JP2018165325A - Complex, practice kit, and method for producing complex - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a force required for peeling a conventional organ model depending on the arrangement of fiber groups, and thus the force is not stable due to variations in product quality. Therefore, there arises a problem that the tactile sensation and sharpness when incising or peeling the composite using hydrogel is different from the tactile sensation and sharpness when incising or peeling the actual tissue. SOLUTION: The composite has two or more hydrogel bodies bonded to each other so as to be peelable, and has a polymer having a weight average molecular weight of 8000 or more on a fracture surface when peeled at the bonding interface. [Selection diagram] Fig. 1

Description

  The present invention relates to a complex, a practice kit, and a method for producing the complex.

  Conventionally, treatment in the body such as surgery using a device such as an endoscope, an ultrasonic scalpel, or an electric scalpel is performed. For example, doctors can remove tumors while checking images of the esophagus, stomach, large intestine, ear canal, or urethra through an endoscope from the nose, mouth, anus, ear, or urinary tract. Do. In addition, the doctor performs a procedure such as bypassing, cutting, or anastomosis of the blood vessel using an ultrasonic scalpel or an electric scalpel. The shape and hardness of tissues such as organs and blood vessels vary depending on the patient or the affected area.

  Recovery after treatment and quality of life (QOL) may depend on the level of procedure by the physician. Therefore, for the purpose of improving the skill level, a surgical practice called a wet lab using a mini pig is performed. However, the shape and hardness of the organs of minipigs are different from humans. In addition, it is difficult to provide minipigs having a disease in an organ at a desired timing. Furthermore, in order to develop an environment where miniature pigs can grow, maintain freshness, and be managed, a very expensive cost is required, so that a wet lab cannot be performed many times. Therefore, in order to increase the success rate of highly difficult tumor extraction surgery, a blood vessel model and an organ model for practicing surgical procedures and the like have been proposed.

  Patent Document 1 is a laminate in which a plurality of layers made of a hydrogel material are laminated, and one or more of the layers are inside the layer and the fiber group is substantially continuous over the planar direction of the layer. An organ model characterized by being an unevenly distributed fiber group-containing layer is disclosed. Patent Document 1 discloses that in this organ model, the layer adjacent to the fiber group-containing layer can be peeled off in the vicinity of the interface between the fiber group-containing layer and the adjacent layer. .

  However, since the force required for peeling off the organ model described above varies depending on the arrangement of the fiber group, it is not stable due to variations in product quality. For this reason, the subject that the tactile sensation and sharpness at the time of incising or exfoliating the complex using hydrogel differs from the tactile sensation and sharpness at the time of incising or exfoliating actual tissue arises.

  In the composite of the invention according to claim 1, two or more hydrogel bodies are detachably bonded, and have a polymer having a weight average molecular weight of 8000 or more on the fracture surface when peeled at the bonding interface.

  ADVANTAGE OF THE INVENTION According to this invention, the tactile feeling when cutting | disconnecting or exfoliating and a sharpness are provided, and the composite | tissue which is close to the tactile feeling when cutting or peeling an actual tissue | tissue and sharpness is provided.

FIG. 1 is a schematic diagram illustrating a modeling apparatus according to an embodiment. FIG. 2 is a perspective view of a mold and a hydrogel body used in the examples. FIG. 3 is a perspective view of a mold and a hydrogel body used in the examples. FIG. 4 is a perspective view of a mold and a hydrogel body used in the examples. FIG. 5 is a perspective view of the composite obtained in the example. FIG. 6 is a conceptual diagram for explaining a process for producing a composite in the example. FIG. 7 is a diagram for explaining a modeling process in the embodiment. FIG. 8 is a perspective view of the composite obtained in the example.

  Hereinafter, modes for carrying out the present invention will be described. In addition, the following description shows only embodiment of this invention and does not limit this invention. In a composite part according to an embodiment of the present invention, two or more hydrogel bodies are detachably bonded, and a polymer A having a weight average molecular weight of 8000 or more is present at an adhesion interface. Hereinafter, the composite will be described.

