JP2010006855A - Method of adhering ionic gel to substrate and method of adhering ionic gel laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of adhering ionic gel to a substrate, and to provide a method of adhering an ionic gel laminate laminated on a substrate. <P>SOLUTION: When adhering the anionic gel to the substrate, anionic fine particles are interposed for the gel containing cationic groups and cationic fine particles are interposed for the gel containing anionic groups and, thereby, the gel can be adhered to the substrate. Further, with respect to the ionic gel laminate prepared by forming the gel on the substrate, the anionic fine particles are interposed between the cationic gels, and the cationic fine particles are interposed between the anionic gels and, thereby, the gel laminates can be adhered to each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to a cross-linked network body that is chemically or physically cross-linked and mainly composed of organic components, that is, a method for adhering a gel to a base material, and a gel surface of a gel laminate comprising a gel and a base material. Regarding the method.

A gel is defined as “a polymer having a three-dimensional network structure that is insoluble in any solvent and its swollen body” (New Edition Dictionary of Polymers (1988)). Among them, a gel that absorbs a large amount of solvent has a property between liquid and solid, and stably incorporates the solvent into a three-dimensional network such as an organic polymer. In particular, gels that use water as a solvent (hereinafter referred to as hydrogels or aqueous gels) are important constituent materials in living organisms. So far, hygiene products, daily necessities, daily necessities, food / packaging, medical medicine, agriculture / horticulture, civil engineering -Widely used in many industrial fields such as architecture, chemical industry, electronic / electric industry, sports and leisure industry (Non-Patent Document 1). Contact lens and diaper absorbents are examples.

  Hydrogel is mainly composed of two kinds of components. One is a three-dimensional network bridged in various ways and the other is water. As a constituent component of the three-dimensional network, either an organic compound or an inorganic compound can be used. In organic compound hydrogels, organic polymers or organic molecules are crosslinked by covalent bonds, hydrogen bonds, ionic bonds, coordination bonds, hydrophobic bonds, or the like, or a physical entanglement or microcrystal is used as a crosslinking point to form a three-dimensional network. Forming.

  Specifically, as an organic molecule that forms a three-dimensional network, a cross-link is formed by a coordinate bond with ovalbumin or serum albumin that is cross-linked by a hydrophobic bond, gelatin or agarose by a helix formation, or an alkaline earth metal ion. In addition to polyacrylic acid, polystyrene sulfonic acid, two types of polymer (polycation and polyanion) cross-linked by ionic bond, fully saponified polyvinyl alcohol cross-linked by hydrogen bond, heat, radiation, light, electron beam, It is known that a covalent bond is formed between organic polymers by plasma irradiation and addition of an organic crosslinking agent.

  On the other hand, as an inorganic substance that forms a three-dimensional network, metal oxides prepared by hydrolysis polycondensation of metal alkoxides (so-called sol-gel reaction) and layered clay minerals having cations between layers are known.

  Inorganic hydrogels are brittle with small strength and elongation, and are therefore rarely used as a single hydrogel material. In contrast, hydrogels composed of organic compounds, especially organic polymer 3D networks and water, such as covalent bonds, are expected to have good mechanical properties, biocompatibility, and high environmental compatibility. Therefore, applications are being developed in a wide range of industrial fields as soft materials and functional gel materials.

  In order to further expand the usefulness of such an organic crosslinked hydrogel, it is important to improve the molding processability of the gel. If gels can be bonded freely, obtain a free shape, or combine two different types of gels, and combine multiple layers of gels to create gel gradient materials and functional materials. It is possible that the usefulness of the gel is further improved.

  However, adhesion of gels, particularly hydrogels containing a large amount of water, is not easy. Saito et al. Of Hokkaido University have found that it is difficult to bond a once cut gel with a so-called adhesive, etc., so that two gel slices are impregnated with a reactive monomer and polymerized. Gel adhesion was achieved by forming another network between the sections. (Non-Patent Document 2) However, this method is complicated and time-consuming. Tamagawa et al. (Gifu University) that hydrogels containing cationic groups and anionic groups, that is, polyelectrolytes, can be bonded using the ion pair effect between polycations and polyanions under limited conditions. And GMSpinks et al. Of Wollongong University, Australia (Non-Patent Document 4). However, these are possible phenomena under the restriction between polycation and polyanion. For example, it is not possible to cut and bond the same gel.

Also, it is difficult to adhere the gel to the substrate, particularly to adhere a hydrogel containing a large amount of water to a nonwoven fabric having a hydrophobic surface. If the gel can be strongly adhered to the substrate, the properties derived from the substrate (durability, impact resistance, wettability, swelling, absorbability, stretchability, etc.) can be imparted to the gel properties, and the ionic gel with various physical properties A laminated body can be designed appropriately. For example, when the base material is non-woven fabric, it can be applied to biocompatible materials and sanitary materials. When the base material is paper, it can be applied to adhesive (or pseudo-adhesive) materials, packaging materials, environmentally compatible materials, etc. Is possible. In addition, it is possible to obtain a laminated composite gel laminate, and it is considered that the possibilities of gel use are widened.
Yoshida Nagata, Satoshi Sugawara "Gel Handbook" Part 3 Application Edition NTS Corporation, 1997 Junji Saito et al. Proceedings of the 17th Polymer Gel Research Conference November 8, 2006 Hirohisa Tamagawa et al. Bull. Chem. Soc. Jpn., 2002, 75, 383 GM Spinks, ACS Polymer Preprints 2007, 48 (1), 645

  The problems to be solved by the present invention are to provide a means for adhering a gel to a base material, and to a gel laminate in which a gel is formed on a base material. With respect to adhesion, it is an object to provide a means for adhering a completely new gel, which enables adhesion between gels very easily and effectively.

  As a result of diligent research to solve the above-mentioned problems, the inventors of the present invention have introduced a cationic group into a gel containing anionic fine particles and a gel containing an anionic group. Found a method that enables adhesion of the gel to the substrate by interposing cationic fine particles. Further, the same ion can be obtained by interposing anionic fine particles to the cationic gel laminate laminated on the base material, and by interposing cationic fine particles to the anionic gel laminate. The present inventors have found a method that enables adhesion between gels of a conductive gel laminate and completed the present invention.

  That is, the present invention is a bonding method and a laminate of a substrate and an ionic gel described in the following (1) to (5), and an ionic gel described in the following (6) to (10): It is the adhesion method of a laminated body, and a laminated body.

(1) A method for adhering a base material and an ionic gel, wherein anionic fine particles are interposed between a gel containing a cationic group as a constituent component and the base material, and an anionic group is contained as a constituent component. A method for adhering a base material and an ionic gel, characterized in that cationic fine particles are interposed between the gel and the base material.
(2) The bonding method according to claim 1, wherein the gel is a hydrogel containing water.
(3) The adhesion method according to (1) or (2), wherein the average particle size of the anionic fine particles and the cationic fine particles is 1 nm or more and 10,000 nm or less.
(4) The bonding method according to any one of (1) to (3), wherein the substrate is paper, nonwoven fabric, or cloth.
(5) An ionic gel laminate produced using the bonding method according to any one of (1) to (4) above.

