dispersion composition of the present invention can be obtained. Further, after adding an inorganic salt, a water-soluble polymer and a surfactant to a polymer such as N-vinylfomamide or a copolymer of N-vinylfomamide or the like and (meth) acrylonitrile, hydrolysis or hydrolysis and amidine Can be performed. Alternatively, after drying a polymer having an amine unit or an amidine unit obtained by hydrolysis or hydrolysis and amidination to form a powder, an inorganic salt, a water-soluble polymer and a surfactant are mixed with the powdered polymer. Then, water is added to obtain an aqueous dispersion composition. The addition of the inorganic salt, the water-soluble polymer and the surfactant need not be simultaneous, for example, adding an inorganic salt during polymerization, adding a water-soluble polymer during hydrolysis, and adding a water-soluble polymer after completion of hydrolysis. And any other addition method. In the composition of the present invention, the polymer having an amine group or an amidine group in an aqueous solution contracts in a polymer chain in the presence of nitrate ions and precipitates in the form of fine particles, thereby forming a dispersion of an insoluble polymer. Also, when the dispersion is diluted with water, the polymer is easily redissolved in water. The addition of the water-soluble polymer imparts viscosity to the aqueous dispersion and prevents sedimentation of the dispersed polymer particles. Further, the surfactant has an action of suppressing coalescence of the dispersed polymer particles. Due to such effects, the aqueous dispersion composition of the present invention becomes a stable dispersion liquid without the cationic polymer particles dispersed in water coalescing or sedimentation-separated.

