JP3513479B2 - High-temperature low-viscosity low-temperature high-viscosity thermosensitive polymer material - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel temperature-sensitive substance which exhibits a viscosity as low as that of water at a temperature higher than the transition temperature, but shows a sharp increase in viscosity at a temperature lower than the transition temperature. Related to water-soluble polymeric materials.

[0002]

2. Description of the Related Art In recent years, a temperature-sensitive polymer material whose behavior with respect to water reversibly changes depending on temperature has been developed, and by utilizing its unique property, a nonionic surfactant adsorbent,
Applied research is being conducted on light-shielding materials, thickeners, stain-proofing agents, marine antifouling materials, artificial muscles, drug delivery system materials, etc.

The inventors of the present invention have also found that the hydrophilic-hydrophobic reversible change type polymer is composed of a polymer or copolymer of N-isopropylacrylamide, Nn-propylacrylamide, N-cyclopropylacrylamide and N, N-diethylacrylamide. We have developed temperature-sensitive polymeric materials, all of which exhibit low viscosity at low temperatures below the transition temperature,
It had a property of exhibiting high viscosity at a temperature higher than the transition temperature.

As a result of further research thereafter, a monomer which forms a hydrophilic-hydrophobic reversible temperature-sensitive polymer when polymerized alone as described above is copolymerized with a reactive surfactant. By doing so, we succeeded in producing heat-sensitive gel microbeads, but when this also dissolves in water, it has a low viscosity below the transition temperature and a high viscosity above the transition temperature. there were.

By the way, contrary to the conventional materials, these temperature-sensitive polymer materials have a low viscosity at a high temperature, but a high viscosity at a low temperature. Although it is clear that the field of application of the temperature-sensitive polymer material will be expanded, such a temperature-sensitive polymer material has not been known so far.

[0006]

DISCLOSURE OF THE INVENTION The present invention provides a novel temperature-sensitive polymer material that behaves in the opposite manner to the conventional hydrophilic-hydrophobic reversible temperature-sensitive polymer material with respect to temperature change. It was made for the purpose of providing.

[0007]

DISCLOSURE OF THE INVENTION The present inventors have found that a monomer forming a temperature-sensitive polymer which shows a hydrophilic-hydrophobic reversible change when it is polymerized alone, or this monomer and other monomers. When a mixture of a copolymerizable monomer and a reactive surfactant is copolymerized, it surprisingly exhibits low viscosity at high temperature and high viscosity at low temperature. It was found that a polymer can be obtained, and the present invention has been completed based on this finding.

That is, the present invention relates to (A) N-propylacryl or methacrylamide and N, N-diethyl ether.
At least one monomer selected from acrylic or methacrylamide , or if desired, this monomer
And (A ') another ethylenic desaturation copolymerizable therewith
Mixture with at least one comonomer selected from compounds
Compound, (B) general formula

[Chemical 3] (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, M is an alkali metal atom or a quaternary ammonium residue) and a reactive surfactant represented by It is intended to provide a high-temperature low-viscosity low-temperature high-viscosity temperature-sensitive polymer material comprising an aqueous solution containing a copolymer at a concentration of 2 to 30% by mass.

[0009]

High temperature and low viscosity low temperature and high viscosity type temperature sensitive polymer material of the embodiment of the present invention is, (A) the specific at least one selected from among acrylic or methacrylic amides monomeric or (A ') and the monomer, and a mixture of at least one comonomer selected from among the acrylic or methacrylamide with copolymerizable ethylenically unsaturated compounds, (B) the general formula (I ), An aqueous solution of a copolymer with a reactive surfactant.

[0010] A <br/> acrylic or methacrylic amides of the component (A) constituting the copolymer is known, in the present invention, any from among the known acrylic or methacrylamide <br/> Can be selected and used.

Used as the component (A) in the present invention
As acrylic or methacrylamide ,
Ropyl acrylamide, ie Nn-propyl acrylamide or methacrylamide , N-isopropyl acrylamide or methacrylamide , N-cyclopropyl acrylamide or methacrylamide,
N, N-diethyl acrylamide or methacrylic acid
There is Mido.

These acrylamide or methacrylic acid
Lamide may be used alone or in combination of two or more kinds.
You may use together.