(6) A method of adhering gel surfaces of an ionic gel laminate in which an ionic gel is laminated on a base material, and for a cationic gel laminate in which a gel containing a cationic group as a constituent component is formed. In addition, for an anionic gel laminate containing an anionic group as a constituent component, an anionic gel laminate is provided by interposing a cationic fine particle between the gels. A method of bonding gel surfaces of each other.
(7) The adhesion method according to (6), wherein the gel is a hydrogel containing water.
(8) The bonding method according to (6) or (7), wherein the average particle size of the anionic fine particles and the cationic fine particles is from 1 nm to 10,000 nm.
(9) The adhesion method according to any one of (6) to (8), wherein the substrate is paper, nonwoven fabric or cloth.
(10) An ionic gel laminate produced using the bonding method according to any one of (6) to (9).

  According to the present invention, for example, after anion silica fine particles (anionic particles) dispersed in water on a base material (nonwoven fabric) are coated, a chemically crosslinked hydrogel containing a quaternary ammonium type cationic group as a constituent component is lightly pressure-bonded. Type hydrogel can be adhered to a substrate. On the other hand, for example, after applying alumina fine particles (cationic particles) dispersed in water to a base material (nonwoven fabric), a chemically crosslinked hydrogel containing a carboxy anion group as a constituent component is lightly pressure-bonded to adhere the anionic hydrogel to the base material. can do. As a result, properties derived from the base material (for example, durability, impact resistance, wettability, swelling, absorbency, stretchability, processability, formability, etc.) can be imparted to the gel properties, and ionic properties with various physical properties A gel laminated body can be designed suitably. For example, when the base material is cloth, application to biocompatible materials, sanitary materials, etc., and when the base material is paper, application to packaging materials, adhesive sheets, environmentally compatible materials, etc. can be considered. A laminated composite gel can also be easily obtained.

  Moreover, the laminated body obtained by this invention can also form the same ionic gel after apply | coating the microparticles | fine-particles with the same code | symbol on both surfaces of a base material. Furthermore, different ionic gels are formed on both sides, such as forming an anionic gel after applying cationic fine particles on one side of the substrate and forming a cationic gel after applying anionic fine particles to the other. You can also The laminate thus obtained becomes a functional material that bends due to, for example, a difference in swelling degree or external stimulation (pH, temperature, charge, hydrophilicity / hydrophobicity of a solvent).

  In addition, with regard to the ionic gel laminate formed from the base material and the ionic gel, anionic fine particles are interposed in the adhesion between the gel surfaces of the cationic gel laminate, and the cationic fine particles are attached to the anionic gel laminate. It can be easily bonded by interposing. Thereby, the application range is wide, such as making it possible to easily obtain a laminated composite gel while utilizing the characteristics derived from the substrate.

  The gel in the present invention refers to “a polymer having a three-dimensional network structure and a swollen body thereof”. That is, the three-dimensional network structure may be chemical crosslinking or physical crosslinking, and may be a polymer (swelling body) containing a solvent (for example, water or an organic solvent) or a polymer not containing it.

First, the inventions (1) to (5) of the present invention will be described. First, the ionic gel of the present invention will be described in the order of a cationic gel and an anionic gel.
A gel (cationic gel) containing a cationic group as a constituent component only needs to contain a cationic group as a constituent component, and the synthesis method is not limited. Most commonly, it has a polymerizable functional group in the molecule, such as a vinyl group, and primary, secondary, and tertiary amino groups (each protonated and used as an ammonium group) or quaternary ammonium in the same molecule A monomer containing a group can be reacted with a crosslinking agent that reacts with the monomer to cause a crosslinking reaction, together with a reaction initiator in a solvent (for example, water) or without a solvent, to obtain a chemically crosslinked gel. At this time, it is not necessary to use only one type of monomer having a cationic group, and two or more types may be used. In addition to the monomer having a cationic group and a crosslinking agent, neutral performance is exhibited over a wide range of conditions. A monomer or a monomer exhibiting anionic performance may be added if the amount is small.

  Examples of these amino-type or quaternary ammonium-type monomers include N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N-dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, allylamine, N-methylallylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylammonium hydrochloride, (3-acrylamidopropyl) trimethylammonium chloride, methacryloylcholine chloride, vinylpyridine and the like can be mentioned. Also included are monomers such as N-vinylformamide that can be converted into an amino group, a substituted amino group, or a quaternary ammonium group after the polymerization reaction.

  Examples of monomers exhibiting neutral performance include acrylamide and derivatives thereof such as acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, N, N-diethylacrylamide, N-hydroxyethylacrylamide, 2-hydroxyethyl methacrylate, 2 -Hydroxyethyl acrylate, hydroxypropyl acrylate, vinylpyrrolidone and the like can be mentioned.

Monomers that exhibit anionic performance include acrylic acid (an alkali metal salt thereof), 2-acrylamido-2-methylpropanesulfonic acid (an alkali metal salt thereof), methacrylic acid (an alkali metal salt thereof), vinylbenzenesulfonic acid ( Alkali metal salt), vinyl naphthalenesulfonic acid (alkali metal salt), and the like.
These monomers are dissolved in a necessary amount in a solvent (for example, water), and there are conventionally known N, N′-methylenebisacrylamide, N, N′-propylenebisacrylamide, di (acrylamidomethyl) ether, , 2-diacrylamide ethylene glycol, 1,3-diacryloyl ethylene urea, ethylene diacrylate, N, N′-bisacryl cystamine, and other bifunctional compounds, triallyl cyanurate, triallyl isocyanurate, etc. A predetermined amount of a functional compound is added, and a water-soluble peroxide such as potassium peroxodisulfate or ammonium peroxodisulfate, a water-soluble azo compound such as VA-044, V-50, V or V is used as an initiator for the polymerization reaction. -501 (both manufactured by Wako Pure Chemical Industries, Ltd.) are added and heated. Ri it is possible to obtain a desired gel. When a peroxide is used as an initiator, polymerization reaction is carried out with a tertiary amine compound such as N, N, N ′, N′-tetramethylethylenediamine or β-dimethylaminopropionitrile as a catalyst instead of heating. You can also start.