<< Polymer A >>
The polymer A is a polymer having a weight average molecular weight of 8000 or more that appears at the adhesion interface when an external force is applied to the composite to separate it into two or more hydrogel bodies. In addition, an adhesion interface is an interface where two or more hydrogel bodies contact at the time of adhesion, and may represent a fracture surface when two or more hydrogel bodies are separated at the interface. The polymer A exists mainly at the adhesive interface, and affects the frictional property, adhesiveness, chargeability, contact angle, surface tension, shape change, and the like of the adhesive interface.

  Polymer A is preferably soluble in methanol. Soluble in methanol means, for example, 1% by mass or more, preferably 3% by mass to 50% by mass, more preferably 5% by mass to 30% by mass with respect to the mass of methanol at 25 ° C. The following properties are dissolved.

  By using the polymer A that is soluble in methanol, methanol can be used as a solvent for attaching the polymer A to the surface of the hydrogel body. In addition, unlike many other organic solvents, methanol has high wettability with respect to the surface of a hydrophilic hydrogel body. After the methanol solution of polymer A is attached to the surface of the hydrogel body, the methanol is easily removed from the hydrogel body. When water instead of an organic solvent is used as the solvent for the polymer A, the aqueous solution of the polymer A is attached to the surface of the hydrogel body, and then the water as the solvent is removed. Water is also removed, affecting the physical properties of the hydrogel.

  The solution used when the polymer A is attached to the hydrogel body is, if necessary, a stabilizer, a surface treatment agent, a polymerization initiator, a colorant, a viscosity modifier, an adhesion promoter, an antioxidant, and aging. You may contain an inhibitor, a crosslinking accelerator, a ultraviolet absorber, a plasticizer, an antiseptic | preservative, a dispersing agent, etc. In order to control surface properties and gloss, the solution may contain an emulsion in which wax, resin fine particles, or inorganic fine particles are dispersed, that is, an aqueous dispersion, an organosol, or an oil dispersion.

  Since the polymer A has adhesiveness to the hydrogel and promotes breakage by having a portion in which the hydrophobic groups are compatible with each other in the layer, a hydroxyl group and a hydroxyl group other than a hydroxyl group that is more hydrophobic than the hydroxyl group are used. It preferably has a substituent, and the ratio of hydroxyl groups to substituents other than hydroxyl groups is preferably in the range of 1.0: 99.0 to 90.0: 10.0. In the present embodiment, the symbol “to” represents a range including values, ratios, ratios, and the like described before and after that. The substituent having a hydrophobicity than the hydroxyl group is a substituent having a hydrocarbon group, a halogen group, or an aromatic group at the terminal, and specific examples include an acetic acid group and a chloro group.

  Polymer A includes low-saponified polyvinyl alcohol; polyvinyl acetate; a polymer of an acrylate monomer containing a hydroxyl group; a copolymer of an acrylate monomer containing a hydroxyl group and at least one of vinyl chloride, vinyl acetate, and ethylene; or Examples thereof include sugars such as glucose, maltose, sucrose, lactose, cellobiose, trehalose, cyclodextrin, glycogen, amylopectin, amylose, starch, and cellulose.

  Of these, polyvinyl alcohol having a saponification degree of 90 mol% or less is preferable, polyvinyl alcohol having a saponification degree of 5% to 50% is more preferable, and polyvinyl alcohol having a saponification degree of 10% to 25% is more preferable. The polymer A having a saponification degree of 90% or less is preferable in that it easily dissolves in a solvent such as methanol.

Among the above polymers, those having a weight average molecular weight of less than 8000 are excluded from the polymer A because they may not exhibit a desired function. By making the weight average molecular weight of the polymer A 8000 or more, preferably 8000 or more and 1,000,000 or less, more preferably 14,000 or more and 120,000 or less, the releasability, particularly the sensation that the hydrogel is pulled immediately after the start of peeling. I can make it. Further, the polymer A is preferably used between ^{0.01mg / cm 2 ~100mg / cm 2} , either present in the layer on the adhesive surface, it is preferably present in a mass of less than 1 cm ³ instead of the layer .