[0013] In addition, Oite to the present invention, the monomer component
Te (A) component of the N- propyl acrylate or methacrylamide and N, N- diethyl-acrylic or methacrylic
A copolymer selected from other ethylenically unsaturated compounds (A ') copolymerizable with them can be used in combination with the amide. Such (A ') component
The ethylenically unsaturated compound of is also already known, and in the present invention, it can be arbitrarily selected and used from these known ethylenically unsaturated compounds.

Examples of such ethylenically unsaturated compounds include acrylamide or methacrylamide, N
-Ethyl acrylamide or methacrylamide, N
-Tert-butylacrylamide or methacrylamide, N-methylolacrylamide or methacrylamide, N-hydroxypropylacrylamide or methacrylamide, unsaturated carboxylic acids such as acrylic acid or methacrylic acid, methyl acrylate or methacrylate, ethyl acrylate or methacrylate , N-butyl acrylate or methacrylate, tert-butyl acrylate or methacrylate, 2-ethylhexyl acrylate or methacrylate, 2-acetoacetoxyethyl acrylate or methacrylate, 2-acetoacetoxypropyl acrylate or methacrylate, 3-acetoacetoxypropyl acrylate or methacrylate, 4 -Cyanoa DOO acetoxyethyl acrylate or methacrylate, 2-hydroxyethyl acrylate or methacrylate, or 3-hydroxypropyl acrylate or acrylic acid esters such as methacrylate and methacrylic acid esters, N- methylol acrylamide or methacrylamide, N-
Acrylamides and methacrylamides such as hydroxypropyl acrylamide or methacrylamide, unsaturated hydrazides such as N-acryloylbenzhydrazide and N-methacryloylbenzhydrazide, unsaturated nitriles such as acrylonitrile and methacrylonitrile, and , Vinyl acetate, vinyl chloride, styrene, α-methyl styrene, N-vinyl imidazole, vinyl methyl ether, vinyl ethyl ether , which are commonly used as monomers . These (A ′) components may be used alone or in combination of two or more.

In the temperature-sensitive polymer material of the present invention,
(A') by selecting the type and content of the comonomer ethylenically unsaturated compound Ru is used as a component, but the transition temperature can be adjusted arbitrarily within a range of 0 to 100 ° C., this At this time, the content ratio of the component (A ') is (A)
Min per 100 parts by mass it is necessary in the range not exceeding 70 parts by mass.

Next, in the present invention, as the component (B), the reactive surfactant represented by the general formula (I),
That is, it is necessary to use an alkyl sulfosuccinic acid alkenyl ether salt type reactive surfactant, and when a reactive surfactant other than this is used, the desired high temperature low viscosity low temperature high viscosity type temperature sensitive polymer material is used. Can't get This alkyl succinic acid alkenyl ether salt type reactive surfactant is commercially available, for example, "Latemur S-
120 "," Latemuru S-120A "," Latemuru S- "
180 "and" Latemur S-180A "(all manufactured by Kao Corporation). These reactive surfactants may be used alone or in combination of two or more.

The copolymer constituting the main component of the high-temperature low-viscosity low-temperature high-viscosity temperature-sensitive polymer material of the present invention comprises a monomer unit derived from the component (A) and optionally a component (A '). Or
It is composed of a monomer unit derived from (B) and a monomer unit derived from the component (B). Based on 0.00
It is selected within the range of 1 to 20 mol%, preferably 0.01 to 10 mol%. When the amount of the monomer unit derived from the component (B) is smaller than that, the viscosity is almost the same as that of water at a temperature higher than the transition temperature, but it is remarkably high below the transition temperature. It is not possible to obtain a temperature-sensitive polymer material having the above-mentioned property, and if the number of monomer units derived from the component (B) is larger than that, the temperature-sensitive property will be impaired.

The above component (A) and optionally (A ')
The copolymer obtained by copolymerizing the component and the component (B) is
At a temperature higher than the transition temperature in an aqueous medium, the viscosity is almost the same as that of water, but below the transition temperature, the viscosity is remarkably high. That is, at a temperature higher than the transition temperature, the reactive surfactant unit more easily takes a micelle structure in water than the strength of the hydrophobic interaction of the temperature-sensitive polymer that constitutes the copolymer, The copolymer has a micellar structure in water, and because the copolymer is dispersed in the water system as submicron-sized particles, it exhibits almost the same low viscosity as water, but below the transition temperature the copolymer is water soluble. It becomes swellable and swells to cause entanglement between copolymer molecules, and exhibits a remarkably high viscosity.