The polymerization temperature can be set in the range of 0 ° C. to 100 ° C. according to the type of polymerization catalyst and initiator. The polymerization time varies depending on the polymerization conditions such as the catalyst, initiator, polymerization temperature, and amount (thickness) of the polymerization solution, and can generally be carried out for several tens of seconds to several hours.
In addition to the above-mentioned radical polymerization by heat, photocrosslinking using photoinitiators, methods of obtaining gels by chemical crosslinking reactions such as radiation (gamma ray and electron beam) crosslinking and plasma crosslinking, IPN (interpenetrating polymer network) gels A cationic gel can be obtained by a known synthesis method such as a method of obtaining a gel by physical crosslinking such as a method of synthesizing a polymer (a gel can be obtained by impregnating a polymer with another component monomer and polymerizing). (Note that the same applies to the anionic gel described below).

Next, an anionic gel is demonstrated.
A gel containing an anionic group as a constituent component (anionic gel) is not limited in the gel synthesis method as long as the anionic group is contained in the constituent component. Most commonly, it reacts with a monomer having a polymerizable functional group in the molecule, such as a vinyl group, and containing an alkali metal base of an acid represented by carboxylic acid or sulfonic acid in the same molecule. It can be reacted with a crosslinking initiator that causes a crosslinking reaction in a solvent (for example, water) or in the absence of a solvent with a reaction initiator to obtain a chemically crosslinked gel. At this time, one type of monomer having an anionic group may be used, or two or more types may be used. In addition to a monomer having an anionic group and a crosslinking agent, a monomer that exhibits nonionicity in a wide range of conditions, If the amount is small, a cationic monomer or an amphoteric (zitter ion) type monomer may be added.
About the representative example of an anionic monomer, the representative example of a neutral monomer, and the representative example of a cationic monomer, the compound as described in the said cationic gel is mentioned.

  Next, the base material used for this invention is demonstrated. The “substrate” is not particularly limited, and examples thereof include paper, cardboard, wood, nonwoven fabric, woven fabric, net, plastic film, and metal plate. Although there is no restriction | limiting in particular as a raw material, Natural fiber, synthetic fibers, such as nylon, polyester, and polylactic acid, glass fiber, carbon fiber, etc. are mention | raise | lifted, such as pulp (cellulose), cotton, and wool. These fibers may contain a functional material (polymer or the like). A plastic film (synthetic resin sheet) and a metal plate are also included, but in order to improve the adhesion to the gel, conventional surface treatment or coating treatment of a polymer compound (gelatin or the like) is effective. These base materials may be coated with a polymer resin (for example, gelatin or the like) or a pigment (for example, a water-absorbing pigment) for giving affinity to the solvent used for the ionic fine particles.

  The “anionic fine particles” used for adhesion of the cationic gel of the present invention need to be stably dispersed in the same solvent or a mixed solvent contained in the gel with the surface charged anionic. . The average particle size is preferably from 1 nm to 10000 nm, particularly preferably from 1 nm to 100 nm.

  Specifically, from the standpoint of performance such as particle stability and uniformity, and because it is industrially manufactured in large quantities, it is easy to obtain and many types can be selected. In view of price, anionic silica is most preferable. More specifically, for example, the Snowtex series manufactured by Nissan Chemical Industries, Ltd. can be mentioned. In water dispersion, ST-XS (average particle size 4-6nm), ST-20 (average particle size 10-20nm), ST-20L (average particle size 40-50nm), ST-YL (average particle size 50- 80 nm) and ST-ZL (average grain size 70-100 nm). Among these, those having a smaller average grain size such as ST-XS and ST-20 tend to exhibit stronger adhesive strength.

  The anionic fine particles may coexist with the anionic polymer. The anionic polymer is obtained by polymerizing, for example, acrylic acid (alkali metal salt thereof), methacrylic acid (alkali metal salt thereof), vinylbenzenesulfonic acid (alkali metal salt thereof), or vinylnaphthalenesulfonic acid (alkali metal salt thereof). Examples include, but are not limited to polymers. Two or more types of polymers may be mixed, or a copolymer in which two or more types of anionic monomers and neutral monomers are mixed may be used. The anionic polymer can coexist as long as the properties of the anionic fine particles are not impaired. It is only necessary that the anionic fine particles can be brought into contact with the substrate or the surface of the cationic gel.

  Although the mechanism by which the cationic gel adheres to the substrate via the anionic fine particles is not completely understood, the anionic particles can penetrate into the unevenness of the substrate or fibers A physical adhesive effect that is entangled in the gel is expressed, and for gels, a large number of cationic groups existing in the vicinity of the interface of the gel and a large number of anionic groups on the fine particles distributed mainly around the interface Seems to be a dynamic interaction. Although it is not clear yet, it is considered that there is a relative optimum relationship between the size of the fine particles and the size of the gel network.

  Adhering a cationic gel to a substrate via anionic fine particles is easily expressed. After applying an appropriate amount of the anionic fine particle dispersion to the cationic gel, it may be lightly pressure-bonded to the substrate, or after applying an appropriate amount of the anionic fine particles to the substrate and then lightly pressure-bonded to the cationic gel, as soon as possible, as soon as possible In a few hours, the substrate and the gel adhere. When the adhesion is strong, the gel breaks down even if it is to be peeled off, and it is difficult to peel off the bonded surface. It is also possible to control the adhesive force by selecting the constituent components of the gel or selecting the anionic fine particles (particularly the particle diameter).

  The gel formed on the substrate via the particles of the present invention may be a gel laminate that is previously bonded to another substrate. For example, a cationic gel laminate laminated on paper can adhere the gel surface to another paper substrate via anionic particles. Since the strength of adhesion can be controlled by the gel structure and the selection of particles, it can be used as an adhesion (or pseudo-adhesion) sheet. Thus, application as an adhesive for paper products and packaging materials is conceivable.

Moreover, the ionic gel laminated body which adhere | attached the gel on the base material of this invention can also adhere | attach a gel surface to a base material, and can also sandwich a gel with two base materials.
In addition, the ionic laminate obtained by the present invention may have a gel formed on both sides as well as on one side of the substrate. The same ionic gel (however, the gel composition need not be exactly the same) can be formed after applying particles having the same sign of charge on both sides of the substrate. Furthermore, after applying cationic particles to one side of the substrate, an anionic gel is formed, and after applying anionic fine particles to the other side, a cationic gel is formed, so that different ionic gels are formed. It can also be formed.

  Although it is the concrete gel shape at the time of applying the bonding method of the present invention, the gel may be in any form such as a block shape, a sheet shape, a three-dimensional shape, a particle shape, and a fiber shape. Adhesion is performed by applying ionic fine particles in the form of a powder or dispersion on the surface of the gel (or base material) to be adhered, and press-bonding to the base material (or gel).

  A typical example of “cationic fine particles” used for adhesion of anionic gel in the present invention is alumina sol. More specifically, they are alumina sol 520 (average particle size 10-20 nm), alumina sol 100 (average particle size 10 × 100 nm) manufactured by Nissan Chemical Industries, Ltd. Further, silica having Al cation treatment on the surface can also be used. Specific examples thereof include Snowtex ST-AK (average particle diameter 10-20 nm) manufactured by Nissan Chemical Industries, Ltd.

