JP5366123B2 - Dilatancy composition comprising a water-soluble ionic polymer mixture - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water soluble composition showing dilatancy and excellent in stability, and also an aqueous solution composition gelling by flowage. <P>SOLUTION: This aqueous solution comprising the following components (A) and (B) has been found to show the dilatancy: (A) a water soluble ionic polymer having &ge;2 meq/g ionic group density; and (B) a water soluble ionic polymer having an opposite ionic property to that of the (A) and having &le;1 meq/g ionic group density. Also, the aqueous solution containing the above water soluble ionic polymers is found to be gelled by flowage. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

The present invention relates to a composition exhibiting dilatancy in an aqueous solution system. The present invention also relates to a composition that gels by flow. The dilatancy composition of the present invention is useful as a shock absorber, other aqueous viscosity modifiers, and a gelling composition by flow. In the present invention, dilatancy means that the viscosity is increased and the fluidity is lowered by applying a shearing force.

A water-soluble polymer aqueous solution generally decreases in viscosity under high shear. On the other hand, a liquid containing fine particles may exhibit dilatancy that increases in viscosity under high shear. Patent Document 1 reports a dilatancy property for a system of fine particles, a dispersant, and a liquid. Patent Document 2 and Non-Patent Document 1 have reports on the dilatancy of oil droplets and water-soluble polymer systems, but both are heterogeneous systems containing oil droplets and the like. There is a problem that it is necessary to emulsify and stabilize oil droplets by adding an agent.
Japanese Patent No. 3922370 Patent No. 4098967 THE JOURNAL OF CHEMICAL PHYSICS 127 No. 144450

The objective of this invention is providing the aqueous solution composition excellent in stability which shows dilatancy property. Another object of the present invention is to provide an aqueous solution composition that gels by flow.

The following components (A) and (B),
(A) a water-soluble ionic polymer having an ionic group density of 2 meq / g or more,
(B) It has been found that an aqueous solution containing a water-soluble ionic polymer having an ionic group density opposite to (A) having an ionic group density of 1 meq / g or less exhibits dilatancy. Moreover, it discovered that the aqueous solution containing this water-soluble ionic polymer gelatinizes by flow.

The dilatancy composition of the present invention is homogeneous, does not require a dispersion stabilizer, a surfactant and the like, has excellent storage stability, and exhibits dilatancy even at a low concentration of 1% or less. In addition, when no flow stimulus is applied, the solution is a low-viscosity uniform aqueous solution. However, when the flow stimulus is applied, the solution rapidly has a high viscosity, the fluidity is lowered, and gelation occurs. The composition of the present invention is useful as a viscosity modifier for high-speed coating adhesives, printing coating liquids, aqueous emulsion compositions, curable resin compositions, cosmetics and the like. It is also useful as a component of power transmission devices such as dampers and clutches, shock absorbers, vibration control devices, vibration control devices and the like.

The dilatancy composition of the present invention contains a water-soluble cationic polymer and a water-soluble anionic polymer. The following components (A) and (B),
(A) Water-soluble ionic polymer having an ionic group density of 2 meq / g or more (B) Water-soluble ionicity having an ionic group density of 1 meq / g or less and ionicity opposite to (A) An aqueous solution containing a polymer exhibits strong dilatancy and gels by flow.

Here, the ionic group density represents an ion equivalent value meq / g per 1 g of the water-soluble ionic polymer. The ionic group density of the water-soluble ionic polymer can be determined by pH titration, colloid titration or the like. The water-soluble ionic polymer of the component (A) and the component (B) may be a synthetic polymer, an ionic natural polymer, or a polymer in which an ionic group is introduced. .