<< Hydrogel body >>
The hydrogel body is not particularly limited and is appropriately selected, and includes, for example, water, a polymer, and a mineral. The polymer and the mineral are compounded to form a three-dimensional network structure, and water is included in the three-dimensional network structure. The hydrogel body may contain an organic solvent, preferably a water-soluble organic solvent. Moreover, the hydrogel body may contain other components other than water, a polymer, a mineral, and a water-soluble organic solvent. Hereinafter, each component of hydrogel is demonstrated.

<Water>
Examples of water include ion-exchanged water, ultrafiltrated water, reverse osmosis water, or distilled water as pure water or ultrapure water. Components such as an organic solvent may be dissolved or dispersed in water for the purpose of imparting moisture retention, imparting antibacterial properties, imparting electrical conductivity, or adjusting hardness.

<Polymer>
Examples of the polymer include polymers having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, or epoxy group. The polymer may be a homopolymer (homopolymer), a heteropolymer (copolymer), a modified polymer, or a known functional group may be introduced. It may be in the form of a salt, but is preferably a homopolymer.

  The polymer is preferably water soluble. “Polymer is water-soluble” means that, for example, when 1 g of a polymer is mixed with 100 g of water at 30 ° C. and stirred, 90% by mass or more thereof is dissolved. As a polymer, you may use what polymerized the below-mentioned monomer.

<Mineral>
There is no restriction | limiting in particular as a mineral, According to the objective, it selects suitably, A water swelling layered clay mineral etc. are illustrated. Water swellability refers to the property that water molecules are inserted between layers of layered clay mineral and dispersed in water. The water-swellable layered clay mineral has a structure in which two-dimensional disk-like crystals with unit lattices in the crystal are stacked.When the water-swellable layered clay mineral is dispersed in water, each single-layered disk-like clay mineral Separate into crystals.

  Examples of the water-swellable layered clay mineral include water-swellable smectite and water-swellable mica, and more specifically, water-swellable hectorite containing sodium as an interlayer ion, water-swellable montmorillonite, water-swellable Examples include saponite and water-swellable synthetic mica. These may be used individually by 1 type and may use 2 or more types together. Among these, a water-swellable hectorite is preferable because a highly elastic porous material can be obtained.

  The water-swellable hectorite may be a commercially available product. Examples of commercially available water-swellable hectorites include synthetic hectorite (Laponite XLG, manufactured by RockWood), SWN (manufactured by Coop Chemical Ltd.), and fluorinated hectorite SWF (manufactured by Coop Chemical Ltd.). . Among these, synthetic hectorite is preferable from the viewpoint of the elastic modulus of the porous material.

  The content of the layered clay mineral is not particularly limited and is appropriately selected depending on the purpose. From the viewpoint of the elastic modulus and hardness of the hydrogel body, it is 1% by mass or more and 40% by mass with respect to the total amount of the hydrogel body. % Or less is preferable and 1 mass% or more and 25 mass% or less are more preferable.

<Organic solvent>
The hydrogel body may contain an organic solvent in order to improve moisture retention.

  Examples of the organic solvent include alkyl alcohols having 1 to 4 carbon atoms such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, and tert-butyl alcohol; dimethylformamide, and Amides such as dimethylacetamide; Ketones or ketone alcohols such as acetone, methyl ethyl ketone, and diacetone alcohol; Ethers such as tetrahydrofuran and dioxane; Ethylene glycol, propylene glycol, 1,2-propanediol, 1,2-butane Diol, 1,3-butanediol, 1,4-butanediol, diethylene glycol, triethylene glycol, 1,2,6-hexanetriol, thioglycol, hexylene glycol And polyalcohols such as polyethylene glycol and polypropylene glycol; ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, and triethylene glycol monomethyl (or ethyl) ) Lower alcohol ethers of polyhydric alcohols such as ether; alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and N-methyl-2-pyrrolidone, 2-pyrrolidone, and 1,3-dimethyl- Examples include 2-imidazolidinone. These may be used individually by 1 type and may use 2 or more types together. Among these, from the viewpoint of moisture retention, water-soluble organic solvents such as polyhydric alcohols are preferable, and glycerin and propylene glycol are more preferable.