The high-temperature low-viscosity low-temperature high-viscosity temperature-sensitive polymer material of the present invention is a solution prepared by dissolving the component (A) and optionally the copolymer of the component (A ') and the component (B) in an aqueous medium. As the aqueous medium, water alone or a mixed solvent of water and a water-soluble organic solvent such as methyl alcohol or ethyl alcohol is used. The copolymer concentration in this solution is 2
It should be in the range of -30% by mass, preferably 3-20% by mass. If this copolymer concentration is less than 2% by mass, no increase in viscosity is observed even if cooled below the transition temperature, and if it is more than 30% by mass, the viscosity is already considerably high even at high temperatures, and the response is high. Becomes defective.

The high-temperature low-viscosity low-temperature high-viscosity temperature-sensitive polymer material of the present invention comprises the above-mentioned component (A) and optionally (A ').
Min and the aqueous solution containing the component (B) can be prepared by radical polymerization according to a conventional method.

The concentration of the aqueous solution in this case is usually
It is selected in the range of 2 to 15% by mass based on the total amount of the monomers, and as the concentration of the reactive surfactant of the component (B),
It is necessary to select a concentration above the critical micelle concentration in order to carry out intra-micellar polymerization. This concentration range is usually 0.001 to 10 mol%, preferably 0.01 to 8 mol% based on the total amount of the monomers. This reactive surfactant is
It plays a role of an emulsifier in a polymerization reaction for forming a predetermined polymer or copolymer. Conventionally, a corresponding cationic surfactant or anionic surfactant has been used as an emulsifier, but these remain in the reaction mixture after completion of the polymerization and are mixed in the produced polymer or copolymer. Therefore, it is necessary to perform a special removal treatment because there is a risk of contamination. On the other hand, in the present invention, since it is incorporated into the molecule as a part of the monomer unit,
It is not necessary to perform such removal processing.

As means for initiating the polymerization, known means such as irradiation with radiation or electron beam, heating in the presence of a radical polymerization initiator, and light irradiation in the presence of a photosensitizer are used. Although methods can be used, among these methods, the method of heating in the presence of a radical polymerization initiator is preferable. The radical polymerization initiator is not particularly limited as long as it is water-soluble. For example, ammonium persulfate, potassium persulfate, hydrogen peroxide, tert-
Butyl hydroperoxide, etc., or redox type initiators such as sulfite, hydrogen sulfite, ceric ammonium nitrate, and 2,2'-azobis-2-amidinopropane hydrochloride, 2,2'-azobis-2 Azo compounds such as 4-dimethylvaleronitrile, 4,4'-azobis-4-cyanovaleric acid and salts thereof can be used. These radical polymerization initiators may be used alone or in combination of two or more.
The amount used is usually 0.01 with respect to the total amount of monomers.
To 100% by mass, preferably 0.05 to 8% by mass.

The reaction temperature is usually selected in the range of 0 to 100 ° C., though it varies depending on the kinds of the monomer and the initiator used. This reaction temperature needs to be a temperature equal to or higher than the transition temperature of the aqueous copolymer solution produced by the polymerization. At a temperature lower than this, the viscosity increases during the reaction and the polymerization does not proceed sufficiently.

By reacting in this way, a copolymerization reaction occurs in the micelles, and a copolymer can be efficiently obtained. After the completion of the polymerization, a dialysis membrane is used to perform a dialysis operation at the transition temperature of the copolymer that produced the reaction solution, whereby a copolymer in which unreacted monomers are completely removed can be obtained.

The fact that the copolymer thus obtained contains a reactive surfactant unit as a constitutional unit of its molecular chain means that its characteristic peak is recognized in the infrared absorption spectrum and that it is washed with water. It has been confirmed that the content of the reactive surfactant in the copolymer does not decrease even if it is repeated.

The temperature-sensitive polymer compound of the present invention is water-soluble at a temperature below the transition temperature, becomes hydrophobic at a temperature higher than the transition temperature, and is dispersed in a water system as particles of submicron size. It has the unique property of exhibiting almost the same low viscosity.

