JP5285839B2 - Method for producing polymer composite gel - Google Patents

Description

  The present invention relates to a polymer gel used in the fields of medicine, architecture, civil engineering, machinery, transportation, electronic components, sewing, household goods, sanitary goods, agriculture, foods, and the like.

  Today, polymer gels are used in a wide range of fields such as medicine, medicine, architecture, civil engineering, machinery, transportation, electronic components, chemical industry, leisure industry, sewing, household goods, sanitary goods, agriculture, food (for example, Gel Handbook, NTS, 1997). For further development of such a polymer gel, it has been necessary to improve mechanical properties and functional properties such as swelling, swelling / shrinkage change, and adhesiveness. Conventional polymer gels using an organic crosslinking agent or prepared by irradiation with an electron beam or γ-ray have the disadvantage that the elongation at break and the mechanical strength are small and they are brittle and the handleability is poor. In recent years, one of the inventors of the present invention has developed a hydrogel having a three-dimensional network formed of a water-soluble organic polymer and an inorganic clay mineral, and has reported that a polymer gel having unprecedented mechanical properties can be obtained. (See Patent Document 1). However, when this polymer gel is to be used practically, there has been a demand for the development of a polymer composite gel with further improved functionality including mechanical properties, swelling properties, surface tackiness, and the like.

JP 2002-53629 A

  The problem to be solved by the present invention is to provide a polymer composite gel that is excellent in mechanical strength and whose surface tackiness and swelling property are controlled according to the purpose, a dried product thereof, and a production method thereof. .

  As a result of diligent research to solve the above-mentioned problems, the present inventor has found that the same or different kinds of crosslinked or uncrosslinked organic polymers are at the molecular level in a gel in which an organic polymer and a clay mineral form a three-dimensional network. It has been found that by including it in a complex, the mechanical properties, swelling and shrinkage can be controlled in a wider range, and an improved polymer composite gel and dried product thereof can be obtained, and the present invention has been completed. .

That is, in the present invention , one or two or more organic polymers (B) are trapped in a state where molecular chains are entangled in the three-dimensional network structure of the organic polymer (A) having a water-swellable clay mineral as a crosslinking point. A method for producing a polymer composite gel, wherein the organic polymer (A) is a polymer of a water-soluble organic monomer, and the water-swellable clay mineral is a crosslinking point of the organic polymer (A). The organic polymer (B) is formed by allowing the same or different organic monomer (Bm) as the water-soluble organic monomer to enter the three-dimensional network structure and then polymerizing the organic monomer (Bm). A method for producing a polymer composite gel is provided.

In addition, the present invention captures a state in which one or two or more organic polymers (B) are entangled in a three-dimensional network structure of an organic polymer (A) having a water-swellable clay mineral as a crosslinking point. A method for producing a polymer composite gel, wherein the organic polymer (A) is a polymer of a water-soluble organic monomer and the water-swellable clay mineral is a crosslinking point. The present invention provides a method for producing a polymer composite gel, wherein the same or different organic polymer (B) as the organic polymer (A) is allowed to enter the three-dimensional network structure .

  The polymer composite gel in the present invention has surface tackiness and swelling property controlled according to the purpose, and is excellent in mechanical strength. Therefore, it is effectively used in a wide range of fields such as medical / medicine, hygiene products, information / electronic materials, civil engineering / building materials, and analytical materials. In addition, the polymer composite (dry polymer composite gel) obtained by removing the solvent from the composite polymer gel is also a gel material that absorbs the solvent as a composite material with excellent mechanical and thermal properties. It is effectively used as

  The polymer composite gel in the present invention is required to be composed of two or more organic polymers having different cross-linked states and that at least one organic polymer forms a three-dimensional network using a clay mineral. . More specifically, the polymer composite gel in the present invention has a three-dimensional network structure of an organic polymer having a clay mineral as a crosslinking point (hereinafter, this crosslinked organic polymer is referred to as an organic polymer (A)). One or two or more organic polymers (hereinafter referred to as organic polymer (B)), either uncrosslinked or crosslinked, are trapped in a state where molecular chains are entangled. It has a structure. In addition, an uncrosslinked organic polymer means a linear and branched organic polymer. Here, the one or two or more organic polymers include not only different types of polymers but also the same type of polymers that have different properties depending on the crosslinking method and degree of crosslinking.