  The content of the organic solvent is preferably 10% by mass or more and 50% by mass or less with respect to the total amount of the hydrogel body. When the content of the organic solvent is 10% by mass or more, the effect of preventing drying is sufficiently obtained, and when it is 50% by mass or less, the layered clay mineral is uniformly dispersed in water.

<< Other ingredients >>
Other components used in the hydrogel body are not particularly limited, but include preservatives, colorants, fragrances, antioxidants, stabilizers, surface treatment agents, polymerization initiators, viscosity modifiers, adhesion promoters, Examples thereof include an antioxidant, a crosslinking accelerator, an ultraviolet absorber, a plasticizer, and a dispersant.

  Preservatives include dehydroacetate, sorbate, benzoate, sodium pentachlorophenol, sodium 2-pyridinethiol-1-oxide, 2,4-dimethyl-6-acetoxy-m-dioxane, and 1, Examples include 2-benzthiazolin-3-one.

  In the composite and the hydrogel body, it is preferable that structures having different colors or hardnesses are arranged at target positions. A composite in which structures having different colors or hardnesses are arranged is suitable as a model for confirming a position where a scalpel is inserted before surgery. Examples of structures include mimetics such as blood vessels, ducts, and diseased parts; and cavities and folds. The hardness in each structure is prepared by changing the content of the water-swellable layered clay mineral contained in the hydrogel body, for example.

  A color is adjusted with the coloring agent added to a hydrogel body, for example. By including a colorant in the hydrogel body, the hydrogel body can be colored in a color that approximates a human organ. There is no restriction | limiting in particular as a coloring agent, According to the objective, it selects suitably, Dye and a pigment are illustrated.

  Examples of the dye include black dyes, magenta dyes, cyan dyes, and yellow dyes.

  As black dyes, MS BLACK VPC (manufactured by Mitsui Chemicals), AIZEN SOT BLACK-1, AIZEN SOT BLACK-5 (manufactured by Hodogaya Chemical Co., Ltd.), RESRORIN BLACK GSN 200%, RESOLIN BLACK BS (manufactured by Bayer Japan) ), KAYASET BLACK A-N (manufactured by Nippon Kayaku Co., Ltd.), DAIWA BLACK MSC (manufactured by Daiwa Kasei Co., Ltd.), HSB-202 (manufactured by Mitsubishi Kasei Co., Ltd.), NEPTUNE BLACK X60, NEOPEN BLACK X58 (manufactured by BASF Japan) ), Oleosol Fast BLACK RL (manufactured by Taoka Chemical Industry Co., Ltd.), Chuo BLACK80, Chuo BLACK80-15 (manufactured by Chuo Synthetic Chemical Co., Ltd.), etc. That.

  Examples of magenta dyes include MS Magenta VP, MS Magenta HM-1450, MS Magenta Hso-147 (manufactured by Mitsui Chemicals), AIZENSOT Red-1, AIZEN SOT Red-2, AIZEN SOT Red-3, AIZEN SOT Pink-1. , SPIRON Red GEHSPECIAL (Hodogaya Chemical Co., Ltd.), RESOLIN Red FB 200%, MACROLEX Red Violet R, MACROLEX ROT 5B (manufactured by Bayer Japan), KAYASET RedB, KAYASET Red 130, KAYASET Japan Manufactured), PHLOXIN, ROSE BENGAL, ACID Red (manufactured by Daiwa Kasei Co., Ltd.), HSR- 1, Diaresin REDK (manufactured by Mitsubishi Kasei Corporation), (manufactured by BASF Japan Ltd.) Oil Red, and Oil Pink330 (manufactured by Central Synthetic Chemical Co., Ltd.) and the like.

