JP2007125762A - Polymer gel laminate and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer gel laminate capable of preventing the drying of a polymer gel having a three-dimensional reticulated structure, which is constituted of an amide group-containing polymer and a clay mineral, over a long time. <P>SOLUTION: A polymer gel can be utilized while ensuring the excellent physical properties of the polymer gel by the polymer gel laminate having a laminated structure of a layer comprising a polymer gel having a three-dimensional reticulated structure constituted of the amide group-containing polymer and the clay mineral and a layer comprising a flexible member with a steam permeability of 100 g/m<SP>2</SP>/24 hr×100 μm or below. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention is a high structure having a laminated structure of a layer composed of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and a clay mineral, and a layer composed of a flexible member having a low water permeability. The present invention relates to a molecular gel laminate and a method for producing the same.

  Since polymer gel can contain a large amount of solvent (water, water-soluble organic solvent, etc.), the polymer gel has excellent transparency, flexibility, solvent absorbability, adsorbability and permeability of specific solutes, In many fields including analysis, chemical industry, agriculture, civil engineering, architecture, and medical fields, it is expected to be widely used as a soft material, a water absorbing material, an adsorbent, a selective separating material, a vibration absorbing material, and the like. However, there have been few polymer gels that have both functional properties and mechanical properties, and many of the polymer gels have the disadvantage that they are particularly weak or brittle. The most commonly used polymer gel is obtained by crosslinking between polymer chains using an organic crosslinking agent or by irradiating γ rays or electron beams. For example, a polymer gel known as a superabsorbent resin is used. Known are cross-linked sodium acrylate, poly (N, N-dimethylacrylamide) gel obtained by crosslinking with N, N′methylenebisacrylamide, and the like. However, these polymer gels (hereinafter abbreviated as organic cross-linked polymer gels) have only very low mechanical properties, and all have the problem of brittle fracture with weak force due to stretching of about 10 to 40%. .

  In contrast, amide group-containing polymers such as poly (N-isopropylacrylamide) (hereinafter abbreviated as PNIPA) and poly (N, N-dimethylacrylamide) (hereinafter abbreviated as PDMAA) and clays such as hectorite. Polymer gels obtained by complexing minerals at the nm level to form a three-dimensional network may exhibit excellent mechanical properties and functionality (such as stimulus responsiveness) as well as excellent transparency and high swellability. It has been reported (Patent Documents 1 and 2). For example, it has been reported that a polymer gel composed of PDMAA and a clay mineral exhibits excellent mechanical properties having a break elongation exceeding 1500% and a high break strength as well as excellent transparency and high swellability (Non-Patent Document). 1). The polymer gel composed of PNIPA and clay mineral has excellent mechanical properties including elongation at break of around 1000%, excellent transparency, and high swellability, as well as excellent functionality such as rapid swelling / contraction due to temperature changes. (Non-Patent Documents 2 and 3). From the above, polymer gels in which amide group-containing polymers and clay minerals form a three-dimensional network are used effectively in many industrial fields due to their excellent transparency, swelling, mechanical properties, and functionality. Is expected to be.

  However, since such a polymer gel has water or a water-soluble solvent as a main constituent, it has been difficult to change its physical properties greatly upon drying. In addition, using the polymer gel's ability to retain the solvent, if the target to which the polymer gel is applied is kept in a wet state, or if an unnecessary solution from the target is absorbed, further from the gel sheet In applications such as when releasing effective solutes as needed, it has been strongly required to prevent drying for a long period of time while maintaining the excellent physical properties of the polymer gel such as transparency and flexibility.

JP 2002-53629 A JP 2005-110604 A Kazutoshi Haraguchi, Robin Aarnworth, Akira Ohbayashi, Toru Takehisa, Macromolecules, vol.36, No.15, 5732-5741 (2003). Kazutoshi Haraguchi, Toru Takehisa, Advanced Materials, vol.14, No.16, 1120-1124 (2002). Kazutoshi Haraguchi, Toru Takehisa, Simon Fan, Macromolecules, vol.35, No.27, 10162-10171 (2002).

  The problem to be solved by the present invention is a polymer gel laminate capable of preventing the drying of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and a clay mineral, and a method for producing the same. Is to provide.