Moreover, the cationic fine particles may coexist with the cationic polymer. Examples of the cationic polymer include N, N-dimethylaminoethyl acrylate, N, N-diethylaminoethyl acrylate, N, N, which are representative examples of the above-mentioned cationic monomers (the following are protonated and used as ammonium salts). -Dimethylaminopropyl acrylate, N, N-diethylaminopropyl acrylate, N, N-dimethylaminoethyl methacrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminopropyl methacrylate, N, N-diethylaminopropyl methacrylate, allylamine, N-methylallylamine, diallylamine, N-methyldiallylamine, N, N-dimethylallylammonium hydrochloride, (3-acrylamidopropyl) trimethylammonium chloride, methacryloylcholine chloride, vinylpyridine N, N-dimethylallyl Ammonium include polymers comprising hydrochloride (polymer) such as a polymerization component is not limited thereto. Two or more kinds or a copolymer mixed with a neutral monomer may be used.
The adhesion operation and the mechanism of the gel and the substrate are the same as in the case of adhering the cationic gel with anionic fine particles.

Subsequently, the inventions (6) to (10) of the present invention will be described. About materials, such as a cationic gel, an anionic gel, and a base material, it is the same as that of above-described invention (1)-(5).
The ionic gel laminate to be bonded in (6) to (10) of the present invention is obtained by laminating the cationic gel or anionic gel on a base material. The lamination form is arbitrary, and any one of those obtained by laminating one or both sides of an ionic gel with a substrate, those obtained by laminating both surfaces of a substrate with an ionic gel, and those obtained by further laminating them may be used. . Moreover, when laminating, it is laminated so that only a part of the ionic gel and the base material adheres, laminated so as to adhere at a plurality of points, or the hydrophilic treatment of the base material is changed. The adhesion state can be made different depending on the location. The amount of the solvent contained in the ionic gel laminate also varies depending on the composition or purpose.

There is no restriction | limiting in particular about the manufacturing method of the ionic gel laminated body used in (6)-(10) of this invention, ie, the method of laminating | stacking ionic gel on a base material. For example, a method in which the base material and the ionic gel are brought into contact with each other and lightly pressure-bonded can be mentioned. Further, a solvent can be evaporated from the laminate, and the gel can be adhered to the base material.
In addition, the same adjustment liquid (monomer, cross-linking agent, initiator, solvent, etc.) as in the method for synthesizing the cationic gel (or anionic gel) was repeatedly subjected to reduced pressure and nitrogen substitution, and then placed in a petri dish. After placing the material (for example, paper), cover with a petri dish without gap (so as to contact the liquid surface) and heat to obtain an ionic laminate in which the substrate is present on or inside the gel. This method is particularly strong.
Further, when ionic fine particles (opposite to the gel) are interposed between the substrate and the ionic gel, an ionic gel laminate is obtained.
In addition, the adjustment liquid (monomer, cross-linking agent, initiator, solvent) is mixed with a polymer compound or thickener to increase the viscosity, or the viscosity adjustment liquid created using an oligomer instead of the monomer. There exists the method of making it gelatinize by heat after apply | coating to a base material using a bar | burr etc. Furthermore, there are also methods in which a gel laminate is obtained by crosslinking using a photopolymerization initiator without using the thermal polymerization initiator of the adjusting liquid, or by radiation (gamma ray or electron beam) crosslinking or plasma crosslinking.

In the production of the ionic gel laminate, the gel laminate having various sizes and shapes can be prepared by changing the shape of the polymerization container or by easily handling the gel laminate after polymerization. For example, an ionic gel laminate having an arbitrary shape such as a fiber shape, a block shape, a rod shape, a flat plate shape, a columnar shape, a spiral shape, or a spherical shape can be prepared.
Adhesion of the same ionic gel laminate occurs very easily. Two cationic gel laminates are prepared, and an appropriate amount of anionic fine particle dispersion is applied to one of the cationic gel surfaces. When the gel surface of the other cationic gel laminate is lightly pressure-bonded to the coated surface, the two gels are bonded immediately in as little as 1 hour or less at the latest. When the adhesion is strong, the gel breaks down even if it is peeled off, and it is difficult to peel off the adhesive surface. On the other hand, it is also possible to control the adhesive force by selecting the gel component (selection of monomer) or the selection of anion fine particles (particularly the particle diameter). What was bonded in this way is also called an ionic gel laminate for convenience.

  The gel laminated | stacked on the gel laminated body at the time of applying the adhesion | attachment method of this invention may be any forms, such as a block shape, a sheet form, a solid shape, a particulate form, and a fiber form. Adhesion is performed by applying ionic fine particles in the form of powder or dispersion on the surface of the gel to be bonded, and pressing the gel onto another gel.

EXAMPLES Next, although an Example demonstrates this invention more concretely, this invention is not limited only to the Example shown below from the first.
The ionic gel can be obtained, for example, by synthesis as follows.
<Synthesis of gel containing cationic group (cationic gel)>
(Synthesis of C-1 gel)
Take 11.0 g (4 × 10 ⁻² mol as a monomer) 75% aqueous solution of (3-acrylamidopropyl) trimethylammonium chloride in a test tube (4 × 10 ⁻² mol as a monomer) and purify it with Millipore ultrapure equipment 10.7 g of Millipore water) was added and mixed well, and 0.123 g of N, N′-methylenebisacrylamide (8 × 10 ⁻⁴ mol, cross-linking agent, Tokyo Chemical Industry Co., Ltd.) was dissolved therein. To this solution, 0.108 g (4 × 10 ⁻⁴ mol, radical polymerization initiator) of potassium peroxodisulfate separately dissolved in 2 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of about 1 mm, cover with the liquid surface (float 1 mm), cover with a petri dish, and heat on a hot plate adjusted to 70 ° C for 3 hours to obtain a cationic gel with a gel concentration of 35% (Sheet shape) was obtained.

(Synthesis of C-2 gel)
Take 5.5 g of (3-acrylamidopropyl) trimethylammonium chloride (Tokyo Chemical Industry Co., Ltd.) 5.5 g (2 × 10 ⁻² mol as a monomer) in a test tube, add 10.6 g of Millipore water, and mix well. 0.154 g of N, N′-methylenebisacrylamide (1 × 10 ⁻³ mol, cross-linking agent, Tokyo Chemical Industry Co., Ltd.) was dissolved. To this solution, 0.054 g (2 × 10 ⁻⁴ mol, radical polymerization initiator) of potassium peroxodisulfate separately dissolved in 2 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of about 2 mm, cover with the liquid surface (float 2 mm), cover with a petri dish, and heat on a hot plate adjusted to 70 ° C for 3 hours to obtain a cationic gel with a gel concentration of 35% Got.