  Examples of cyan dyes include MS Cyan HM-1238, MS Cyan HSo-16, Cyan Hso-144, MS Cyan VPG (manufactured by Mitsui Chemicals), AIZEN SOT Blue-4 (manufactured by Hodogaya Chemical Co., Ltd.), and RESOLIN BR. Blue BGLN 200%, MACROLEX Blue RR, CERES BlueGN, SIRIUS SUPRATURQ. Blue Z-BGL, SIRIUS SUTRA TURQ. Blue FB-LL 330% (manufactured by Bayer Japan), KAYASET Blue Fr, KAYASET Blue N, KAYASET Blue 814, Turq. Blue GL-5 200, LightBlue BGL-5 200 (manufactured by Nippon Kayaku Co., Ltd.), DAIWA Blue 7000, Olesol Fast Blue GL (manufactured by Daiwa Kasei Co., Ltd.), DIARESINBlue P (manufactured by Mitsubishi Kasei Co., Ltd.), SUDAN Blue 6 NEOPEN Blue 808, ZAPON Blue 806 (manufactured by BASF Japan) and the like are exemplified.

  As yellow dyes, MS Yellow HSm-41, Yellow KX-7, Yellow EX-27 (manufactured by Mitsui Chemicals), AIZENSOT Yellow-1, AIZEN SOT YellowW-3, AIZEN SOT Yellow-6 (Hodogaya Chemical Co., Ltd.) ), MACROLEX Yellow 6G, MACROLEX FLUOR, Yellow 10GN (manufactured by Bayer Japan), KAYASET Yellow SF-G, KAYASET Yellow 2G, KAYASET Yellow A-G, KAYASET Y YDA 330HB (manufactured by Daiwa Kasei Co., Ltd.), HSY-68 (manufactured by Mitsubishi Kasei Co., Ltd.), SUDAN Yellow 146 NEOPEN Yellow 075 (manufactured by BASF Japan Ltd.), and Oil Yellow 129 (manufactured by Central Synthetic Chemical Co., Ltd.) and the like.

  Examples of the pigment include various organic and inorganic pigments. Specific examples include azo pigments such as azo lakes, insoluble azo pigments, condensed azo pigments, and chelate azo pigments; phthalocyanine pigments; perylene pigments; anthethequinone pigments; quinacridone pigments; Examples include pigments; thioindigo pigments; isoindolinone pigments; and polycyclic pigments such as quinophthalone pigments. Specific examples of the pigment include organic or inorganic pigments of red or magenta, blue or cyan, green, yellow, or black having the following numbers described in the color index.

  Pigment Red 3, 5, 19, 22, 31, 38, 43, 48: 1, 48: 2, 48: 3, 48: 4, 48: 5, 49: 1, 53: 1 as red or magenta pigment 57: 1, 57: 2, 58: 4, 63: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 88, 104, 108, 112, 122, 123, 144, 146 149, 166, 168, 169, 170, 177, 178, 179, 184, 185, 208, 216, 226, 257, Pigment Violet 3, 19, 23, 29, 30, 37, 50, 88, and Pigment Orange 13, 16, 20, 36 etc. are illustrated.

  Pigment Blue 1, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17-1, 22, 27, 28, 29, 36, 60 as blue or cyan pigments Etc. are exemplified.

  Examples of the green pigment include Pigment Green 7, 26, 36, 50, and the like. As the yellow pigment, Pigment Yellow 1, 3, 12, 13, 14, 17, 34, 35, 37, 55, 74, 81, 83, 93, 94, 95, 97, 108, 109, 110, 137, 138 139, 153, 154, 155, 157, 166, 167, 168, 180, 185, 193 and the like. Examples of the black pigment include Pigment Black 7, 28, 26, and the like.