  As a result of diligent research to solve the above-mentioned problems, the present inventor has found that a layer composed of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and a clay mineral, and a moisture impermeable property. It has been found that a polymer gel can be used while ensuring excellent physical properties of the polymer gel by a laminate in which layers made of flexible members are laminated, and the present invention has been completed.

That is, the present invention includes a layer made of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and clay mineral, water vapor ^{permeability, 100g / m 2 / 24hr ·} 100μm or less flexible The present invention provides a polymer gel laminate having a laminate structure with layers made of members.

  The polymer gel laminate obtained by the present invention includes a layer made of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and a clay mineral, and a layer made of a moisture-impermeable flexible member. And the inherent properties of the polymer gel (transparency, flexibility, high toughness, wettability, swelling, absorption, solute release, impact resistance, temperature response, etc.) The effect can be exerted on the object and the effect lasts for a long time.

  Furthermore, it is possible to appropriately design a polymer gel laminate having various physical properties by applying a flexible member having transparency, reversible stretchability, or flexibility depending on the application to be used. .

  In the polymer gel laminate obtained in the present invention, a layer composed of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and a clay mineral and a layer composed of a flexible member are laminated. Is.

[Polymer gel]
The amide group-containing polymer forming the polymer gel is obtained by polymerizing an amide group-containing vinyl monomer having a property of being dissolved in water as a main component, and the resulting amide group-containing polymer is dissolved in water or Those that swell are particularly preferred.

  Specific examples of amide group-containing vinyl monomers for obtaining amide group-containing polymers include amides such as N-alkylacrylamide, N, N-dialkylacrylamide, N-alkylmethacrylamide, N, N-dialkylmethacrylamide, and acrylamide. One type or two or more types of monomers selected from group-containing vinyl monomers may be mentioned. For example, N-methylacrylamide, N-ethylacrylamide, N-cyclopropylacrylamide, N-isopropylacrylamide, methacrylamide, N-methylmethacrylamide, N-cyclopropylmethacrylamide, N-isopropylmethacrylamide, N, N-dimethyl Acrylamide, N, N-dimethylaminopropylacrylamide, N-methyl-N-ethylacrylamide, N-methyl-N-isopropylacrylamide, N-methyl-Nn-propylacrylamide, N, N-diethylacrylamide, N-acryloyl Examples include pyrrolidine, N-acryloylmorpholine, N-acryloylpiperidine, N-acryloylmethylhomopiperazine, N-acryloylmethylpiperazine, acrylamide and the like. That.

  Further, the combined use of the amide group-containing vinyl monomer and other polymerizable monomers is possible as long as the polymer gel referred to in the present invention is formed. In particular, in order to improve the adhesion of the polymer gel, it is effective to use a polymerizable monomer containing a carboxylic group, an amino group, a hydroxyl group and the like together. In addition, a stimulus-responsive water-soluble polymer having a critical temperature showing a phase transition such as poly (N-isopropylacrylamide) or poly (N, N-diethylacrylamide) and changing the gel volume by external stimulus is Particularly preferably used.

  The clay mineral that forms the polymer gel is preferably a water-swellable clay mineral that has a charge on the surface and swells or dissociates in layers in water, and more preferably a single unit or multiple layers of small units. It is finely dispersed in water. Specific examples of preferable clay minerals include water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable saponite, and water-swellable synthetic mica.

  The amount of the amide group-containing polymer and the clay mineral that forms the polymer gel used in the present invention is not particularly limited as long as the amide group-containing polymer and the clay mineral can form a three-dimensional network. The mass ratio of the group-containing polymer compound is preferably 0.001 to 10, more preferably 0.05 to 5, particularly preferably 0.1 to 1.

  The polymer gel used in the present invention is a flexible and tough material that can realize excellent physical properties such as a tensile elastic modulus of 1 kPa or more, a tensile strength of 20 kPa or more, and a breaking elongation of 50% or more, preferably tensile elasticity. The tensile strength is 50 kPa or more, the breaking elongation is 50% or more, more preferably the tensile elastic modulus is 10 kPa or more, the tensile strength is 80 kPa or more, and the breaking elongation is 100% or more. Particularly preferably, the tensile elastic modulus is 10 kPa or more, the tensile strength is 80 kPa or more, and the elongation at break is 300% or more. In addition, although the upper limit is not particularly limited for these physical properties, in applications where various deformations are assumed, those having a sufficient softness and a tensile elastic modulus of 100 kPa or less are particularly suitable.