  The organic polymer (A) used in the present invention that interacts with a clay mineral to form a three-dimensional network with the clay mineral is preferably a water-soluble polymer that dissolves in water, swells, or absorbs moisture. Hydrophilic polymers and amphiphilic polymers are used. However, a hydrophobic polymer can be used as long as a three-dimensional network can be formed by interaction with the clay mineral. Examples of the monomer (organic monomer (Am)) of the organic polymer (A) before polymerization include functional groups such as amide group, amino group, carboxylic acid group, ether group and hydroxyl group that interact with clay minerals and quaternary. Those containing an ionic group such as an ammonium ion in the main chain or side chain are preferred, particularly preferably those having an amide group and water-soluble that swells or dissolves in water or a mixed solvent of water and an organic solvent. It is. As the amide group-containing organic polymer, those that dissolve or swell in water are particularly preferable. In addition to the amide group, a functional group having an affinity for water (for example, a hydroxyl group, an amino group, an ester group, a carboxylic acid group, an ether group). May also be included.

  For example, specific examples of the amide group-containing organic polymer (A) include amide groups such as N-alkylacrylamide, N, N-dialkylacrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide, and acrylamide. Examples thereof include a polymer obtained by polymerizing one or more selected from polymerizable monomers. For example, poly (N-methylacrylamide), poly (N-ethylacrylamide), poly (N-cyclopropylacrylamide), poly (N-isopropylacrylamide), poly (methacrylamide), poly (N-methylmethacrylamide), Poly (N-cyclopropylmethacrylamide), poly (N-isopropylmethacrylamide), poly (N, N-dimethylacrylamide), poly (N, N-dimethylaminopropylacrylamide), poly (N-methyl-N-ethyl) Acrylamide), poly (N-methyl-N-isopropylacrylamide), poly (N-methyl-Nn-propylacrylamide), poly (N, N-diethylacrylamide), poly (N-acryloylpyrrolidine), poly ( N-acryloylmorpholine), po (N- acryloyl Lupi peri Din), poly (N- acryloyl methyl homo piperazinyl Laden), poly (N- acryloyl-methylpiperazinyl Laden), poly (acrylamide), and the like. Further, the combined use of the amide group-containing monomer and other polymerizable monomers can be used as long as a three-dimensional network with the clay mineral referred to in the present invention can be formed.

  The organic polymer (B) may be the same as or different from the organic polymer (A). As the organic polymer (B), any of a non-crosslinked linear (or branched) organic polymer and a crosslinked organic polymer can be used, and a composite gel can be formed with the organic polymer (A). For example, the type of organic polymer, the presence or absence of crosslinking, and the type of crosslinking can be selected according to the purpose. For example, as the crosslinked organic polymer (B), an organic polymer crosslinked with an organic crosslinking agent (covalently), an organic polymer crosslinked with a clay mineral, and other methods (for example, ion Any organic polymer cross-linked by a bond, a coordinate bond, a hydrogen bond, a hydrophobic bond, a microcrystal formation, a helix formation, etc. can be used. Further, when the organic polymer (B) is an organic polymer crosslinked with a clay mineral, the organic polymer (A) may be crosslinked even if the organic polymer (A) and the clay mineral are cross-linked. It may be cross-linked using another clay mineral. The number of types of the organic polymer (B) in the present invention is at least one, and it is possible to include a plurality of the same or different organic polymers (B).

  The organic polymer (B) in the present invention may be the same or different from the organic polymer (A), and can penetrate into the three-dimensional network of the organic polymer (A) at the molecular level. Used. Specific examples of the organic polymer (B) include organic polymers having an ester group, a hydroxyl group, an amino group, and a carboxylic acid group in addition to the examples given for the amide group-containing polymer described in the organic polymer (A). Is included. For example, poly (2 methoxyethyl acrylate), poly (2-hydroxyethyl acrylate), polyvinyl alcohol, polyethyleneimine, polyethylene oxide, polyvinylpyrrolidone, carboxymethylcellulose, methylcellulose, gelatin, collagen, sodium chondrotin sulfate, agar, carrageenan, hydroxyethylcellulose Hydroxypropyl cellulose, polystyrene, polybutylene, polymethyl methacrylate, polyamide resin, polyimide, epoxy resin, phenol resin, and the like. In addition, the organic polymer (B) is not necessarily limited to a monomer (organic monomer (Bm)) before polymerization, but may be soluble or dispersible in an organic solvent. In addition, as a compound applicable to an organic monomer (Bm), not only a low molecular weight compound but an oligomer is included.