Usually, when a water-soluble cationic polymer and a water-soluble anionic polymer are mixed, an ion complex is formed and insolubilized and precipitated in the vicinity of a neutralization point having an equal ion balance. In particular, in the case of polymers having a high ionic group density and a large molecular weight, an insoluble material is instantly formed by mixing regardless of the ion balance. However, when the water-soluble ionic polymer and the water-soluble ionic polymer having the opposite charge have a certain ionic group density, it is difficult to form an insoluble ion complex, and the mixed aqueous solution is dilatant. It was found that it gelled by flow.

In the case of the synthetic polymer, the water-soluble ionic polymer (A) is composed of an ionic monomer and a nonionic hydrophilic monomer, and ions of 2 meq / g or more per 1 g of the obtained polymer. It is obtained by polymerizing to have a functional group. It may be obtained only from an ionic monomer. Examples of the anionic monomer among the ionic monomers include (meth) acrylic acid, itaconic acid, maleic acid, styrene sulfonic acid, acrylamide 2-methylpropane sulfonic acid, and salts thereof.
Examples of cationic monomers among ionic monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth) acrylamide. , And salts thereof, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, (meth) ) Acryloyloxy 2-hydroxypropyltrimethylammonium chloride, diallyldimethylammonium chloride, allylamine, diallylmethylamine Etc., and the like. Examples of nonionic hydrophilic monomers are (meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone, vinylformamide, vinylacetamide, glycerol (meth) acrylate, hydroxyethyl (meth) An acrylate etc. are mentioned.

In the case where the water-soluble ionic polymer (B) is a synthetic polymer, the ionic monomer and the nonionic hydrophilic monomer are 1 meq / g or less per 1 g of the obtained copolymer. It is obtained by copolymerizing so as to have an ionic group. Examples of the anionic monomer among the ionic monomers include (meth) acrylic acid, itaconic acid, maleic acid, styrene sulfonic acid, acrylamide 2-methylpropane sulfonic acid, and salts thereof. Examples of cationic monomers among the ionic monomers include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, and diethylaminopropyl (meth). Acrylamide and salts thereof, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, ( (Meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, diallyldimethylammonium chloride, allylamine, diallylmethylamine And the like. Examples of nonionic hydrophilic monomers are (meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone, vinylformamide, vinylacetamide, glycerol (meth) acrylate, hydroxyethyl (meth) An acrylate etc. are mentioned.

In the case of a synthetic polymer, the water-soluble ionic polymer of the component (A) and the component (B) can be obtained by an ordinary radical polymerization method. The method in the case of solution polymerization will be described below.

The polymerization conditions are usually appropriately determined according to the monomer used, the polymerization initiator, and the like. The polymerization temperature is in the range of 0 to 100 ° C. The monomer aqueous solution is adjusted so that the concentration of the monomer is 1 to 30% by weight, more preferably 5 to 20% by weight, and nitrogen substitution is performed. Polymerization is then started.

For the initiation of polymerization, a radical polymerization initiator is used. These initiators are preferably water-soluble and can be polymerized in any of azo, redox and peroxide systems. Examples of water-soluble azo initiators include 2,2′-azobis (2-methylpropionamidine) dichloride, 2,2′-azobis [2- (2-imidazolin-2-yl) propane] And hydrogen chloride, 4,4′-azobis (4-cyanovaleric acid), and the like. Examples of redox systems include a combination of ammonium persulfate and sodium sulfite, sodium hydrogen sulfite, trimethylamine, tetramethylethylenediamine and the like. Further, examples of peroxides include ammonium or potassium persulfate, hydrogen peroxide, and the like. Of these, water-soluble azo initiators are preferred.

The weight average molecular weight of the water-soluble ionic polymer (A) by light scattering method is 10,000 to 15 million, more preferably 100,000 to 10 million. The weight average molecular weight of the water-soluble ionic polymer (B) by the light scattering method is 500,000 to 15 million, more preferably 1 million to 10 million. The molecular weight of the water-soluble ionic polymer as the component (B) is stronger than the molecular weight of the water-soluble ionic polymer as the component (A).