  The polymer gel used in the present invention exhibits good mechanical properties against other mechanical deformations, and has excellent toughness, for example, even against large compression, tension or bending deformation. Specifically, a polymer gel whose shape is not destroyed even when it is compressed and deformed to a thickness of 1/3 or less in the thickness direction compared to the original polymer gel, or an angle of 100 degrees or more at the center point of the length Even if it is bent and deformed, it can be a polymer gel whose shape is not destroyed.

  The polymer gel used in the present invention can be highly transparent. The degree of transparency varies depending on the amount ratio of the clay mineral to the amide group-containing polymer compound, the water content, and the like. The degree is preferably such that when the thickness of the polymer gel is 2 mm, the visible light transmittance at a wavelength of 600 nm in the thickness direction is 70% or more, more preferably 80%. The above-described ones are particularly preferably 90% or more.

  The polymer gel used in the present invention contains a solvent in its three-dimensional network. As the solvent, water, an organic solvent miscible with water, or a mixed solvent thereof is used. Water or a solvent containing water as a main component is preferable.

  In the present invention, the amount of water or solvent contained in the polymer gel is set according to the purpose and is not generally defined, but preferably the amide group-containing polymer compound in the polymer gel and the water-swellable clay mineral. Although the thing whose mass ratio of water or a solvent with respect to a total mass is about 300 can be obtained, in order to obtain the above suitable physical properties, it is preferable to make this mass ratio into 50 or less, 30 is more preferable.

  As described above, the polymer gel used in the present invention exhibits excellent transparency, swellability, absorptivity, and mechanical properties (flexibility, high toughness, high extensibility, and compression resistance). Depending on the intended use, it can be appropriately adjusted to the required properties.

  The production method for obtaining the polymer gel in the present invention is carried out by a polymerization reaction of an amide group-containing monomer in the presence of a clay mineral. The polymerization reaction can be performed by radical polymerization using a conventional method such as the presence of a radical polymerization initiator, heating, or ultraviolet irradiation.

  Specifically, first, after preparing a uniform dispersion containing an amide group-containing monomer, a clay mineral, and water, a polymer gel is prepared by polymerizing the amide group-containing monomer in the presence of the clay mineral. Here, a polymer gel in which a three-dimensional network of an amide group-containing monomer polymer and a clay mineral is formed is obtained by the clay mineral exfoliated in a layer form acting as a crosslinking agent. Since the polymer gel has the three-dimensional network structure formed as described above, it can hold water or water and an aqueous solution therein, and has the above-described excellent physical properties.

  The radical polymerization initiator and the polymerization accelerator can be appropriately selected from conventional radical polymerization initiators and polymerization accelerators, preferably have water dispersibility and are uniformly contained in the entire system. Things can be used. Particularly preferred is a radical polymerization initiator having a strong interaction with the layered clay mineral. Specifically, water-soluble peroxides such as potassium peroxodisulfate, ammonium peroxodisulfate, and water-soluble azo compounds can be preferably used. As the water-soluble azo compound, VA-044, V-50, V-501 and the like manufactured by Wako Pure Chemical Industries, Ltd. can be preferably used. In addition, a water-soluble radical initiator having a polyethylene oxide chain can also be used. As the polymerization accelerator, tertiary amine compounds such as N, N, N ′, N′-tetramethylethylenediamine and β-dimethylaminopropionitrile can be preferably used.

  What is necessary is just to select suitably the temperature at the time of the said polymerization reaction according to the kind of amide group containing monomer to be used, a polymerization accelerator, an initiator, etc., for example, it can set it to the range of 0 to 100 degreeC.

  The polymerization time varies depending on polymerization conditions such as a polymerization accelerator, an initiator, a polymerization temperature, and a polymerization solution amount (thickness) and cannot be generally defined, but generally may be adjusted between several tens of seconds to several tens of hours.