  In addition, as the organic polymer (A) and / or (B) in the present invention, those having stimulus responsiveness, for example, those showing a phase transition due to changes in heat, salt concentration, pH, etc. are functionally expressed, It is preferably used in terms of controlling swelling / shrinking. Specifically, for example, poly (N-isopropylacrylamide) and poly (N, N-diethylacrylamide) are particularly preferably used.

  As the clay mineral in the present invention, it is essential to have swelling with water or an organic solvent. Preferably, it is a swellable clay mineral that can be uniformly dispersed in water or a mixed solvent of water and an organic solvent, and particularly preferably a swellable clay mineral that can be uniformly dispersed at a molecular level or a level close to that in a solvent containing water. . In addition, it is essential that clay minerals can form a three-dimensional network by interacting with organic polymers. Examples of such clay minerals include swellable clay minerals such as water-swellable smectite and water-swellable mica. Specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water Examples include swellable saponite and water-swellable synthetic mica. In the present invention, the swellable clay mineral is preferably finely and uniformly dispersed in the solution before the polymerization of the organic monomer (Am), more preferably at a nanometer level (thickness) within 1 to 10 layers. It is distributed. The amount of the clay mineral contained is not particularly limited as long as it forms a three-dimensional network with the organic polymer. For example, the mass ratio of the clay mineral to the organic polymer in the organic polymer (A) (clay mineral / organic high The molecule is preferably from 0.001 to 10, more preferably from 0.05 to 5, particularly preferably from 0.1 to 1. In addition, for the formation of a three-dimensional network of clay mineral and organic polymer, the interaction between the clay mineral surface and the end of the organic polymer, or the clay mineral surface and the functional group of the main chain or side chain of the organic polymer. Interactions and the like are used alone or in combination. Various types of interactions can be selected depending on the types and combinations of clay minerals and organic polymers. For example, ionic interaction, coordination bond, hydrogen bond, covalent bond, hydrophobic interaction, etc. are singly or plural. Used in combination.

  In the present invention, a polymer gel in which the concentration of at least one organic polymer is inclined from the surface to the inside of the polymer gel is also effectively used. Here, the organic polymer exhibiting a concentration gradient may be one or a plurality selected from the organic polymer (A) or the organic polymer (B). The concentration gradient may be selected as long as the concentration of the organic polymer varies depending on the position, such as inside and outside, top and bottom, depending on the shape of the polymer gel. There is no particular limitation. Further, in the present invention, the case where the inclined distribution is a distribution of the degree of crosslinking of the organic polymer is also included. For example, when the organic polymer (B) is highly crosslinked with an organic crosslinking agent, and the concentration of the organic polymer (B) is high near the surface and the inside is low, the surface tack which is the effect of the present application is achieved. In addition to low mechanical properties and swelling properties and excellent mechanical strength, it also has excellent insolubility, low adsorptivity, low swelling properties, and the like. On the other hand, when the non-crosslinked organic polymer (B) is localized and complexed in the vicinity of the surface so as to have strong entanglement, not only the mechanical properties which are the effects of the present application are excellent, but also surface tackiness and adhesiveness. Can be made particularly high.