The dilatancy composition of the present invention can be obtained by mixing the water-soluble ionic polymer (A) and the water-soluble ionic polymer (B) at a certain ratio. The mixing ratio is the ratio of the ion equivalent a meq of the ionic group derived from the water-soluble ionic polymer (A) to the ion equivalent b meq of the ionic group derived from the water-soluble ionic polymer (B). 0.01 ≦ b / a ≦ 1.3 is preferable. When it is less than 0.01, no dilatancy is exhibited, and when it is greater than 1.3, an insoluble precipitate is formed and no dilatancy is exhibited. More preferably, 0.03 ≦ b / a ≦ 1.1. A mixture of the water-soluble ionic polymer (A) and the water-soluble ionic polymer (B) exhibits dilatancy by diluting with water to a total polymer concentration of 0.01 to 5% by mass. It is also possible to add other water-soluble polymers, fine particles, organic substances such as methanol to the present composition.

(Example)
EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not restrict | limited to a following example, unless the summary is exceeded. In the examples, the viscosity was measured using a Brookfield viscometer with a rotation speed of 100 rpm and a No. 3 rotor. The weight average molecular weight was analyzed using DAWN HELEOS manufactured by Wyatt Technology. The ionic group density of the anionic polymer was determined by pH titration, and the ionic group density of the cationic polymer was determined by colloid titration.

  (Production Example 1) 225.0 g of deionized water and 75.0 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution were added to a four-necked 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube. A uniform mixed solution was obtained. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 45 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 0.06 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. This is designated as cationic polymer A1. The weight average molecular weight by the light scattering method was about 900,000. The ionic group density was 4.69 meq / g.

(Production Example 2) 138.5 g of deionized water and 161.5 g of 65% diallyldimethylammonium chloride aqueous solution were added to a 4-neck 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube. A mixed solution was obtained. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 50 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 1.05 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. The polymerization was continued for 8 hours to complete the reaction. This is designated as cationic polymer A2. The weight average molecular weight by the light scattering method was about 300,000. The ionic group density was 5.85 meq / g.

(Production Example 3) A four-neck 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen inlet tube was charged with 228.0 g of deionized water, 30.3 g of an 80% acryloyloxyethyltrimethylammonium chloride aqueous solution, 50%. 41.6 g of acrylamide was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 33 to 35 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. The polymerization was continued for 20 hours to complete the reaction. This is designated as cationic polymer A3. The weight average molecular weight by the light scattering method was about 4.9 million. The ionic group density was 2.65 meq / g.

(Production Example 4) A four-necked 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube was charged with 224.2 g of deionized water, 23.6 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution, and 50%. 52.2 g of acrylamide was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 35 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. This is designated as cationic polymer A4. The weight average molecular weight by the light scattering method was about 6.300,000. The ionic group density was 2.08 meq / g.

(Production Example 5) 255.0 g of deionized water and 45.0 g of sodium acrylamide 2-methylpropanesulfonate were added to a four-necked 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, and homogeneous A mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 35 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.05 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. This is designated as anionic polymer A5. The weight average molecular weight was 2 million by the light scattering method. The ionic group density was 4.2 meq / g.

Production Example 6 A four-neck 200 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube was charged with 79.2 g of deionized water, 0.83 g of 60% aqueous acrylic acid solution, and 19.0 g of 50% acrylamide. Was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 45 ° C. using a constant temperature water bath. After 30 minutes from the introduction of nitrogen, 0.01 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. The polymerization was continued for 22 hours to complete the reaction. The weight average molecular weight by the light scattering method was about 5.5 million. The ionic group density was 0.54 meq / g. This is designated as anionic polymer B1.

(Production Example 7) A four-neck 300 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube was charged with 120.3 g of deionized water, 0.25 g of a 60% aqueous acrylic acid solution, and 29.5 g of 50% acrylamide. Was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 40 ° C. using a constant temperature water bath. 30 minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. The polymerization was continued for 22 hours to complete the reaction. The weight average molecular weight by the light scattering method was about 6.5 million. The ionic group density was 0.12 meq / g. This is designated as anionic polymer B2.