(Synthesis of C-3 gel)
In a test tube, allylamine hydrochloride (purchased from Tokyo Chemical Industry Co., Ltd.) 0.75 g (0.8 × 10 ⁻² mol as monomer) and acrylamide (purchased from Tokyo Chemical Industry Co., Ltd.) 1.14 g (1.6 × 10 ⁻² mol as monomer) Then, 16 g of Millipore water was added and mixed well, and 0.019 g of N, N′-methylenebisacrylamide (1.23 × 10 ⁻⁴ mol, crosslinking agent, purchased from Tokyo Chemical Industry Co., Ltd.) was dissolved therein. To this solution, 0.027 g (1.2 × 10 ⁻⁴ mol, radical polymerization initiator) of ammonium peroxodisulfate dissolved separately in 1 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of about 2 mm, cover with the liquid surface (float 2 mm), cover with the petri dish, and heat on a hot plate adjusted to 70 ° C for 3 hours to obtain a gel with a gel concentration of 10% Got.

(Synthesis of C-4 gel)
In a test tube, diallylamine hydrochloride (purchased from Tokyo Chemical Industry Co., Ltd.) 3.21 g (2.4 × 10 ⁻² mol as monomer) and acrylamide (purchased from Tokyo Chemical Industry Co., Ltd.) 0.57 g (0.8 × 10 ⁻² mol as monomer) Then, 7.8 g of Millipore water was added and mixed well, and 0.025 g of N, N′-methylenebisacrylamide (1.6 × 10 ⁻⁴ mol, crosslinking agent, purchased from Tokyo Chemical Industry Co., Ltd.) was dissolved therein. To this solution, 0.036 g (1.6 × 10 ⁻⁴ mol, radical polymerization initiator) of ammonium peroxodisulfate dissolved separately in 1 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of 1 mm, cover with the liquid surface (float 1 mm), cover with the petri dish, and heat on a hot plate adjusted to 70 ° C for 3 hours to obtain a gel with a gel concentration of 30% Got.

(Synthesis of C-5 gel)
2.75 g of (3-acrylamidopropyl) trimethylammonium chloride aqueous solution (Tokyo Chemical Industry Co., Ltd.) 2.75 g (1 × 10 ⁻² mol as monomer) and 2.13 g of acrylamide (purchased from Tokyo Chemical Industry Co., Ltd.) in a test tube 3 × 10 ⁻² mol), and 35.0 g of purified water (hereinafter referred to as Millipore water) was added and mixed well. 0.062 g of N, N′-methylenebisacrylamide ( 4 × 10 ⁻⁴ mol, a cross-linking agent, Tokyo Chemical Industry Co., Ltd.) was dissolved. To this solution, 0.108 g (4 × 10 ⁻⁴ mol, radical polymerization initiator) of potassium peroxodisulfate separately dissolved in 2 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of about 2 mm, cover with the petri dish (floating 2 mm), cover with a petri dish, and heat on a hot plate adjusted to 70 ° C. for 3 hours to form a cationic gel with a gel concentration of 10%. (Sheet shape) was obtained.

<Synthesis of gel containing anionic group (anionic gel)>
(Synthesis of A-1 gel)
Take 2.9 g of acrylic acid (purchased from Tokyo Chemical Industry Co., Ltd.) (4 × 10 ⁻² mol as a monomer) in a test tube, add 7.8 g of Millipore water, mix well, and add 0.123 g of N, N′− Methylenebisacrylamide (8 × 10 ⁻⁴ mol, crosslinking agent, purchased from Tokyo Chemical Industry Co., Ltd.) was dissolved. To this solution, 5.6 g of 10N sodium hydroxide solution prepared separately was slowly added to neutralize acrylic acid. A test tube containing 0.108 g of potassium peroxodisulfate dissolved in 2 g of Millipore water (4 × 10 ⁻⁴ mol, radical polymerization initiator) dissolved separately in this solution was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was performed. Repeated 10 times. Pour the prepared solution into the petri dish to a depth of about 2 mm, cover with the petri dish (floating 2 mm), cover with a petri dish, and heat on a hot plate adjusted to 70 ° C. for 6 hours to anionic gel with a gel concentration of 25% Got.

<Synthesis of neutral gel (for comparative example)>
Take 2.27 g of acrylamide (purchased from Tokyo Chemical Industry Co., Ltd.) in a test tube (3.2 × 10 ⁻² mol as a monomer), add 19.4 g of Millipore water, mix well, and add 0.049 g of N, N′-methylenebis. Acrylamide (3.2 × 10 ⁻⁴ mol, crosslinking agent, purchased from Tokyo Chemical Industry Co., Ltd.) was dissolved. To this solution, 0.0365 g (1.6 × 10 ⁻⁴ mol, radical polymerization initiator) of ammonium peroxodisulfate dissolved in 1 g of Millipore water separately prepared was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into the petri dish to a depth of 2 mm, cover it with the petri dish (floating 2 mm), cover with a petri dish, and heat for 4 hours on a hot plate adjusted to 70 ° C. A gel was obtained.

<Experiment and results of adhesion of ionic gel to substrate>
(Experiment 1) (C-1 gel laminate (neutral paper) production)
The 1 mm thick gel synthesized in C-1 was cut into 1 cm square using scissors. Drop one drop (0.02 to 0.03 g) of Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) manufactured by Nissan Chemical Industries, Ltd. on one side of this sheet-like gel, The sections were blended evenly. Immediately thereafter, the paper was laminated on neutral paper (thickness 0.26 mm, mass 125 g / m ² , trade name: qualitative filter paper, manufactured by ADVANTEC) and lightly crimped.
At each time point 5 minutes after bonding, 1 hour later, and 1 day later, the cut surface was pulled off, and the behavior at that time was evaluated according to the following evaluation criteria A to X.
If the cut surface sticks firmly and pulls with force, the gel bulk instead of the cut surface breaks (◎). If the cut surface sticks firmly, but pulls with force, peels off the cut surface ( ○) When the adhesion of the cut surface is weak and easily peeled off from the cut surface when pulled with force (△), or peeled off during handling without sticking (×).
Based on the above evaluation criteria, when C-1 gel was adhered to a substrate with ST-XS, all evaluations were ◎ regardless of the time after pressure bonding.

(Experiment 2) (C-2 gel laminate (neutral paper) production)
C-2 gel was used instead of C-1 gel in Experiment 1 above, and Snowtex ST-20 (average particle size 10-20 nm, SiO ₂ min 20%) was used instead of Snowtex ST-XS. The adhesion state was evaluated in the same manner as in Experiment 1. As a result, when the C-2 gel was adhered to the base material with ST-20, the evaluation was all excellent regardless of the time after the pressure bonding.