  The polymer composite gel according to the present invention is a composite in which a three-dimensional network composed of an organic polymer (A) and a clay mineral is entangled with a crosslinked or uncrosslinked organic polymer (B) at the molecular level and coexists. The manufacturing method is not necessarily limited, but preferably, the following method is specifically exemplified. First, after forming a three-dimensional network composed of an organic polymer and a clay mineral, the organic monomer (Bm) is contained alone or together with an organic crosslinking agent in the gel or a dried gel obtained by drying the gel. The manufacturing method which superposes | polymerizes an organic monomer (Bm). Alternatively, the organic polymer (B) is introduced together with a solvent into a gel or a dried gel product. Here, before the organic monomer (Bm) or the organic polymer (B) is contained, it is used as an effective means to replace the solvent with water. Further, as another method, after the clay mineral and the organic monomer (Am) are contained in a solution or gel containing the organic polymer (B) that is uncrosslinked or cross-linked other than the clay mineral, the organic monomer (Am) ) Is polymerized. Here, the clay mineral may be included in advance. As another method, after preparing an aqueous solution containing both organic monomers (Am), organic monomers (Bm) and clay minerals having different polymerization properties, the polymerization of each organic monomer is selected by selecting, for example, the type of catalyst or initiator. , And a method of manufacturing by shifting. In any method, the solvent contained in the gel is used in any case of water, an organic solvent, or a mixed solvent of water and an organic solvent, and when the organic monomer is liquid, it is used without water or an organic solvent. It is also possible. Solvents contained in the gel are different in solvent type and ratio as needed in the manufacturing process by drying the gel once and then impregnating it with another solvent or replacing the solvent in the gel state. It is possible to change. Moreover, in the manufacturing method of the polymer composite gel in this invention, a suitable initiator and / or catalyst are selected and used for the polymerization of the organic monomer as required. Irradiation with visible light, ultraviolet rays, electron beams, gamma rays, heat, etc. is also used as necessary. The production method of the polymer composite gel having a concentration gradient is not necessarily limited.For example, by setting the concentration of at least one of the organic monomer, the crosslinking agent, the initiator, and the catalyst to be a local or short impregnation time, etc. Examples thereof include a method in which the gel surface is changed in an inclined manner from the surface to the inside or from the top to the bottom.

  Furthermore, the present invention includes a dried polymer composite gel obtained by removing part or all of the solvent from the polymer composite gel. It is effective to perform stretching, compression, cutting, etc. in the process of removing the solvent. The dried polymer composite gel is used as it is as a composite material, and also as a dried gel that absorbs a solvent reversibly.

  EXAMPLES Next, although an Example demonstrates this invention more concretely, this invention is not limited only to the Example shown below from the first.

(Reference Example 1)
As the clay mineral, a water-swellable synthetic hectorite (trademark Laponite XLG, manufactured by Nippon Silica Co., Ltd.) having a composition of [Mg _5.34 Li _0.66 Si ₈ O ₂₀ (OH) ₄ ] Na ⁺ _0.66 was vacuumed at 100 ° C. for 2 hours. Used after drying. The organic monomer was used after purifying N-isopropylacrylamide (NIPA: manufactured by Kojin Co., Ltd.). As the polymerization initiator, potassium peroxodisulfate (PPS: manufactured by Kanto Chemical Co., Inc.) was diluted with pure water at a ratio of KPS / water = 0.384 / 20 (g / g) and used as an aqueous solution. As the catalyst, N, N, N ′, N′-tetramethylethylenediamine (TEMED: manufactured by Kanto Chemical Co., Inc.) was used as it was. As the water, ultrapure water was used. All water was used after bubbling high-purity nitrogen in advance for 3 hours or more to remove oxygen.

  In a constant temperature bath at 20 ° C., 18.98 g of ultrapure water was placed in an approximately 50 ml glass container equipped with a stirrer and purged with nitrogen, and 0.48 g of Laponite XLG and 2.26 g of NIPA were added to obtain a uniform colorless transparent solution. . Subsequently, 1.04 g of KPS aqueous solution and 16 μl of TEMED were added to obtain a colorless transparent solution. This solution was placed in a 5 cm × 10 cm flat bottom container until the thickness reached 3 mm, sealed, and then allowed to stand at 20 ° C. for 20 hours for polymerization. The operations from preparation of the solution to polymerization were all performed in a nitrogen atmosphere in which oxygen was blocked. After 20 hours, a clear, transparent, uniform polymer gel (organic polymer A1) is formed in a flat-bottomed glass container with a three-dimensional network of elastic and tough poly N-isopropylacrylamide (PNIPA) and clay minerals. did. PNIPA and layered exfoliated clay minerals form a three-dimensional network. The transparency, mechanical properties, swelling properties, and thermogravimetric analysis (clay mineral content measurement) for dry gels, transmission electron This was confirmed by microscopic observation (observation of the dispersion state of the layered exfoliated clay mineral), X-ray diffraction (confirmation of layered exfoliation of the clay mineral), and differential scanning calorimetry (measurement of the glass transition temperature of PNIPA). Transparency was measured at 600 nm using a UV / VIS spectrometer manufactured by JASCO Corporation, and the transmittance was 98%. The physical properties of the polymer gel were cut into a width of 10 mm, a thickness of 3 mm, and a length of 100 mm, and subjected to a stretching test using a universal testing machine AGS-H manufactured by Shimadzu Corporation. Obtained. Further, the swelling ratio (water / dry solid mass ratio) in water at 20 ° C. for 200 hours was 68.