Therefore, the reaction solution obtained by the polymerization reaction is a specific bluish dispersion liquid which is close to pure water in a state of being maintained at the temperature at the time of polymerization, that is, the transition temperature of the produced copolymer or more. However, when it is cooled to a temperature lower than the transition temperature, the micelle structure is destroyed, the copolymer molecules are dissolved or swelled in water, and it changes into a transparent ultrahigh viscosity aqueous liquid. When this aqueous liquid is heated again, the viscosity decreases with increasing temperature until it reaches the transition temperature,
When the transition temperature is exceeded, the action of the reactive surfactant unit of the component (B) to try to take a micelle structure in water is stronger than the hydrophobic interaction strength of the thermosensitive polymer constituting the copolymer. You will win. The copolymer has a micelle structure in water, and since the copolymer is dispersed in the water system as submicron-sized particles, it exhibits a viscosity as low as that of water.

Therefore, when the temperature-sensitive polymer compound of the present invention is dispersed in various aqueous media, it can control a wide range of viscosity from low viscosity to high viscosity and no fluidity in a wide temperature range. You can enable it. The transition temperature can be adjusted by changing the type and content of each component in the monomer mixture, or by adding salt or alcohol to the medium.

[0029]

EXAMPLES Next, the present invention will be described in more detail by way of examples.

Example 1 500 m with a V-shaped tube equipped with a capillary stopper and a cooling tube
In a 1-volume Erlenmeyer flask, 200 g of distilled water, 8.94 g of N-isopropylacrylamide and an alkenyl ether alkylsuccinate reactive surfactant (Kao Corporation, trade name “Latemur S-180A”, active ingredient content 50) (Mass%) 1.40 g was introduced, and nitrogen gas was passed for 30 minutes, then 0.05 g of ammonium persulfate was added, and the mixture was heated to 60 ° C. while stirring under a nitrogen stream to initiate polymerization. After polymerization was carried out at 60 ° C. for 3 hours while stirring, air was blown in to stop the polymerization, and the reaction mixture was allowed to cool to room temperature.

Next, the obtained reaction mixture was dialyzed with a dialysis membrane at the transition temperature (34 ° C.) of the produced copolymer to remove impurities, and then freeze-dried to obtain an unreacted unit amount. A temperature-sensitive copolymer having a completely removed body was obtained. Then, a predetermined amount of distilled water at 20 ° C. was added to this temperature-sensitive copolymer to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass, 3% by mass and 5% by mass. For each of these aqueous solutions, the relationship between temperature and viscosity at the time of temperature rise and temperature decrease was investigated, and a graph was prepared as shown in FIG.
Shown in. As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in viscosity at a transition temperature (34 ° C.) or lower, whereas an aqueous solution having a concentration of less than 2% by mass shows an increase in viscosity. Hardly recognized.

Example 2 In place of N-isopropylacrylamide in Example 1, Nn-propylacrylamide was used.
A temperature-sensitive copolymer was produced in the same manner as in. Next, a predetermined amount of distilled water was added to this temperature-sensitive copolymer to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass, 3% by mass and 5% by mass. For each of these aqueous solutions, the relationship between temperature and viscosity at the time of temperature increase and temperature decrease was investigated, and a graph is shown in FIG. As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in viscosity at a transition temperature (20 ° C.) or lower, whereas an aqueous solution having a concentration of less than 2% by mass
Almost no increase in viscosity is observed.

Example 3 N-isopropylacrylamide in Example 1 8.
N, N-diethylacrylamide 25. instead of 94 g.
A temperature-sensitive copolymer was produced in the same manner as in Example 1 using 43 g. Next, a predetermined amount of distilled water was added to this temperature-sensitive copolymer to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass, 3% by mass and 5% by mass. For each of these aqueous solutions, the relationship between temperature and viscosity at the time of temperature increase and temperature decrease was investigated, and a graph is shown in FIG. As can be seen from this figure, an aqueous solution having a concentration of 2% by mass or more shows a sharp increase in the viscosity at a transition temperature (28 ° C.) or lower, whereas an aqueous solution having a concentration of less than 2% by mass does not increase the viscosity. Hardly recognized.