  In order to improve the properties of the polymer gel of the present invention, a part of the amide group-containing polymer compound in the polymer gel can be crosslinked by a covalent bond. The shape stability is improved by covalently bonding a part of the amide group-containing polymer compound in the polymer gel. Examples of the method of cross-linking a part of the amide group-containing polymer compound by covalent bond include a method of irradiating the polymer gel with radiation to covalently bond the amide group-containing polymer compound to each other.

[Flexible member]
In the present invention, the water vapor permeability, a layer of a flexible member of 100g / m 2 / 24hr ^· 100μm or less moisture-impermeable, by laminating a layer made of a polymer gel, a polymer gel It is possible to prevent the volatilization of a solvent such as water or an organic solvent from the layer, and to maximize the excellent characteristics of the polymer gel.

  In addition, by appropriately selecting a flexible member to be used, it is possible to appropriately design a laminate having characteristics according to various uses. The polymer gel used in the present invention is excellent in toughness, stretchability, elasticity and the like. However, when the shape stability is required or the bending property is maintained, the extensibility is preferably 50. %, More preferably 100% or more, particularly preferably 300% or more, or those having a tensile elastic modulus of preferably 100 kPa or less, more preferably 50 kPa or less, particularly preferably 10 kPa or less.

  Furthermore, since the polymer gel used in the present invention is excellent in transparency, the visible light transmittance of 600 nm wavelength in the thickness direction at a thickness of 100 μm is preferably 50 as a flexible member. % Or more, particularly preferably 70% or more, more preferably 80% or more, by making use of the transparency of the polymer gel, and suitably observing changes over time of the object to be applied. Can do.

  Such a flexible member is not particularly limited as long as it has flexibility for securing the physical properties of the polymer gel and moisture permeability that prevents volatilization of the solvent for a long time. Specifically, polyurethane, polyester, polyolefin, polyamide, and elastomers thereof, silicon rubber, natural rubber and the like can be mentioned.

[Polymer gel laminate]
The polymer gel laminate of the present invention is obtained by laminating a layer made of the above polymer gel and a layer made of a flexible member, and the shape of these layers is a sheet shape, a film shape, a plate shape, Various shapes such as a cylindrical shape can be taken. The thickness of the layer made of a flexible member is not limited by the moisture impermeableness, transparency, and mechanical properties of the film, but also changes depending on the period of use of the polymer gel (allowable dryness), flexibility, transparency, etc. However, it is preferably 1 to 500 μm, more preferably 5 to 300 μm, and particularly preferably 20 to 100 μm.

  Moreover, even if only one surface of the layer made of the polymer gel is laminated with the layer made of the flexible member, the layer made of the flexible member is laminated on both surfaces. Also good. Furthermore, these layers may be laminated in a plurality of layers.

  In the polymer gel laminate of the present invention, when only one side of the layer made of the polymer gel is laminated with the layer made of the flexible member, the other side is used from the viewpoint of handleability and preservability before use. The surface is preferably combined with a moisture-proof release film. The release film may be not particularly transparent, and the degree of flexibility can be arbitrarily selected from use and storage properties.

  The method of laminating the layer made of the polymer gel and the layer made of the flexible member in the present invention is not necessarily limited as long as it is in close contact, but specifically, it is a sheet or film prepared separately from each material. A method of adhering two layers with an adhesive, a method of stitching them together, a method of mechanically pressing them together, or a method in which one layer is produced and then the other layer is directly polymerized and laminated on the layer , Etc. Here, the method of laminating a layer made of a polymer gel and a layer made of a flexible member without an adhesive is preferable because an adhesive that affects the physical properties of the laminate is not used. In particular, the method of directly polymerizing the other layer on one layer is more preferable because both layers can be firmly integrated.

  In the present invention, the following method is preferably used as a method of bonding the polymer gel and the flexible member without an adhesive. First, the surface of the flexible member is subjected to plasma treatment, and then a polymer gel reaction solution is introduced onto the surface to advance the polymerization reaction, thereby adhering the flexible member and the polymer gel. The polymer gel laminate in which the polymer gel is firmly adhered to the flexible member can be produced without using any material. Here, in order to increase the adhesive strength between the polymer gel and the flexible member, as a constituent of the polymer gel and / or the flexible member, a hydroxyl group, a carboxylic acid group, an amine, an alkoxysilyl group, an epoxy group, etc. It is effectively used to introduce.