(Reference Example 2)
A uniform transparent polymer gel was prepared in the same manner as in Example 1 except that 1.98 g of N, N-dimethylacrylamide (DMAA: manufactured by Kojin Co., Ltd.) was used as the organic monomer. It was confirmed that the obtained polymer gel was a polymer gel (organic polymer A2) in which poly N, N-dimethylacrylamide (PDMAA) and clay mineral formed a three-dimensional network. The light transmittance at 600 nm was 99%, and the elastic modulus, strength, and elongation at break were 3.5 kPa, 81 kPa, and 1504%, respectively. Further, the swelling ratio (water / dry solid mass ratio) in water at 20 ° C. for 200 hours was 83.

Example 1
A polymer gel (organic polymer A1) (5 cm × 10 cm × 3 mm) composed of PNIPA and clay mineral prepared in Reference Example 1 was washed with a large amount of pure water for 5 hours, then at room temperature for 24 hours, and then at 80 ° C. under vacuum for 3 hours. After drying for a time, a gel dried product was obtained. The gel dried product was treated with DMAA as an organic monomer (Bm), DMAA / water / KPS was 0.74 g / 15 g / 0.015 g, and N, N′-methylenebisacrylamide (BIS) was added at 1 mol% of DMAA. It was immersed in the containing organic monomer (Bm) aqueous solution and kept at 1 ° C. until the entire amount was swollen. Next, the temperature was raised to 20 ° C. and left to stand for 48 hours to polymerize the organic monomer (Bm) and BIS to obtain a polymer composite gel. From the subsequent dry weight, the polymerization yield of the organic monomer (Bm) was almost 100%. In this way, a polymer composite gel in which poly (N, N-dimethylacrylamide) is compounded at the molecular level in a gel in which poly (N-isopropylacrylamide) forms a clay mineral and a three-dimensional network. Was prepared. This polymer composite gel was cut into a width of 10 mm, a thickness of 3 mm, and a length of 100 mm, and subjected to a stretching test in the same manner as in Reference Example 1. As a result, an elastic modulus of 24.5 kPa, strength of 187 kPa, and elongation at break of 910% were obtained. The light transmittance measured at 600 nm was 95%. The swelling ratio in water (mass ratio of water / dry solid) at 20 ° C. for 200 hours was 20. As can be seen from the comparison with Comparative Example 1 having almost the same composition, the polymer composite gel obtained in this example contains (NIPA, DMAA, Compared with the polymer gel (which was prepared by copolymerizing clay mineral and water with almost the same composition), it showed extremely high mechanical properties. In addition, it was observed that the polymer composite gel obtained in Example 1 showed a knurled fine pattern during the stretching process. On the other hand, the swelling property in water was suppressed to a low level. Further, it was confirmed that the polymer composite gel was a gel with less surface tack and no stickiness as compared with the polymer gel of Reference Example 1.

(Example 2)
Using N-isopropylacrylamide (NIPA: manufactured by Kojin Co., Ltd.) as the organic monomer (Bm), the composition of the organic monomer (Bm) aqueous solution (NIPA / water / KPS / BIS) for immersing the gel dried product is 0.84 g / A polymer composite gel was prepared in the same manner as in Example 1 except that it was 1 mol% of 15 g / 0.01 g / NIPA. The gel obtained had a light transmittance of 93% (600 nm), and mechanical properties (elastic modulus, strength, elongation at break) by a tensile test were 25.6 kPa, 166 kPa, and 895%. Further, the swelling ratio (water / dry solid mass ratio) in water at 20 ° C. for 200 hours was 18. It was observed that the polymer composite gel obtained in Example 1 also showed a knurled fine pattern during the stretching process. On the other hand, the swelling property in water was suppressed to a low level. Further, it was confirmed that the polymer composite gel was a gel with less surface tack and no stickiness as compared with the polymer gel of Reference Example 1. Thus, also in Example 2, compared with the polymer gel of Comparative Example 2 having almost the same composition, it shows extremely high mechanical properties and surface property changes, and the characteristics of the polymer composite gel due to the mutual penetration of different cross-linked states are Clearly shown.