Example 4 500 m with a V-shaped tube equipped with a capillary stopper and a cooling tube
In a 1-volume Erlenmeyer flask, 200 g of distilled water, 9.53 g of N-isopropylacrylamide, 1.21 g of N-tert-butylacrylamide and an alkenyl ether alkylsuccinate reactive surfactant (Kao Corporation, trade name "Latemur" S-180A ", active ingredient content 50
%) 1.40 g, and nitrogen gas was passed through for 30 minutes, then ammonium persulfate 0.05 g was added, and the mixture was heated to 60 ° C. while stirring under a nitrogen stream to initiate polymerization. After conducting polymerization for 2 hours while stirring at 60 ° C., air was blown in to stop the polymerization, and the reaction mixture was allowed to cool to room temperature.

Next, the obtained reaction mixture was dialyzed with a dialysis membrane at the transition temperature (27 ° C.) of the produced copolymer to remove impurities, and then lyophilized to obtain an unreacted monomer. A temperature-sensitive copolymer in which the monomer was completely removed was obtained. Next, this temperature-sensitive copolymer was dissolved in distilled water at 20 ° C. to prepare an aqueous liquid having a concentration of 5.5 mass%, and the change in viscosity depending on the temperature was examined, and the graph is shown in FIG. As you can see from this figure,
This aqueous solution shows a sharp increase in viscosity below the transition temperature (27 ° C.).

Example 5 N-isopropylacrylamide in Example 4 9.
53g and N-tert-butylacrylamide 1.21
N-isopropylacrylamide 9.82 instead of g
g and 1.54 g of dimethylacrylamide were used to produce a temperature-sensitive copolymer in the same manner as in Example 4. Next, this temperature-sensitive copolymer was dissolved in distilled water at 20 ° C. to prepare an aqueous liquid having a concentration of 6% by mass, and the change in viscosity depending on the temperature was examined, and the graph is shown in FIG. As you can see from this figure,
This aqueous solution shows a sharp increase in viscosity below the transition temperature (37 ° C.).

Comparative Example 1 500 m with a V-shaped tube equipped with a capillary stopper and a cooling tube
In a 1-volume Erlenmeyer flask, add 200 g of distilled water and 9.00 g of N-isopropylacrylamide to the formula.

[Chemical 4] 0.70 g of a reactive surfactant represented by (Daiichi Kogyo Seiyaku Co., Ltd., trade name "Aqualon HS-10") was put in, nitrogen gas was passed for 30 minutes, and then 0.05 g of ammonium persulfate was added, While stirring under a nitrogen stream,
Polymerization was initiated by heating to 60 ° C. After carrying out the polymerization for 4 hours while stirring at 60 ° C., air was blown in to stop the polymerization, and the reaction mixture was allowed to cool to room temperature.

Next, the obtained reaction mixture was dialyzed with a dialysis membrane at the transition temperature (34 ° C.) of the produced copolymer to remove impurities, and then freeze-dried to obtain an unreacted monomer. A temperature-sensitive copolymer in which the monomer was completely removed was obtained. Then, a predetermined amount of distilled water at 20 ° C. was added to this temperature-sensitive copolymer to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass, 3% by mass and 5% by mass. The relationship between the temperature and the viscosity at the time of temperature increase and temperature decrease was investigated, and a graph is shown in FIG. As can be seen from this figure, the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity even when the temperature is lowered to the transition temperature (34 ° C.) or lower, and the temperature-sensitive copolymer does The reversible behavior of is also not recognized.

Comparative Example 2 A 500 ml Erlenmeyer flask with a V-shaped tube equipped with a capillary stopper and a cooling tube was placed, and 200 g of distilled water, 40 g of N-isopropylacrylamide and the general formula were used.

[Chemical 5] (R in the formula is a saturated hydrocarbon group having 12 to 13 carbon atoms) Reactive surfactant (manufactured by Sanyo Chemical Industry Co., Ltd., trade name "Eleminol JS-2", active ingredient 3
(8% by mass), and after passing nitrogen gas for 30 minutes, add 0.05 g of ammonium persulfate to 60 ° C.
Polymerization was carried out for 2 hours with stirring in a nitrogen stream. The reaction mixture was allowed to cool to room temperature, then dialyzed for purification and freeze-dried to obtain a temperature-sensitive copolymer.
The temperature-sensitive copolymer thus obtained was dissolved in a predetermined amount of distilled water to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass and 3% by mass. The relationship between the temperature and the viscosity of these aqueous solutions was investigated, and the result is shown as a graph in FIG. As can be seen from this figure, the aqueous solution of the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity below the transition temperature (30 ° C.).