  The plasma treatment method for the surface of the flexible member, which is used for bonding the polymer gel and the flexible member, is usually performed as a surface modification of the film, and is not particularly limited. The plasma output is 1 to 1000 W, the oscillation frequency is 1 MHz to 10 GHz, and the introduced gas is preferably a method such as air, oxygen, or argon. By performing under these conditions, it is possible to maintain the physical properties of the flexible member that adheres to the polymer gel.

  The polymer gel laminate of the present invention is preferably a laminate using a sheet-like polymer gel, so that the laminate has flexibility, and the object and the polymer gel are easily brought into contact with each other. Observation of changes over time of the object, protection of the object from external impacts, maintenance of the wet environment of the object, absorption of excess moisture and solution from the object, and release of solute to the object can be effectively performed.

  The polymer gel laminate having such characteristics can retain the chemical solution in the polymer gel layer for a long period of time, and has a high ability to absorb exudate, and the shape can be stably maintained even after the exudate is absorbed. Therefore, it is extremely useful as a wound dressing that can be used continuously on the wound surface for a long period of time. Moreover, what has transparency can observe the degree of healing in the state affixed on the wound surface. In addition, it is excellent in flexibility and can be applied to uneven wound surfaces, and particularly applicable to joints and positions where vibrations and impacts are imposed by movement.

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

(Production Example 1)
As the clay mineral, a water-swellable synthetic hectorite (“Laponite XLG” manufactured by Rockwood Ltd.) having a composition of [Mg _5.34 Li _0.66 Si ₈ O ₂₀ (OH) ₄ ] Na ⁺ _0.66 , The organic monomer was used after purifying N, N-dimethylacrylamide (manufactured by Kojin Co., Ltd .: hereinafter abbreviated as DMAA). The polymerization initiator was potassium peroxodisulfate (manufactured by Kanto Chemical Co., Inc .: hereinafter abbreviated as KPS), and the polymerization accelerator was N, N, N ′, N′-tetramethylethylenediamine (Wako Pure Chemical Industries, Ltd.). Manufactured: hereinafter abbreviated as TEMED.). All of the ultrapure water was used after removing oxygen contained by nitrogen bubbling or the like.

  To a flat bottom glass container, 57.06 g of ultrapure water, 2.4 g of Laponite XLG and 5.94 g of DMAA were added to obtain a colorless transparent solution. In addition, KPS and TEMED were added. This solution was transferred to a press-fitting container having a thickness of 2 mm, a length of 100 mm, and a width of 100 mm so as not to be exposed to oxygen, then sealed, and allowed to stand in a constant temperature water bath at 20 ° C. for 20 hours for polymerization. These operations were performed with oxygen shut off. Twenty hours after the start of polymerization, a sheet-like polymer gel (A) having a uniform thickness of 2 mm was obtained in the press-fitting container.

  Thermogravimetric analysis (TG-DTA220 manufactured by Seiko Denshi Kogyo Co., Ltd .: room temperature to 600 ° C.), Fourier transform infrared absorption spectrum measurement (Fourier transform infrared spectrophotometer FT / manufactured by JASCO Corporation) IR-550), by dry weight measurement, 99.5% or more of the monomer (DMAA) was polymerized, and it was confirmed to be a polymer gel containing clay mineral (Laponite XLG) in almost the same proportion as the initial reaction solution. . Wide-angle X-ray diffraction (Science Instruments: X-ray diffractometer RINTULTIMA) and transmission electron microscope observation (JEOL Ltd. JEM-200CX: acceleration voltage 100 KV) cause the clay mineral to delaminate inside the gel and become molecular It was confirmed that it was dispersed. In addition, it was confirmed that by immersing the dried polymer gel in water at 20 ° C., the polymer gel absorbs water and returns to an elastic gel having the same shape as before drying. , N-dimethylacrylamide) and clay were confirmed to form a three-dimensional network structure.