[0010]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the present invention. In Examples and Comparative Examples, the viscosity of the aqueous dispersion composition was measured using a rotational viscometer.
Measured at 5 ° C. The re-solubility of the aqueous dispersion composition in water was determined by adding the aqueous dispersion composition to 100 g of water so that the concentration of the cationic polymer was 0.1% by weight, and stirring the mixture gently. It was determined from the appearance of the mixture. Production Example 1 (Polymer Having Amine Unit) N-vinylformamide 71.0 was placed in a 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube.
g (1.0 mol) and 310 g of water were charged, and the atmosphere was replaced with nitrogen. The temperature was raised to 60 ° C. with stirring, 1.0 g of a 10% aqueous solution of 2,2′-azobis (2-amidinopropane) dihydrochloride was added, and polymerization was continued for 5 hours while maintaining the temperature at 60 ° C. Concentrated hydrochloric acid 98.
1 g (1.0 mol as hydrogen chloride) was added and reacted for 4 hours while heating and refluxing to hydrolyze the polymer. The polymer solution after hydrolysis was added to acetone, and the precipitated polymer was dried in vacuum. Of this cationic polymer,
The intrinsic viscosity measured at 30 ° C. using a 1N aqueous solution of sodium chloride as a solvent was 4.5 dl / g. The colloid equivalent of this cationic polymer was 8.8 at pH = 4.
Nine. This polymer is referred to as polymer A. Production Example 2 (Polymer having amidine unit) 35.5 N-vinylformamide was placed in a 500 ml flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube.
g (0.5 mol), acrylonitrile 26.5 g (0.5
Mol) and 310 g of water, and the atmosphere was replaced with nitrogen. The temperature was raised to 60 ° C. with stirring, and 2,2′-azobis (2
1.0 g of a 10% aqueous solution of amidinopropane) dihydrochloride
Was added and polymerization was continued for 5 hours while maintaining the temperature at 60 ° C. 98.1 g of concentrated hydrochloric acid (1.0 mol as hydrogen chloride) was added to the suspension in which the polymer was precipitated in water, and the mixture was reacted for 4 hours while heating and refluxing to amidine the polymer. The obtained polymer solution was added to acetone, and the precipitated polymer was dried under vacuum. The intrinsic viscosity of the cationic polymer measured at 30 ° C. using a 1N aqueous solution of sodium chloride as a solvent was 3.5 dl / g. The colloid equivalent of this cationic polymer was 6.5 at pH = 4. This polymer is referred to as polymer B. Example 1 Polymer A was stirred into 67 g of water with vigorous stirring using a stirrer.
Was gradually added and dispersed and dissolved in water, and then allowed to stand overnight to prepare a high-concentration aqueous solution.
Then, while slowly stirring the aqueous solution with a stirrer, a mixture of 15 g of sodium nitrate and 8 g of sodium chloride was gradually added to dissolve these inorganic salts in the aqueous solution. As a result, the polymer gradually began to precipitate as fine particles. ,
The viscosity of the aqueous solution has decreased. After the addition of all the inorganic salts, stirring was continued for 8 hours, left standing overnight, and further stirred for 1 hour the next day to obtain an aqueous dispersion composition as a cloudy fluid slurry. The viscosity of this aqueous dispersion composition is
It was 6,500 cP. When 1 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Example 2 The exactly same operation as in Example 1 was repeated using 60 g of water, 20 g of polymer B powder and 20 g of sodium nitrate,
An aqueous dispersion composition as a cloudy fluid slurry was obtained. The viscosity of this aqueous dispersion composition was 1,250 cP. Further, 0.5 g of this aqueous dispersion composition was added to 10 parts of water.
When the solution was added to 0 g and stirred gently, it was redissolved to form a clear aqueous solution. Example 3 56 g of water, 20 g of polymer B powder, sodium nitrate 1
The exactly same operation as in Example 2 was repeated using 6 g and 8 g of sodium chloride. The viscosity of the obtained cloudy fluid slurry was 650 cP. When 0.5 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Example 4 20 g of polymer B powder was gradually added to 59.5 g of water while being vigorously stirred with a stirrer, dispersed and dissolved in water, and allowed to stand overnight to prepare a high-concentration aqueous solution. Then, while slowly stirring the aqueous solution with a stirrer,
18 g of sodium nitrate, 2 g of sodium sulfate and a copolymer of methyl quaternary chloride and acrylamide of dimethylaminoethyl acrylate (intrinsic viscosity of 8.9 dl / g measured at 30 ° C. using 1N sodium nitrate as a solvent, pH =
A mixture of 0.5 g of the colloid equivalent (4.0 meq / g) in Example 4 was slowly added to dissolve these inorganic salts and the water-soluble polymer in the aqueous solution. As a result, the polymer gradually began to precipitate as fine particles. Has decreased in viscosity. After all of the inorganic salt and the water-soluble polymer were added, stirring was continued for 8 hours, left standing overnight, and further stirred for 1 hour the next day to obtain an aqueous dispersion composition as a cloudy fluid slurry. The viscosity of this aqueous dispersion composition is 1,
It was 055 cP. In addition, the aqueous dispersion composition 0.1.
When 5 g was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Example 5 20 g of polymer B powder was gradually added to 48.2 g of water with vigorous stirring with a stirrer, dispersed and dissolved in water, and allowed to stand overnight to prepare a high-concentration aqueous solution. Then, while slowly stirring the aqueous solution with a stirrer,
15 g of sodium nitrate, 8 g of sodium chloride, 8.3 g of a polycondensate of dimethylamine and epichlorohydrin and polyoxyethylene nonylphenyl ether (HLB1
4.5) 0.5 g of the mixture was gradually added, and the inorganic salt, the water-soluble polymer and the surfactant were dissolved in the aqueous solution. As a result, the polymer gradually began to precipitate as fine particles, and the viscosity of the aqueous solution was gradually increased. Has declined. After adding inorganic salt, water-soluble polymer and surfactant,
Stirring was continued for 8 hours, left overnight, and further stirred for 1 hour the next day to obtain an aqueous dispersion composition as a cloudy fluid slurry. The viscosity of this aqueous dispersion composition is 4,350
cP. When 0.5 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Example 6 Water 42 g, Polymer B powder 30 g, sodium nitrate 2
The same operation as in Example 1 was repeated using 0 g and 8 g of sodium chloride to obtain an aqueous dispersion composition as a cloudy fluid slurry. The viscosity of this aqueous dispersion composition was 13,500 cP. When 0.33 g of this aqueous dispersion composition was added to 100 g of water and gently stirred, it was redissolved to form a transparent aqueous solution.