(Experiment 3) (C-2 gel laminate (paper) production)
Except for using C-2 gel instead of C-1 gel in Experiment 1 above and using paper (mass: 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX) instead of neutral paper as the base material The adhesion state was evaluated in the same manner as in Experiment 1. As a result, when the C-2 gel was bonded with ST-XS, it was evaluated as ◎ regardless of the time after crimping.

(Experiment 4) (C-4 gel laminate (paper) creation)
The same operation as in Experiment 1 except that C-4 gel was used instead of C-1 gel in Experiment 1 above, and paper (mass: 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX) was used as the base material. Then, the adhesion state was evaluated. As a result, when the C-4 gel was adhered to the substrate with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 5) (C-5 gel laminate (paper) creation)
The same operation as in Experiment 1 except that C-5 gel was used instead of C-1 gel in Experiment 1 above, and paper (mass: 64 g / m ² , trade name: high quality PPC paper, manufactured by XEROX) was used as the base material. Then, the adhesion state was evaluated. As a result, when C-5 gel was bonded with ST-XS, all evaluations were ◎, regardless of the time after pressure bonding.

(Experiment 6) (C-3 gel laminate (nonwoven fabric) production)
Use C-3 gel instead of C-1 gel in Experiment 1 above, and use non-woven fabric instead of neutral paper as base material (50% polyester, 50% polyethylene, liquid paraffin added, trade name: flooring wiper and dry sheet ( (Okura Sangyo Co., Ltd.) was used in the same manner as in Experiment 1 to evaluate the adhesion state. As a result, when bonding was performed using ST-XS, it took 5 minutes or more to adhere firmly and solid bonding was required. When the C-3 gel laminate after one day of adhesion was immersed in Millipore water for 24 hours, the gel absorbed water and the total weight approximately doubled and reached almost equilibrium, so the nonwoven fabric slightly stretched The gel adhesion was maintained in the state. When the gel was pulled off whether it peeled off from the substrate and the adhesion state was evaluated, it was evaluated as ◎.

(Experiment 7) (C-3 gel laminate (woven fabric) creation)
Using C-3 gel instead of C-1 gel in Experiment 1 above and using a cloth (100% cotton) woven instead of neutral paper, the same operation as in Experiment 1 Evaluated. As a result, in the case of bonding using ST-XS, all were evaluated as ◎. Next, the C-3 gel laminate 1 day after bonding was immersed in Millipore water for 1 day. The gel absorbed water and the total weight approximately doubled and reached almost equilibrium. The gel was kept in a slightly stretched state with the adhesive attached. The gel was peeled off or pulled from the substrate, and the adhesion state was evaluated.

(Experiment 8) (Preparation of A-1 gel laminate (neutral paper))
Experiment 1 except that A-1 gel was used instead of C-1 gel and alumina sol 520 (average particle size 10-20 nm, Al ₂ O ₃ min 21%) was used instead of Snowtex ST-XS The adhesion state was evaluated in the same manner as described above. As a result, since the gel showed a slightly hard property, the gel itself was apt to collapse, but all the adhesions were evaluated regardless of the time after pressure bonding.

(Experiment 9) (C-1 gel laminate (nonwoven fabric-DRY product))
Regarding the C-1 gel of Experiment 1, a gel laminate using a non-woven fabric instead of paper as a base material was stored at 100 ° C. for 3 hours at a constant temperature machine (DK400 manufactured by Yamato) and kept at room temperature after drying (containing 10 moisture) %)), The adhesion state was evaluated by the same operation and evaluation criteria as in Experiment 1. The gel taken out from the drier was in close contact with the substrate and was evaluated as ◎.

(Experiment 10) (C-3 gel laminate (neutral paper) production)
Use C-3 gel instead of C-1 gel in Experiment 1 above, and instead of Snowtex ST-XS alone, 1 g of Snowtex ST-XS and polyacrylic acid (25% aqueous solution purchased from Wako Pure Chemical) The adhesion state was evaluated in the same manner as in Experiment 1 except that 0.5 g of 5% aqueous solution was used. As a result, when the C-1 gel was adhered with a mixed solution of particles and polymer, all evaluations were ◎ regardless of the time after pressure bonding.

(Comparative experiment 1)
In the above Experiment 6, the same operation as in Experiment 6 except that Millipore water was used in place of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution manufactured by Nissan Chemical Industries, Ltd. The gel was tried to adhere. As a result, all adhesions were evaluated as x regardless of time after crimping.

(Comparative experiment 2)
Experiment 6 except that a 20% aqueous solution of sodium sulfate was used in place of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution manufactured by Nissan Chemical Industries, Ltd. The same operation was performed to try to adhere the gel. As a result, all adhesions were evaluated as x regardless of time after crimping.

(Comparative Experiment 3)
In the above experiment 6, instead of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) liquid manufactured by Nissan Chemical Industries, Ltd., alumina sol 520 (average particle size 10-20 nm, Al ₂ Except for using O ₃ min 21%), the same procedure as in Experiment 6 was performed to try to adhere the gel. As a result, all adhesions were evaluated as x regardless of time after crimping.

(Comparative Experiment 4)
In the experiment 8, instead of the alumina sol 520 (average particle size 10-20 nm, Al ₂ O ₃ minutes 21%) liquid, Snowtex ST-XS (average particle size 4-6 nm, manufactured by Nissan Chemical Industries, Ltd.) Except for using SiO ₂ min 20%), an attempt was made to adhere the gel in the same manner as in Experiment 8. As a result, all adhesions were evaluated as x regardless of the time after crimping.

(Comparative Experiment 5)
In Experiment 6, the same procedure as in Experiment 6 was performed except that the neutral polymer gel was used instead of the C-3 gel, and an attempt was made to adhere the gel. As a result, all adhesions were evaluated as x regardless of time after crimping.
Next, an ionic gel laminate was manufactured, and an adhesion experiment of the laminate was performed.
The method for producing the ionic gel laminate includes the following lamination methods other than the “adhesive bonding of the gel to the substrate using ionic particles” shown in Experiments 1 to 10 above. Examples are given, but not limited to these.
The adhesion experiment and evaluation were performed by the same evaluation method as the adhesion experiment of the ionic gel to the base material described in Experiment 1.

<Adhesion experiment and results between ionic gel laminates>
(Experiment 11)
<Manufacture of gel laminate>
In a test tube, allylamine hydrochloride (purchased from Tokyo Chemical Industry Co., Ltd.) 0.75 g (0.8 × 10 ⁻² mol as monomer) and acrylamide (purchased from Tokyo Chemical Industry Co., Ltd.) 1.14 g (1.6 × 10 ⁻² mol as monomer) Then, 16 g of Millipore water was added and mixed well, and 0.019 g of N, N′-methylenebisacrylamide (1.23 × 10 ⁻⁴ mol, crosslinking agent, purchased from Tokyo Chemical Industry Co., Ltd.) was dissolved therein. To this solution, 0.027 g (1.2 × 10 ⁻⁴ mol, radical polymerization initiator) of ammonium peroxodisulfate dissolved separately in 1 g of Millipore water was added. The test tube was connected to a nitrogen line, and the operation of depressurization and nitrogen replacement was repeated 10 times. Pour the prepared solution into a petri dish to a depth of about 4 mm, put neutral paper on it, soak in the solution, cover with a petri dish floated 4 mm, and heat on a hot plate adjusted to 70 ° C for 3 hours. A gel laminate having a gel concentration of 10% was obtained.