Comparative Example 3 500 m with a V-shaped tube equipped with a capillary stopper and a cooling tube
In a 1-volume Erlenmeyer flask, add 195 g of distilled water and 26.5 g of N-isopropylacrylamide

[Chemical 6] Reactive surfactant represented by (manufactured by Sanyo Kasei Co., Ltd., trade name "Eleminol RS-30", active ingredient 50
(% By mass) was introduced, and nitrogen gas was passed through for 30 minutes, then 0.05 g of ammonium persulfate was added, and polymerization was carried out at 60 ° C. for 1.5 hours while stirring in a nitrogen stream. The reaction mixture was allowed to cool to room temperature, then dialyzed for purification and freeze-dried to obtain a temperature-sensitive copolymer. The temperature-sensitive copolymer thus obtained was dissolved in a predetermined amount of distilled water to prepare an aqueous liquid having a concentration of 1% by mass, 2% by mass 3% by mass and 5% by mass. The relationship between the temperature and the viscosity of these aqueous solutions was investigated, and the results are shown as a graph in FIG. In addition, sp18 is measured using the spindle 18 in a Brookfield viscometer, and sp34 is measured using the spindle 34. As can be seen from this figure, the aqueous solution of the temperature-sensitive copolymer obtained in this example does not show a sharp increase in viscosity below its transition temperature (34 ° C.).

As is clear from the above comparative examples,
When a reactive surfactant other than the reactive surfactant represented by the general formula (I) is used as the component (B), a high-temperature low-viscosity low-temperature high-viscosity thermosensitive polymer material cannot be obtained. .

[0042]

EFFECTS OF THE INVENTION According to the present invention, a novel temperature-sensitive polymer material having specific properties that have never been known is obtained. This temperature-sensitive polymer material is suitable as a thickener for paints for coated paper.

[Brief description of drawings]

1 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Example 1. FIG.

FIG. 2 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Example 2.

FIG. 3 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Example 3.

FIG. 4 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Example 4.

FIG. 5 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Example 5.

FIG. 6 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Comparative Example 1.

7 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Comparative Example 2. FIG.

FIG. 8 is a graph showing the relationship between temperature and viscosity of the aqueous copolymer solution obtained in Comparative Example 3.

Front page continued (72) Akira Agata Inventor Akira Agata 2-10-5 Nihonbashi, Chuo-ku, Tokyo 2nd SK building 9th floor Patent Capital Stock Association In-house (72) Inami Inoue 2-10-5 Nihonbashi, Chuo-ku, Tokyo 2nd SK building 9th floor Patent Capital Stock Association In-house (56) Reference JP-A-11-189626 (JP, A) JP-A-61-247716 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C08F 220/54-220/60 C08F 216/12-216/14 C09K 3/00

Claims (4)

(57) [Claims] 1. (A) N-propyl acryl or methacrylamide and N, N-diethyl acryl or
At least one monomer selected from methacrylamide , and (B) a general formula: (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, M is an alkali metal atom or a quaternary ammonium residue) and a reactive surfactant represented by A high-temperature low-viscosity low-temperature high-viscosity thermosensitive polymeric material comprising an aqueous solution containing a copolymer in a concentration of 2 to 30% by mass. 2. (A) N-propyl acrylic or polymer
Tacrylamide and N, N-diethyl acryl or
Mixture of at least one monomer selected from methacrylamide and (A ') with at least one comonomer selected from other ethylenically unsaturated compounds copolymerizable therewith . And (B) general formula: (Wherein R is an aliphatic saturated or unsaturated long-chain hydrocarbon group having 10 to 20 carbon atoms, M is an alkali metal atom or a quaternary ammonium residue) and a reactive surfactant represented by A high-temperature low-viscosity low-temperature high-viscosity thermosensitive polymeric material comprising an aqueous solution containing a copolymer in a concentration of 2 to 30% by mass. 3. The high temperature, low viscosity, low temperature, high temperature according to claim 1, wherein the content of the reactive surfactant as the component (B) in the copolymer is 0.001 to 20 mol% of all the monomers. Viscosity type thermosensitive polymer material. 4. The high-temperature low-viscosity low-temperature high-viscosity temperature-sensitive property according to claim 2, wherein the content ratio of the component (A ′) to the component (A) is 70 parts by mass or less per 100 parts by mass of the former. Polymeric materials .