Comparative Example 1 The same operation as in Example 1 was repeated except that no inorganic salt was added. That is, 10 g of polymer A powder was gradually added to 90 g of water with vigorous stirring by a stirrer, dispersed and dissolved in water, and allowed to stand overnight to prepare a high-concentration aqueous solution. Then, the aqueous solution was stirred for 8 hours.
Stirring was continued slowly for an hour, allowed to stand overnight, and further stirred for 1 hour the next day, whereby a transparent gel-like aqueous composition was obtained. The viscosity of this aqueous composition was as high as 360,000 cP. In addition, 1 g of this aqueous composition was
When the mixture was added to 00 g and gently stirred, it was redissolved to form a transparent aqueous solution, and the resolubility was good. Comparative Example 2 The same operation as in Example 1 was repeated using only sodium sulfate as the inorganic salt. That is, into 70 g of water,
10 g of polymer A powder was gradually added with vigorous stirring with a stirrer, dispersed and dissolved in water, and allowed to stand overnight to prepare a high-concentration aqueous solution. Next, 20 g of sodium sulfate was gradually added and dissolved while slowly stirring the aqueous solution with a stirrer. As a result, the polymer gradually began to precipitate as fine particles, and the viscosity of the aqueous solution was decreasing. After all the sodium sulfate was added, stirring was continued for 8 hours, and the mixture was allowed to stand overnight, and then stirred for another hour on the next day.
An aqueous dispersion composition as a cloudy slurry was obtained. The viscosity of this aqueous dispersion composition was 650 cP. Further, 1 g of this aqueous dispersion composition was added to 100 g of water and stirred gently, but the polymer did not redissolve and remained cloudy. It was found that the polymer, in which the polymer chains contracted in the presence of sulfate ions and precipitated in fine particles, did not have resolubility. Comparative Example 3 The same operation as in Example 2 was repeated except that no inorganic salt was blended. That is, 20 g of polymer B powder was gradually added to 80 g of water with vigorous stirring by a stirrer, dispersed and dissolved in water, and allowed to stand as it was overnight to prepare a high-concentration aqueous solution. Then, the aqueous solution was stirred for 8 hours.
Stirring was continued slowly for an hour, allowed to stand overnight, and further stirred for 1 hour the next day, whereby a transparent gel-like aqueous composition was obtained. The viscosity of this aqueous composition was 870,000 cP, which was extremely high. Further, when 0.5 g of this aqueous composition was added to 100 g of water and gently stirred, it was redissolved to form a transparent aqueous solution, and the resolubility was good. Comparative Example 4 The effect was examined by reducing the amount of sodium nitrate added. That is, when exactly the same operation as in Example 2 was repeated using 75 g of water, 20 g of the powder of polymer B and 5 g of sodium nitrate, a slightly cloudy gel-like aqueous dispersion composition was obtained. The viscosity of the aqueous dispersion composition is 8
The viscosity was 2,500 cP, and it was found that the viscosity was not sufficiently reduced if the amount of sodium nitrate was small. When 0.5 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Comparative Example 5 The effect was examined using another inorganic salt and a surfactant instead of sodium nitrate. That is, into 59 g of water, while stirring vigorously with a stirrer,
g was gradually added, and after dispersing and dissolving in water, the mixture was allowed to stand overnight to prepare a high-concentration aqueous solution. Then, while slowly stirring the aqueous solution with a stirrer, sodium sulfate 2
g, 18 g of sodium chloride and 1 g of polyoxyethylene nonylphenyl ether (HLB 14.5) were gradually added to dissolve these inorganic salts and the surfactant in the aqueous solution. After the addition of all the inorganic salt and the surfactant, stirring was continued for 8 hours, allowed to stand overnight, and further stirred for 1 hour the next day to obtain a transparent gel-like aqueous composition. The viscosity of this aqueous composition was as high as 150,000 cP. Also, 0.5 g of this aqueous composition was added to 10 parts of water.
When the solution was added to 0 g and stirred gently, it was redissolved to form a clear aqueous solution. Comparative Example 6 The effect was examined using only a surfactant without using sodium nitrate. That is, into 89 g of water,
10 g of polymer B powder was gradually added with vigorous stirring with a stirrer, dispersed and dissolved in water, and allowed to stand as it was overnight to prepare a high-concentration aqueous solution. Next, while slowly stirring the aqueous solution with a stirrer, 1 g of polyoxyethylene nonylphenyl ether (HLB14.5) was gradually added and dissolved in the aqueous solution. After all the polyoxyethylene nonyl phenyl ether was added, stirring was continued for 8 hours, allowed to stand overnight, and further stirred for 1 hour the next day to obtain a transparent gel-like aqueous composition. The viscosity of this aqueous composition was as high as 47,500 cP, and it was found that the viscosity could not be sufficiently reduced only by the surfactant. When 1 g of the aqueous composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Table 1 summarizes the formulations and results of Examples 1 to 6 and Comparative Examples 1 to 6.