  The pigment may be a commercially available product. Commercially available pigments include chromofine yellow 2080, 5900, 5930, AF-1300, 2700L, chromofine orange 3700L, 6730, chromofine scarlet 6750, chromofine magenta 6880, 6886, 6891N, 6790, 6887, chromofine violet. RE, Chromofine Red 6820, 6830, Chromofine Blue HS-3, 5187, 5108, 5197, 5085N, SR-5020, 5026, 5050, 4920, 4927, 4937, 4824, 4933GN-EP, 4940, 4993, 5205, 5208, 5214, 5221, 5000P, chromo fine green 2GN, 2GO, 2G-550D, 5310, 5370, 6830, chromophy Black A-1103, Seika Fast Yellow 10GH, A-3, 2035, 2054, 2200, 2270, 2300, 2400 (B), 2500, 2600, ZAY-260, 2700 (B), 2770, Seica Fast Red 8040, C405 (F), CA120, LR-116, 1531B, 8060R, 1547, ZAW-262, 1537B, GY, 4R-4016, 3820, 3891, ZA-215, Seika Fast Carmine 6B1476T-7, 1483LT, 3840, 3870, Seika Fast Bordeaux 10B-430, Seikalite Rose R40, Seikalite Violet B800, 7805, Seika Fast Maroon 460N, Seika Fast Orange 900, 2900, Seika Light Blue C718, A6 12, Cyanine Blue 4933M, 4933GN-EP, 4940, 4973 (manufactured by Dainichi Seika Kogyo Co., Ltd.); KET Yellow 401, 402, 403, 404, 405, 406, 416, 424, KET Orange 501, KET Red 301 , 302, 303, 304, 305, 306, 307, 308, 309, 310, 336, 337, 338, 346, KET Blue 101, 102, 103, 104, 105, 106, 111, 118, 124, KET Green 201 (Above, manufactured by DIC Corporation); Colortex Yellow 301, 314, 315, 316, P-624, 314, U10GN, U3GN, UNN, UA-414, U263, Finecol Yellow T-13, T-0 5, Pigment Yellow 1705, Colortex Orange 202, Colortex Red 101, 103, 115, 116, D3B, P-625, 102, H-1024, 105C, UFN, UCN, UBN, U3BN, URN, UGN, UG276, U456, 45 105C, USN, Colortex Maroon 601, Colortex Brown B610N, Colortex Violet 600, Pigment Red 122, Colortex Blue 516, 517, 518, 519, A818, P-908, 510, Colortex Green 402, 403 Made by company); Lionol Yellow 1 05G, Lionol Blue FG7330, FG7350, FG7400G, FG7405G, ES, ESP-S (above, manufactured by Toyo Ink Mfg. Co., Ltd.); Carbon Black # 2600, # 2400, # 2350, # 2200, # 1000, # 990, # 980, # 970, # 960, # 950, # 850, MCF88, # 750, # 650, MA600, MA7, MA8, MA11, MA100, MA100R, MA77, # 52, # 50, # 47, # 45, # 45L, # 40, # 33, # 32 , # 30, # 25, # 20, # 10, # 5, # 44, CF9 (manufactured by Mitsubishi Chemical Corporation) and the like.

  There is no restriction | limiting in particular in the addition amount of a coloring agent, Although it selects suitably according to the objective, 0.1 mass% or more and 5 mass% or less are preferable with respect to the whole quantity of a hydrogel body.

<< Liquid for forming hydrogel >>
The hydrogel body may be formed by a hydrogel-forming liquid. The hydrogel-forming liquid contains the above water, minerals, organic solvents, and other components as components of the hydrogel body, and includes a monomer and a polymerization initiator as components for producing a polymer in the hydrogel body. You may contain.

<Monomer>
The monomer used in the hydrogel-forming liquid is preferably a compound having one or more unsaturated carbon-carbon bonds, and examples thereof include monofunctional monomers and polyfunctional monomers. Examples of the polyfunctional monomer include a bifunctional monomer, a trifunctional monomer, a trifunctional or higher monomer, and the like. A monomer may be used individually by 1 type and may use 2 or more types together.