<Adhesion experiments and results>
The evaluation method and evaluation criteria were the same as the method for the adhesion experiment of the ionic gel to the base material described in Experiment 1 above.
The obtained 4 mm thick gel laminate was cut into 2 cm square using scissors to create a gel laminate. Two sheets were made. Two drops (0.03-0.05g) of Snotex ST-XS (average particle size 4-6nm, SiO ₂ min 20%) solution are dropped onto one gel surface of this gel laminate, and cut with a glass rod. Was evenly blended. Immediately thereafter, the gel surfaces of the other gel laminate were put together and lightly crimped. The adhesion state between sheets was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 12)
Using the two C-1 gel laminates (neutral paper) prepared in Experiment 1, an adhesion experiment in the same manner as Experiment 11 was performed. As a result, when the gel surfaces of the C-1 gel laminate (neutral paper) were bonded to each other, the evaluation was ◎ regardless of the time after pressure bonding.

(Experiment 13)
Using two sheets of C-1 gel laminate (neutral paper) prepared in Experiment 1, instead of Snowtex ST-XS, Snowtex ST-50 (average particle size 20-30 nm, SiO ₂ min 20 %) Was used, and an adhesion experiment was conducted in the same manner as in Experiment 11. As a result, when the gel surfaces of the C-1 gel laminate (neutral paper) were bonded to each other, they were all evaluated as ○ regardless of the time after the press bonding.

(Experiment 14)
Using two sheets of A-1 gel laminate (paper) prepared in Experiment 8 above, instead of Snowtex ST-XS, alumina sol 520 (average particle size 10-20 nm, Al ₂ O ₃ minutes 21%) An adhesion experiment was conducted in the same manner as in Experiment 11 except that was used. As a result, when the gel surfaces of the A-1 gel laminate (paper) were bonded to each other, the evaluations were all excellent regardless of the time after pressure bonding.

(Experiment 15)
Using the two C-3 gel laminates (nonwoven fabrics) prepared in Experiment 6, an adhesion experiment similar to Experiment 11 was performed. However, instead of Snowtex ST-XS alone, a solution in which 1 g of Snowtex ST-XS and 0.5 g of 5% aqueous solution of polyacrylic acid (25% aqueous solution purchased from Wako Pure Chemical Industries) was used was used. As a result, when the gel surfaces of the C-3 gel laminate (nonwoven fabric) were bonded to each other, they were all evaluated as か か わ ら ず regardless of the time after pressure bonding.

(Experiment 16)
An adhesion experiment was performed on the gel surface of the C-2 gel laminate (paper) prepared in Experiment 3 and the gel surface of the C-5 gel laminate (paper) prepared in Experiment 5 in the same manner as in Experiment 11. It was. As a result, when the gel surface of the C-2 gel laminate (paper) and the gel surface of the C-5 gel laminate (paper) were bonded with ST-XS, all evaluations were ◎ regardless of the time after crimping. It was.

(Experiment 17)
After applying Snowtex ST-XS to the paper side of the C-2 gel laminate (paper) prepared in Experiment 3 in the same manner as in Experiment 11, the C-3 gel prepared in the synthesis of the cationic gel was used. Was put on and lightly pressure-bonded to obtain a laminate in which different types of cationic gels were adhered to both sides of the paper. The adhesion between the base material (paper) and the gel surface was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 18)
<Method for producing gel laminate>
The C-3 gel prepared in the above synthesis of the cationic gel was placed on paper (mass 64 g / m ² , product name: high-quality PPC paper, manufactured by XEROX), and lightly pressed to obtain a cationic gel laminate. .
<Adhesion experiments and results>
The obtained gel laminate was subjected to the same adhesion experiment as Experiment 11. Two gel laminates were prepared, and the adhesion state when the gel surfaces were bonded together was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 19)
For the C-3 cationic gel laminate of Experiment 18 above, 2 drops (0.03 to 0.03) of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution was applied to the gel surface of the gel laminate. 0.05g) was added dropwise and evenly applied to the sections with a glass rod. Immediately thereafter, it was laminated with paper (mass 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX), and the adhesion state was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 20)
For the C-2 cationic gel laminate (paper) of Experiment 3 above, two drops of the gel surface of this gel laminate and Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution (0.03 to 0.05 g) was dropped and adhered to paper (mass: 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX), which was uniformly blended with a glass rod or the like, and the adhesion state was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 21)
The synthesized cationic C-3 gel was laminated on paper (mass: 64 g / m ² , product name: high-quality PPC paper, manufactured by XEROX), lightly pressure-bonded, and then at a constant temperature machine (yamato DK400) at 100 ° C. Stored for 3 hours and kept at room temperature (gel moisture content around 15%). After applying ST-XS to the gel surface of this gel laminate, two sheets were prepared in the same manner as in Experiment 11, and the adhesion state when the gel surfaces were bonded together was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 22)
The synthesized cationic C-3 gel was laminated on paper (mass: 64 g / m ² , product name: high-quality PPC paper, manufactured by XEROX), lightly pressure-bonded, and then at a constant temperature machine (yamato DK400) at 100 ° C. Stored for 3 hours and kept at room temperature (gel water content about 15%). Two drops (0.03 to 0.05 g) of ST-XS were dropped on the gel surface of this gel laminate, and the sections were uniformly blended with a glass rod or the like. Immediately thereafter, it was laminated with paper (mass 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX), and the adhesion state was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 23)
The synthesized cationic C-1 gel was laminated on paper (mass: 64 g / m ² , product name: high-quality PPC paper, manufactured by XEROX), lightly pressure-bonded, and then at a constant temperature machine (yamato DK400) at 100 ° C. Stored for 3 hours and kept at room temperature (gel moisture content 15%). Two drops (0.03 to 0.05 g) of ST-XS were dropped on the gel surface of this gel laminate, and the sections were uniformly blended with a glass rod or the like. Immediately thereafter, it was laminated with paper (mass 64 g / m ² , trade name: high-quality PPC paper, manufactured by XEROX), and the adhesion state was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 24)
<Manufacture of gel laminate>
4.5 g (1.6 × 10 ⁻² mol as a monomer) of a 75% aqueous solution of (3-acrylamidopropyl) trimethylammonium chloride (Tokyo Chemical Industry Co., Ltd.) was taken and 0.13 g of N, N′-methylenebisacrylamide (0.8 × 10 6) ⁻³ mol, cross-linking agent, Tokyo Chemical Industry Co., Ltd.) was dissolved. Further, 8 g of 20% aqueous solution prepared by dissolving 0.8 g of polyacrylamide (molecular weight: 200,000, purchased from Wako Pure Chemical Industries) in Millipore water was added. This adjustment solution was applied to a film (PET-75, manufactured by Panac) using a bar, and immediately under an atmosphere of nitrogen gas, an electron beam irradiation device (ESI electrocurtain) was used to accelerate voltage 200 kV, current 3.3 mA, speed. The electron beam was irradiated twice under the condition of 8 m / min. Upon touching the coated surface after irradiation, it was found that the paint had hardened and became a hydrogel. A gel laminate having a thickness of 0.19 mm was obtained.