[0012]

[Table 1]

Example 7 Polymer A was poured into 60 g of water while stirring vigorously with a stirrer.
Was gradually added and dispersed and dissolved in water, and then allowed to stand overnight to prepare a high-concentration aqueous solution.
Next, while slowly stirring the aqueous solution with a stirrer, 10 g of sodium nitrate was gradually added and dissolved, and the polymer gradually began to precipitate as fine particles, and the viscosity of the aqueous solution was decreasing. After all the sodium nitrate had been added, stirring was continued for 8 hours, allowed to stand overnight, and further stirred for 1 hour the next day to obtain an aqueous dispersion composition as a slightly turbid high-viscosity fluid liquid. The viscosity of the aqueous dispersion composition is 15
It was 0.000 cP. When 0.33 g of this aqueous dispersion composition was added to 100 g of water and gently stirred, it was redissolved to form a transparent aqueous solution. Example 8 Polymer B into 80 g of water with vigorous stirring with a stirrer
Was gradually added and dispersed and dissolved in water, and then allowed to stand overnight to prepare a high-concentration aqueous solution.
Next, while slowly stirring the aqueous solution with a stirrer, 10 g of sodium nitrate was gradually added and dissolved, and the polymer gradually began to precipitate as fine particles, and the viscosity of the aqueous solution was decreasing. After the addition of all the inorganic salts, stirring was continued for 8 hours, allowed to stand overnight, and further stirred for 1 hour the next day to obtain a slightly turbid solution-type aqueous dispersion composition.
The viscosity of this aqueous dispersion composition was 1,850 cP. When 1 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Example 9 The same operation as in Example 8 was repeated except that the amount of the powder of the polymer B of Example 8 was increased to 20 g and the amount of water was reduced to 70 g. A dispersion composition was obtained. The viscosity of this aqueous dispersion composition was 9,800 cP. When 0.5 g of this aqueous dispersion composition was added to 100 g of water and gently stirred, it was dissolved again to form a transparent aqueous solution. . Example 10 Instead of 10 g of sodium nitrate of Example 9, 15 g of sodium nitrate and 5 g of sodium chloride were used, and polyoxyethylene nonylphenyl ether (HLB1
4.5) 10 g was blended and the amount of water was changed to 50 g, and the same operation as in Example 9 was repeated. As a result, an aqueous dispersion composition of a cloudy fluid slurry was obtained. The viscosity of the aqueous dispersion composition was 1,050 cP, and 0.5 g of the aqueous dispersion composition was added to 100 g of water and gently stirred. . Example 11 Instead of the polyoxyethylene nonyl phenyl ether of Example 10, a copolymer of methyl quaternary chloride of dimethylaminoethyl acrylate and acrylamide (1N
An intrinsic viscosity of 8.9 dl / g measured at 30 ° C. using sodium nitrate as a solvent, and a colloid equivalent of 4.0 meq / g at pH = 4.
g) The same operation as in Example 10 was repeated using 5 g and 5 g of cetyltrimethylammonium bromide, whereby an aqueous dispersion composition of a cloudy fluid slurry was obtained. The viscosity of the aqueous dispersion composition was 960 cP, and 0.5 g of the aqueous dispersion composition was
g and gently stirred, then redissolved to form a clear aqueous solution. Comparative Example 7 The same operation as in Example 7 was repeated except that no inorganic salt was blended. That is, 30 g of polymer A powder was gradually added to 70 g of water with vigorous stirring by a stirrer, dispersed and dissolved in water, and allowed to stand as it was overnight to prepare a high-concentration aqueous solution. Then, the aqueous solution was stirred for 8 hours.
Stirring was continued slowly for an hour, allowed to stand overnight, and further stirred for 1 hour the next day, whereby a rubber-like aqueous composition was obtained. The viscosity of this aqueous composition was 2,000,000 cP or more. When 0.33 g of this aqueous composition was added to 100 g of water and gently stirred, it was redissolved to form a transparent aqueous solution, and the resolubility was good. Comparative Example 8 The same operation as in Example 2 was repeated except that the amount of sodium nitrate was changed to 40 g and the amount of water was reduced from 60 g to 40 g instead of 20 g of sodium nitrate of Example 2. An aqueous dispersion composition of a cloudy fluid slurry was obtained, in which sodium nitrate remained partially insoluble. It was found that when the amount of sodium nitrate was too large, a uniform aqueous dispersion composition could not be obtained. The viscosity of this aqueous dispersion composition is 825 cP,
When 0.5 g of the aqueous dispersion composition was added to 100 g of water and gently stirred, the mixture was redissolved to form a transparent aqueous solution. Comparative Example 9 The effect was examined by increasing the blending amount of the cationic polymer. That is, 40 g of the polymer B powder was gradually added to 40 g of water with vigorous stirring with a stirrer, dispersed and dissolved in water, and allowed to stand overnight to prepare a high-concentration aqueous solution. Then, while slowly stirring the aqueous solution with a stirrer, 15 g of sodium nitrate and 5 g of sodium chloride
Was slowly added to dissolve these inorganic salts in the aqueous solution. After all the inorganic salts had been added, stirring was continued for 8 hours, allowed to stand overnight, and further stirred for 1 hour the next day. The obtained aqueous dispersion composition is rubbery and has a viscosity of 2.0.
It was more than 00,000 cP. It was found that if the amount of the cationic polymer was too large, a fluid, low-viscosity aqueous dispersion composition could not be obtained. However, when 0.25 g of this rubbery aqueous composition was added to 100 ml of water and gently stirred, it was redissolved to give a transparent aqueous solution. Table 2 summarizes the results of Examples 7 to 11 and Comparative Examples 7 to 9.