(Production Example 8) In a four-neck 300 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen inlet tube, 119.1 g of deionized water, 0.48 g of sodium acrylamide 2-methylpropanesulfonate, 50% acrylamide 29.52 g was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 40 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. The weight average molecular weight by the light scattering method was 5.2 million. The ionic group density was 0.06 meq / g. This is designated as anionic polymer B3.

(Production Example 9) In a four-neck 300 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer, and a nitrogen introduction tube, 119.8 g of deionized water, 0.96 g of dimethylaminoethyl methacrylate, 50% acrylamide 28 0.1 g and 96% sulfuric acid 0.31 g were added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 40 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. The weight average molecular weight by the light scattering method was about 5.2 million. The ionic group density was 0.37 meq / g. This is designated as cationic polymer B4.

(Comparative Production Example 1) In a four-necked 500 ml separable flask equipped with a stirrer, reflux condenser, thermometer and nitrogen inlet tube, 214.5 g of deionized water, 7.5 g of 80% methacryloyloxyethyltrimethylammonium chloride aqueous solution, 50 A 7% aqueous acrylamide solution was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 35 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.05 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. The weight average molecular weight was about 6.2 million. The ionic group density was 0.53 meq / g. This is designated as comparative cationic polymer A6.

(Comparative Production Example 2) In a four-neck 500 ml separable flask equipped with a stirrer, a reflux condenser, a thermometer and a nitrogen introduction tube, 218.2 g of deionized water, 13.8 g of an aqueous solution of 80% methacryloyloxyethyltrimethylammonium chloride, 50 68.0 g of% acrylamide was added to obtain a uniform mixed solution. Thereafter, nitrogen was introduced from the nitrogen introduction tube while stirring to remove dissolved oxygen. During this time, the internal temperature was adjusted to 35 ° C. using a constant temperature water bath. Thirty minutes after the introduction of nitrogen, 0.02 g of 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added to initiate polymerization. Polymerization was continued for 20 hours to complete the reaction. This is designated as comparative cationic polymer A7. The weight average molecular weight was about 6.8 million. The ionic group density was 1.05 meq / g.

(Comparative Production Example 3) In a four-necked 300 ml separable flask equipped with a stirrer, a reflux condenser, and a nitrogen inlet tube, 3.4 g of 60% aqueous acrylic acid solution, 12.0 g of 1N-NaOH, 16.0 g of 50% aqueous acrylamide solution, 67.7 g of deionized water and 0.01 g of sodium phosphinate monohydrate were added to obtain a uniform mixed solution. While maintaining the temperature at 20 ° C., nitrogen was introduced from the nitrogen introduction tube while stirring, and the system was purged with nitrogen. Next, 0.01 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added, and the flask was heated to a temperature of 50 ° C. to initiate polymerization. It was. The polymerization was terminated after 10 hours. The weight average molecular weight was 700,000. The ionic group density was 2.6 meq / g. This is designated as comparative anionic polymer B5.

(Comparative Production Example 4) In a four-necked 300 ml separable flask equipped with a stirrer, a reflux condenser, and a nitrogen introduction tube, 1.7 g of 60% aqueous acrylic acid solution, 6.0 g of 1N-NaOH, 18.0 g of 50% acrylamide aqueous solution, 74.3 g of deionized water and 0.01 g of sodium phosphinate monohydrate were added to obtain a uniform mixed solution. While maintaining the temperature at 20 ° C., nitrogen was introduced from the nitrogen introduction tube while stirring, and the system was purged with nitrogen. Next, 0.01 g of 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride was added, and the flask was heated to a temperature of 50 ° C. to initiate polymerization. It was. The polymerization was terminated after 10 hours. The weight average molecular weight was 800,000. The ionic group density was 1.32 meq / g. This is designated as comparative anionic polymer B6. The results are shown in Table 1.