(Example 3)
Use of a polymer gel (organic polymer A2) having a three-dimensional network composed of the organic polymer (PDMAA) and clay mineral obtained in Reference Example 2, and N-isopropylacrylamide (NIPA) as the organic monomer (Bm) A polymer composite gel was prepared in the same manner as in Example 1 except that the organic crosslinking agent was not used. The physical properties of the obtained gel were measured in the same manner as in Example 1. The light transmittance was 96%, and the mechanical properties (elastic modulus, strength, elongation at break) of the tensile test were elastic modulus 5.5 kPa, strength 143 kPa, and elongation at break 1410%. Moreover, it was observed that it became white when immersed in water at a temperature of 50 ° C., and showed temperature responsiveness. On the other hand, the elution of the organic polymer (B: PNIPA) was not observed even in the volume shrinkage at 50 ° C. Due to the improvement of mechanical properties, temperature responsiveness, non-eluting property, etc., the obtained polymer composite gel can share two kinds of organic polymers (A, B) independently while sharing the same clay mineral. It was considered to form a three-dimensional network with clay minerals. Note that the polymer gel of Reference Example 2 does not exhibit temperature responsiveness.

Example 4
A polymer composite as in Example 1 except that the polymer gel obtained in Reference Example 2 was used, and 2-methoxyethyl acrylate was used as the organic crosslinking monomer (Bm) and no organic crosslinking agent was used. A gel was prepared. The swelling rate of the polymer composite gel was as small as about 5, and the surface tackiness was very small. Next, this was dried at room temperature for 24 hours and at 80 ° C. for 3 hours, and a polymer composite gel containing poly-2-methoxyethyl acrylate as a linear polymer in a three-dimensional network composed of PDMAA and clay mineral. A dried product was obtained. The obtained dried product was an organic / inorganic composite having no surface tackiness, a strength of 13 Mpa, and mechanical toughness.

(Example 5)
From the polymer composite gel obtained in Example 2, the solvent water was vacuum dried at 50 ° C. under normal pressure for 24 hours and at 80 ° C. for 3 hours to obtain a hard, uniform polymer composite gel dried product. By pulverizing the obtained dried polymer composite gel to an average particle size of 43 μm and holding it in water at 20 ° C., a swollen granular shape (average particle size 101 μm) tough polymer composite gel is obtained. It was. Further, when the temperature was set to 50 ° C., water was released and a polymer composite gel having white (non-tacking) surface hydrophobicity was obtained.

(Example 6)
Using the polymer gel obtained in Reference Example 2, using polyethylene glycol (molecular weight 4 million) as the organic polymer (B), the polymer gel in a 5 wt% aqueous solution of the organic polymer (B) for 20 hours. By the dipping method, a polymer composite gel in which polyethylene glycol chains were entangled with the gel polymer chains on the gel surface was prepared. The mechanical properties of the polymer composite gel were almost the same as those of Reference Example 2, while the surface tackiness was extremely large and the gel was excellent in adhesiveness.

(Comparative Example 1)
In the same manner as in Reference Example 1, water / laponite XLG / NIPA / DMAA / KPS was 20 g / 0.48 g / 2.26 g / 0.99 g / 0.00 so that the final composition was almost the same as in Example 1. In addition, 0 mol of N, N′-methylenebisacrylamide (BIS: manufactured by Kanto Chemical Co., Inc.), which is an organic crosslinking agent, was added at 1 mol% of DMAA and 16 μl of catalyst (TMEDA) to prepare a homogeneous reaction solution. . This aqueous solution was poured into a 5 cm × 10 cm flat bottom reaction vessel by the same method as in Reference Example 1 until the thickness became 3 mm, and allowed to stand at 20 ° C. for 20 hours for polymerization to obtain a polymer gel. Since the polymer gel obtained by copolymerization containing all components at the same time as described above is not a polymer composite gel composed of organic polymers having different cross-linked states as in the present invention (Example 1), That is, since the copolymer polymer is a single system crosslinked with an organic crosslinking agent and a clay mineral, it was only weak and brittle mechanically. In fact, the measurement results of mechanical properties by a tensile test were an elastic modulus of 21 kPa, a strength of 12 kPa, and an elongation at break of 48%. Further, the swelling ratio at 20 ° C. for 200 hours was 26.