[0014]

[Table 2]

[0015]

According to the present invention, an aqueous dispersion of a high-concentration and low-viscosity cationic polymer can be obtained by adding nitrate to an aqueous solution of a cationic polymer having an amine unit or an amidine unit. The composition of the present invention can be reduced in volume because of its high concentration, is excellent in handleability and economical efficiency in transportation and storage, and is excellent in safety because it is an aqueous dispersion.

──────────────────────────────────────────────────続 き Continuation of front page (72) Inventor Masayuki Murano 3-4-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo Kurita Kogyo Co., Ltd. (56) References JP-A-5-255565 (JP, A) JP-A-5-255565 JP-A-5-192513 (JP, A) JP-A-6-218400 (JP, A) JP-A-6-123096 (JP, A) JP-A-58-11553 (JP, A) JP-A-8-59740 (JP JP-A-7-256299 (JP, A) JP-A-8-49190 (JP, A) JP-A-7-223000 (JP, A) JP-A-8-188983 (JP, A) (58) Field surveyed (Int. Cl. ⁷ , DB name) C08L 39/00 B01D 21/01 107 C02F 11/14

Claims (1)

(57) [Claims] (1) 10 to 30% by weight of a polymer having an amine unit of the general formula [1] or a polymer having an amidine unit of the general formula [2] or (3), and (b) nitrate alone or nitrate (C) 0 to 10% by weight of a nonionic or cationic water-soluble polymer, (d) 0 to 10% by weight of a nonionic or cationic surfactant, 20. An aqueous dispersion composition of a cationic polymer having fluidity, comprising 20% by weight and (e) water. Embedded image (Wherein, R ¹ and R ² are hydrogen or a methyl group, and X ⁻ is a negative ion.)