<Adhesion experiments and results>
The evaluation method and evaluation criteria were the same as the method for the adhesion experiment of the ionic gel to the base material described in Experiment 1 above. The obtained gel laminate was cut into 2 cm squares using scissors to create a gel laminate. Two sheets were made. Two drops (0.03-0.05g) of Snotex ST-XS (average particle size 4-6nm, SiO ₂ min 20%) solution are dropped onto one gel surface of this gel laminate, and cut with a glass rod. Was evenly blended. Immediately thereafter, the gel surfaces of the other gel laminate were put together and lightly crimped. The adhesion state between sheets was evaluated. As a result, in the case of bonding with ST-XS, it was evaluated as ◎ regardless of the time after pressure bonding.

(Experiment 25)
<Manufacture of gel laminate>
Take 6.66 g (2.4 × 10 ⁻² mol as a monomer) of a 75% aqueous solution of (3-acrylamidopropyl) trimethylammonium chloride (Tokyo Chemical Industry Co., Ltd.), and further polyacrylamide (molecular weight 200,000, purchased from Wako Pure Chemical) 1.3 6.5 g of a 20% aqueous solution in which g was dissolved in Millipore water was added. A gel laminate having a thickness of 0.1 mm was obtained from this adjustment liquid in the same manner as in Experiment 24. As a result of evaluating the adhesion state between the sheets, it was evaluated as ◎ regardless of the time after the press bonding when bonded with ST-XS.

(Comparative Experiment 6)
The same operation as in Experiment 12 except that Millipore water was used in place of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution manufactured by Nissan Chemical Industries, Ltd. in Experiment 12 above. The gel was tried to adhere. As a result, all adhesions were evaluated as Δ regardless of time after crimping.

(Comparative Experiment 7)
Experiment 12 is the same as Experiment 12 except that a 20% aqueous solution of sodium sulfate was used instead of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) solution manufactured by Nissan Chemical Industries, Ltd. The same operation was performed to try to adhere the gel. As a result, all adhesions were evaluated as x regardless of time after crimping.

(Comparative Experiment 8)
In the above experiment 12, instead of the Snowtex ST-XS (average particle size 4-6 nm, SiO ₂ min 20%) liquid manufactured by Nissan Chemical Industries, Ltd., alumina sol 520 (average particle size 10-20 nm, Al ₂ Except for using O ₃ min 21%), the same operation as in Experiment 12 was performed to try to adhere the gel. As a result, all adhesions were evaluated as x regardless of time after crimping.

(Comparative Experiment 9)
In the above experiment 14, instead of the alumina sol 520 (average particle size 10-20 nm, Al ₂ O ₃ minute 21%) liquid, Snowtex ST-XS (average particle size 4-6 nm, manufactured by Nissan Chemical Industries, Ltd.) Except for using SiO ₂ min 20%), an attempt was made to adhere the gel in the same manner as in Experiment 14. As a result, all adhesions were evaluated as x regardless of time after crimping.

<Summary of Examples>
As shown in the above examples, a gel containing a cationic group can be strongly bonded to a substrate by anionic particles, and a gel having an anionic group can be strongly bonded to a substrate by cationic particles. On the other hand, when an attempt was made to adhere a gel having a liquid interposition without particles or an anionic group with anionic particles, it did not adhere. In particular, the hydrophobic surface of the nonwoven fabric and the neutral polymer gel did not adhere with the anionic particles.
In addition, a gel laminate having a cationic group has an anionic particle intervening between gels, or when a mixture of anionic particles and anionic resin is applied, the gel laminate having an anionic group Strong particles can be bonded with the sex particles. On the other hand, when trying to bond gels with water, when trying to bond with a solution containing polyvalent ions instead of charged particles, or when trying to bond gels with cationic groups with cationic particles In this case, when the gel having an anionic group was to be bonded with anionic particles, the gel was not bonded. By repeating the adhesion between the gel and the substrate, an ionic gel laminate having a multilayer structure was easily obtained.

  As described above, the effect of the present invention is clear, such as gel molding, gel processing, and generation of a multilayer body containing a gel, and the applicability of the present technology is great. Functional materials that are bent by the field of paper products (adhesive or pseudo-adhesive sheets) and packaging materials, external stimuli (pH, charge, temperature, solvent hydrophilicity / hydrophobicity), especially aqueous gels are biocompatible Since it is expected to have high environmental compatibility, it has applications in a wide range of industrial fields as soft materials and functional gel materials.

Claims (10)

A method for adhering a base material and an ionic gel, wherein an anionic fine particle is interposed between a gel containing a cationic group as a constituent and the base, and the gel containing the anionic group as a constituent and the base A method for adhering a base material and an ionic gel, characterized in that cationic fine particles are interposed between the material and the material. The bonding method according to claim 1, wherein the gel is a hydrogel containing water. The bonding method according to claim 1 or 2, wherein the average particle size of the anionic fine particles and the cationic fine particles is 1 nm or more and 10,000 nm or less. The adhesion method according to any one of claims 1 to 3, wherein the substrate is paper, nonwoven fabric or cloth. The ionic gel laminated body manufactured using the adhesion | attachment method in any one of Claims 1-4. A method of adhering gel surfaces of an ionic gel laminate in which an ionic gel is laminated on a substrate, and for a cationic gel laminate in which a gel containing a cationic group as a constituent component is formed, In addition, for an anionic gel laminate containing an anionic group as a constituent component, anionic fine particles are interposed between the gels, so that the gel surface of the ionic gel laminate can be obtained. A method of bonding together. The adhesion method according to claim 6, wherein the gel is a hydrogel containing water. The adhesion method according to claim 6 or 7, wherein the average particle size of the anionic fine particles and the cationic fine particles is 1 nm or more and 10,000 nm or less. The adhesion method according to any one of claims 6 to 8, wherein the substrate is paper, nonwoven fabric or cloth. The ionic gel laminated body manufactured using the adhesion | attachment method in any one of Claims 6-9.