  The sheet-like polymer gel (A) thus obtained is cut into a size of 1 cm × 5 cm, and a tensile test device (manufactured by Shimadzu Corporation, desktop type universal test is made so as not to slip on the chuck portion. Machine AGS-H), and a tensile test was performed at a distance of 30 mm between the scores and a pulling speed of 100 mm / min. As a result, the tensile strength was 85 kPa, the elongation at break was 1520%, the elastic modulus was 5.2 kPa, and it was confirmed that both had softness and toughness.

  Further, the sheet-shaped polymer gel (A) is fixed in an ultraviolet-visible spectrophotometer (V-530 manufactured by JASCO Corporation), and the light transmittance in the thickness direction of the sheet-shaped polymer gel (A) is measured. Went. As a result, it was confirmed that the light transmittance was 92% at a wavelength of 600 nm.

  This sheet-shaped polymer gel (A) was cut into a size of 2 cm × 2 cm to obtain a sheet-shaped polymer gel (B). Next, 20 degreeC distilled water was put into a 100 ml container, and the sheet-like polymer gel (B) was carefully put in it, stirring slowly. Thereafter, while keeping the temperature of the distilled water at 20 ° C., the sheet-like polymer gel (B) was sometimes taken out and weighed. Ten days after the start of measurement, the weight became almost constant and reached equilibrium swelling. At this time, the mass ratio of water to the total mass of the amide group-containing polymer and clay mineral contained in the sheet-like gel was 250.

Example 1
Size of 5 cm × 10 cm in thickness 30μm of polyurethane film (visible light transmittance: 70%, water vapor transmission ^{rate: 56g / m 2 / 24hr ·} 100μm) (T-6085, manufactured by DIC-Bayer Polymer Ltd.) Was put in a chamber of a plasma processing apparatus (PR31, manufactured by Yamato Kagaku) and subjected to plasma processing. The processing conditions were an output of 60 W, an oscillation frequency of 18.53 MHz, an introduced gas: argon, and plasma irradiation was performed for 5 minutes. After the plasma treatment, the polyurethane film was laid so that no gap was formed on the inner bottom surface of the same press-fitting container as used in Production Example 1. Using a press-fit container with this polyurethane film laid on the bottom, a sheet-like polymer gel was prepared on the polyurethane film in the same manner as in Production Example 1, and a urethane film layer and a polymer gel layer were laminated. A polymer gel laminate (1) was obtained. The polymer gel layer in the obtained polymer gel laminate (1) and the plasma-treated polyurethane film layer were not easily peeled off and were firmly bonded. The obtained polymer gel laminate (1) can be stretched by 300% or more, and immediately recovered to its original shape after stretching.

  When the light transmittance of the obtained polymer gel laminate (1) was measured by the same method as in Production Example 1, the light transmittance at 600 nm wavelength was 80%, and the polyurethane film and the polymer gel were laminated. As a result, a higher value than the light transmittance of the polyurethane film alone was obtained. Next, the moisture drying time of the polymer gel laminate (1) was measured. When the polyurethane film layer of the polymer gel laminate (1) cut into 3 cm × 3 cm is faced up and placed on a polypropylene tray and left to stand in an atmosphere at 25 ° C., the weight change was observed. While the water content of the polymer gel layer of the molecular gel laminate (1) was 88%, the water content after 24 hours from the start of measurement was 80%, and the water content was 50% even after 100 hours from the start of measurement. Yes, the water content was kept sufficiently flexible.

  Furthermore, the solvent absorption test of the polymer gel laminated body (1) was conducted. As the solvent, ultrapure water, physiological saline and bovine plasma were used. Place a polymer gel laminate (1) of 5 cm x 5 cm on an acrylic plate with holes of 2 cm x 2 cm so that the polymer gel layer is in contact with each solvent and polymer gel from the bottom of the hole. The laminate (1) was brought into contact. Each solvent was appropriately supplied so that contact between the solvent and the gel could be continuously performed by absorption of the sheet-like gel. The measurement was performed in an atmosphere at 25 ° C., and the weight of the polymer gel laminate (1) was appropriately measured. As a result, with respect to the original weight of the polymer gel laminate (1), the change in weight with respect to each solvent 4 hours after the start of measurement was 1.3, 1. 2 and 1.15 times, and 1.8 hours, 1.5 times and 1.3 times after 12 hours from the start of measurement, respectively, and the polymer gel laminate (1) absorbs each solvent, It was confirmed that it increased over time.