(Comparative Example 2)
In the same manner as in Reference Example 1, 20 g / 0.48 g / 3.39 g / 0.035 g of water / laponite XLG / NIPA / KPS was contained so that the final composition was almost the same as that of Example 2, and BIS was further contained. A uniform reaction solution was prepared by adding 16 μl of 1/3 mol% of NIPA and catalyst (TMEDA). This aqueous solution was poured into a 5 cm × 10 cm flat bottom reaction vessel by the same method as in Reference Example 1 until the thickness became 3 mm, and allowed to stand at 20 ° C. for 20 hours for polymerization to obtain a polymer gel. Since the polymer gel obtained by copolymerization containing all components at the same time as described above is not a polymer composite gel composed of organic polymers having different cross-linked states as in the present invention (Example 2), That is, since the copolymer polymer is a single system crosslinked with an organic crosslinking agent and a clay mineral, it was only weak and brittle mechanically. In fact, the measurement results of mechanical properties by a tensile test were an elastic modulus of 24 kPa, a strength of 11 kPa, and an elongation at break of 44%. Further, the swelling rate at 20 ° C. for 200 hours was 24.

(Comparative Example 3)
Water / NIPA / KPS / TEMED (each 5 g / 1.7 g / 0.01 g / 8 μl) was reacted at 20 ° C. for 20 hours to obtain a viscous aqueous solution of poly N-isopropylacrylamide. On the other hand, water / DMAA / KPS / TEMED (each 5 g / 0.74 g / 0.01 g / 8 μl) was reacted at 20 ° C. for 20 hours to obtain a viscous aqueous solution of poly N, N-dimethylacrylamide. An attempt was made to prepare a polymer gel having almost the same composition as in Example 1 and Comparative Example 1 by mixing these and a liquid containing 5 g / 0.36 g of water / clay mineral (Laponite XLG). Due to its nature, it contained many bubbles, was white, had a very sticky surface, and only a non-uniform viscous material separated from each other was obtained. The mechanical properties could not be measured. A uniform polymer composite gel cannot be prepared by mixing.

Claims (5)

A polymer composite in which one or two or more organic polymers (B) are trapped in a state where molecular chains are entangled in a three-dimensional network structure of the organic polymer (A) having a water-swelling clay mineral as a crosslinking point. A method for producing a gel, comprising:
The organic polymer (A) is a polymer of a water-soluble organic monomer, and the water-soluble organic monomer is incorporated into the three-dimensional network structure of the organic polymer (A) having the water-swellable clay mineral as a crosslinking point. infested with the same or different organic monomers (Bm), a high molecular method for manufacturing a composite gel you characterized in that subsequent to forming the organic monomer (Bm) by polymerization organic polymer (B). The method for producing a polymer composite gel according to claim 1, wherein the organic monomer (Bm) and an organic crosslinking agent or clay mineral are polymerized by invading into the three-dimensional network structure of the organic polymer (A). The water-soluble organic monomer is one or more monomers selected from N-alkylacrylamide, N, N-dialkylacrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide and acrylamide. A method for producing a polymer composite gel according to 1 or 2. A polymer composite in which one or two or more organic polymers (B) are trapped in a state where molecular chains are entangled in a three-dimensional network structure of the organic polymer (A) having a water-swelling clay mineral as a crosslinking point. A method for producing a gel, comprising:
The organic polymer (A) is a polymer of a water-soluble organic monomer, and the organic polymer (A) is included in the three-dimensional network structure of the organic polymer (A) having the water-swellable clay mineral as a crosslinking point. ) And the same or different organic polymer (B) is allowed to invade, and a method for producing a polymer composite gel. The water-soluble organic monomer is one or more monomers selected from N-alkylacrylamide, N, N-dialkylacrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide and acrylamide. 4. A method for producing a polymer composite gel according to 4.