( Table 1 )

The ionic polymers from Production Examples 1 to 9 were mixed under the conditions shown in Table 2 . The viscosity after standing for one day and the viscosity after manually shaking for 5 seconds at an amplitude of about 10 cm and a frequency of 4 times / S were placed in a 50 mL sample bottle, and the dilatancy was evaluated from the ratio. Moreover, the presence or absence of adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was observed. The results are shown in Table 2. The mixture composed of the ionic polymer of the production example showed dilatancy, and adhesion of a gel-like material to the inner wall of the sample bottle after shaking was observed.

(Comparative Example 1) Comparative Examples The ionic polymers of Production Examples 1 to 4 were mixed under the conditions shown in Table 2. The viscosity after standing for 1 day and the viscosity after shaking for 5 seconds at an amplitude of about 10 cm and a frequency of 4 times / S were put into a 50 mL sample bottle, and the dilatancy was evaluated from the ratio. Moreover, the presence or absence of adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was observed.
The results are shown in Table 2.

In Comparative Example 1-1, anionic polymer B1 / comparative cationic polymer A6 (mass ratio) was mixed in the range of 0.05 to 1.0, but no dilatancy occurred. Moreover, adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was not observed. The results are shown in Table 2.

In Comparative Example 1-2, anionic polymer B1 / comparative cationic polymer A7 (mass ratio) was mixed in the range of 0.1 to 1.0, but no dilatancy occurred. Moreover, adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was not observed. The results are shown in Table 2.

In Comparative Example 1-3, comparative anionic polymer B5 / cationic polymer A1 (mass ratio) was mixed in the range of 0.1 to 5.0, but dilatancy did not occur. Moreover, adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was not observed. The results are shown in Table 2.

In Comparative Example 1-4, comparative anionic polymer B6 / cationic polymer A1 (mass ratio) was mixed in the range of 0.2 to 5.0, but dilatancy did not occur. Moreover, adhesion of the gel-like substance to the inner wall of the sample bottle after shaking was not observed. The results are shown in Table 2.

(Table 2)
Molar ratio of ionic group = (B component ion equivalent / A component ion equivalent), dilatancy strength = viscosity after shake / viscosity before shake, total polymer concentration; g / mL

Claims (2)

The following components (A) and (B),
(A) ionic group density Ri der 2 meq / g or more, a water-soluble ionic polymer (B) an ionic group density weight average molecular weight of 100,000 10 million is less 1 meq / g, (A ) Contains a water-soluble ionic polymer that is ionic opposite to b), the ion equivalent of the ionic group derived from the component (B) is b meq, and the ion equivalent of the ionic group derived from the component (A) a
When meq
A dilatancy composition having 0.01 ≦ b / a ≦ 1.3, and an anionic monomer constituting the water-soluble ionic polymer of (A) and (B), (meth) acrylic acid, It is selected from itaconic acid, maleic acid, styrene sulfonic acid, acrylamide 2-methylpropane sulfonic acid, and salts thereof, and as a cationic monomer, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate , Dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, and salts thereof, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloylaminopropyltrimethyl Nonionic hydrophilic monomer selected from ammonium chloride, (meth) acryloylaminopropyldimethylbenzylammonium chloride, (meth) acryloyloxy 2-hydroxypropyltrimethylammonium chloride, diallyldimethylammonium chloride, allylamine, diallylmethylamine , (Meth) acrylamide, dimethylacrylamide, diethylacrylamide, isopropylacrylamide, hydroxyethylacrylamide, vinylpyrrolidone, vinylformamide, vinylacetamide, glycerol (meth) acrylate, hydroxyethyl (meth) acrylate Sex composition. Claim 1 dilatancy composition according weight average molecular weight of the water-soluble ionic polymer is characterized in that it is more than 500,000 (B).