(Example 2)
A polymer gel laminate (2) was produced in the same manner as in Example 1 except that a polyurethane film having a thickness of 60 μm was used.

The resulting polymer gel laminate (2) is on a surface opposite to the side which is laminated with a polyurethane film, a polyester film water vapor transmission rate of ^{6.9g / m 2 / 24hr · 100μm} ( trade name: Lumirror S10, manufactured by Toray Industries, Inc.) was laminated to obtain a polymer gel laminate (2 ′). This polymer gel laminate (2 ′) was very easy to handle because both surfaces of the laminate were laminated with a polyurethane film and a polyester film.

  When the light transmittance of the polymer gel laminate (2 ″) obtained by releasing the polyester film laminated on the polymer gel laminate (2 ′) was measured by the same method as in Production Example 1, the wavelength was 600 nm. The light transmittance was 66%, which was higher than the light transmittance (60%) of the polyurethane film alone. Next, when the moisture drying time of the polymer gel laminate (2 ″) was measured in the same manner as in Example 1, the polymer gel portion of the polymer gel laminate (2 ″) before measurement was measured. However, the moisture content of the sheet-like gel was only slightly reduced to 85% after 24 hours from the start of measurement, and the moisture content was 70% even after 100 hours from the start of measurement. The water content was kept flexible.

  Furthermore, when the absorption test with respect to the solvent was conducted using the polymer gel laminate (2 ″) in the same manner as in Example 1, the polymer gel laminate (2 ″) was compared with the original weight. The change in weight with respect to each solvent 4 hours after the start of measurement is 1.3, 1.2, and 1.15 times for water, physiological saline, and bovine plasma, respectively. The solvent absorption capacity of the polymer gel laminate (2 ″) was 1.8, 1.5, and 1.3 times, and was the same as that of the polymer gel laminate (1).

(Example 3)
A polyurethane film similar to that used in Example 1 is placed on the surface of the sheet-like gel (A) obtained in Production Example 1, and the entire gel end and polyurethane film are placed using a medical silk suture. The polymer gel laminate (3) was obtained by sewing. In the obtained polymer gel laminate (2), the polymer gel layer and the polyurethane film layer are not adhered, but one surface of the polymer gel layer is covered with the polyurethane film and is easily covered. It did not peel off.

  When the light transmittance of the obtained polymer gel laminate (3) was measured in the same manner as in Production Example 1, the light transmittance at a wavelength of 600 nm was 70%, and the light transmittance of the polyurethane film alone was measured. The rate was almost the same. Next, when the moisture drying time of the polymer gel laminate (3) was measured in the same manner as in Example 1, the moisture content of the polymer gel layer portion of the polymer gel laminate (3) before the measurement was measured. Was 88%, but the water content after 24 hours from the start of measurement was 77%, a decrease of about 10%, and the water content was 45% even after 100 hours from the start of measurement. The moisture content to keep was maintained.

  Furthermore, when a solvent absorption test was performed using the polymer gel laminate (3) in the same manner as in Example 1, the measurement was started 4 with respect to the original weight of the polymer gel laminate (3). The change in weight with respect to each solvent after time is 1.3, 1.2, and 1.15 times for water, physiological saline, and bovine plasma, respectively, and 1.8 hours after 12 hours from the start of measurement. It was 1.5 and 1.3 times, and it was confirmed that each solvent absorption capacity of the polymer gel laminate (3) was the same as that of the sheet gel (B).

Example 4
When the sheet-like polymer gel (A) obtained in Production Example 1 was placed on a transparent polystyrene container and allowed to stand in an atmosphere at 25 ° C., the moisture content was 88% before standing, and the standing was 2 After a time, it became 70%, and the water content decreased slightly. A polyurethane film for medical use with an adhesive on the upper surface of this slightly low water content sheet-like polymer gel (A ′) (trade name: Biocrucible, manufactured by Johnson & Johnson Co., Ltd., visible light transmittance 70%, thickness 45 μm) was affixed to obtain a polymer gel laminate (4). The obtained polymer gel laminate (4) was fixed without a gap by a polyurethane film, and was in close contact with a polystyrene container.

  When the light transmittance of the polymer gel laminate (4) thus obtained was measured in the same manner as in Production Example 1 while placed on a polystyrene container, the light transmittance at a wavelength of 600 nm was 75%. A value higher than the light transmittance of the polyurethane film alone was obtained. Next, when the moisture drying time of the polymer gel laminate (4) covered with the polyurethane film was measured in the same manner as in Example 1, the polymer of the polymer gel laminate (4) before measurement was measured. While the moisture content of the gel part was 70%, the moisture content of the sheet-like polymer gel was 64%, which is a decrease of less than 10% after 24 hours from the start of measurement. The rate was 50%, and the moisture content was maintained sufficiently flexible.

  Furthermore, when the absorption test with respect to the solvent was conducted using the polymer gel laminate (4) in the same manner as in Example 1, the measurement was started 4 with respect to the original weight of the polymer gel laminate (4). The change in weight with respect to each solvent after time is 1.3, 1.2, and 1.15 times for water, physiological saline, and bovine plasma, respectively, and 1.8 hours after 12 hours from the start of measurement. It was 1.5 and 1.3 times, and it was confirmed that each solvent absorption capacity of the polymer gel laminate (4) was not different from that of the sheet gel (B).

(Comparative example)
When the moisture drying time of the sheet gel (A) was measured in the same manner as in Example 1 using the sheet gel (A) obtained in Production Example 1 and not coated with the polyurethane film, The water content of the sheet gel (A) before the measurement was 88%, whereas the water content of the sheet gel was 10% after 24 hours from the start of the measurement. As a result, flexibility and functionality have been lost.

Claims (11)

A layer made of a polymer gel having a three-dimensional network structure composed of an amide group-containing polymer and clay mineral, water vapor permeability, a layer consisting of a flexible member 100g / m 2 / 24hr ^· 100μm A polymer gel laminate having the laminate structure of 2. The polymer gel laminate according to claim 1, wherein a visible light transmittance of a wavelength of 600 nm in a thickness direction at a thickness of 100 μm of the flexible member is 50% or more. The polymer gel laminate according to claim 1, wherein the flexible member has reversible stretchability. The polymer gel laminate according to claim 1, wherein the flexible member has a tensile elastic modulus of 100 kPa or less. 5. The polymer gel according to claim 1, wherein the polymer gel has a tensile elastic modulus of 5 kPa or more, a tensile strength of 50 kPa or more, and a breaking elongation of 100% or more under the condition of a solvent content of 90%. The polymer gel laminate described. The amide group-containing polymer is at least one monomer selected from the group consisting of N-substituted acrylamide derivatives, N, N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, or N, N-disubstituted methacrylamide derivatives. The polymer gel laminate according to any one of claims 1 to 5, which comprises: The clay mineral is at least one selected from the group consisting of water-swellable hectorite, water-swellable montmorillonite, water-swellable saponite, or water-swellable synthetic mica. The polymer gel laminate described. The polymer gel composite according to any one of claims 1 to 7, wherein the polymer hydrogel is obtained by polymerizing a water-soluble organic monomer in the presence of a clay mineral uniformly dispersed in water. The polymer gel composite according to any one of claims 1 to 8, which has a moisture-proof release film on the surface of the layer made of the polymer gel. The surface of the layer made of the flexible member is subjected to plasma treatment, and then a dispersion containing an amide group-containing monomer, a clay mineral, and water is applied on the surface, and the amide group-containing monomer is polymerized in the presence of the clay mineral. A method for producing a polymer gel laminate, comprising a step of laminating a layer made of a polymer gel on the surface of a layer made of a flexible member. The polymer gel laminate according to claim 10, wherein the layer made of the flexible member has at least one group selected from the group consisting of a hydroxyl group, a carboxylic acid group, an amine, an alkoxysilyl group, or an epoxy group on the surface thereof. Body manufacturing method.