  A monofunctional monomer is a compound having one unsaturated carbon-carbon bond. Examples of monofunctional monomers include acrylamide, N-substituted acrylamide derivatives, N, N-disubstituted acrylamide derivatives, N-substituted methacrylamide derivatives, N, N-disubstituted methacrylamide derivatives, and other monofunctional monomers. The

  Examples of N-substituted acrylamide derivatives include N-isopropyl (meth) acrylamide. An example of the N, N-disubstituted (meth) acrylamide derivative is N, N-dimethyl (meth) acrylamide (DMAA).

  Other monofunctional monomers include 2-ethylhexyl (meth) acrylate (EHA), 2-hydroxyethyl (meth) acrylate (HEA), 2-hydroxypropyl (meth) acrylate (HPA), acryloylmorpholine (ACMO), caprolactone Modified tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, lauryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, isodecyl (meth) ) Acrylate, isooctyl (meth) acrylate, tridecyl (meth) acrylate, caprolactone (meth) acrylate, ethoxylated nonylphenol (meth) acrylate, and urea (Meth) acrylate and the like.

  The content of the monofunctional monomer is not particularly limited and may be appropriately selected depending on the purpose, but is preferably 1% by mass or more and 10% by mass or less, and preferably 1% by mass or more and 5% by mass with respect to the total amount of the hydrogel-forming liquid. The mass% or less is more preferable. When the content of the monofunctional monomer is in the range of 1% by mass or more and 10% by mass or less, the dispersion stability of the mineral in the hydrogel-forming liquid is maintained, and the stretchability of the resulting hydrogel body is improved. There are advantages. Stretching refers to a property that stretches and does not break when the hydrogel body is pulled.

  By polymerizing these monofunctional monomers, a water-soluble polymer having an amide group, amino group, hydroxyl group, tetramethylammonium group, silanol group, epoxy group or the like can be obtained. A water-soluble polymer having an amide group, an amino group, a hydroxyl group, a tetramethylammonium group, a silanol group, or an epoxy group is effective for maintaining the strength of the hydrogel.

  Examples of the bifunctional monomer include tripropylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol hydroxypivalate ester di (meta ) Acrylate (MANDA), hydroxypivalic acid neopentyl glycol ester di (meth) acrylate (HPNDA), 1,3-butanediol di (meth) acrylate (BGDA), 1,4-butanediol di (meth) acrylate (BUDA) ), 1,6-hexanediol di (meth) acrylate (HDDA), 1,9-nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate (DEGDA) , Neopentyl glycol di (meth) acrylate (NPGDA), tripropylene glycol di (meth) acrylate (TPGDA), caprolactone-modified hydroxypivalate neopentyl glycol ester di (meth) acrylate, propoxylated neopentyl glycol di (meth) acrylate And ethoxy-modified bisphenol A di (meth) acrylate, polyethylene glycol 200 di (meth) acrylate, polyethylene glycol 400 di (meth) acrylate, and methylene bisacrylamide.

  Trifunctional monomers include trimethylolpropane tri (meth) acrylate (TMPTA), pentaerythritol tri (meth) acrylate (PETA), triallyl isocyanate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, ethoxylation Examples include trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, and propoxylated glyceryl tri (meth) acrylate.

  Tri- or higher functional monomers include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hydroxypenta (meth) acrylate, ethoxylated pentaerythritol tetra (meth) acrylate, penta (meth) acrylate Examples include esters and dipentaerythritol hexa (meth) acrylate (DPHA).

  As content of a polyfunctional monomer, 0.001 mass% or more and 1 mass% or less are preferable with respect to the whole quantity of the liquid for hydrogel formation, and 0.01 mass% or more and 0.5 mass% or less are more preferable. When the content of the polyfunctional monomer is in the range of 0.001% by mass to 1% by mass, the elastic modulus and hardness of the resulting hydrogel body can be adjusted to an appropriate range.

<Polymerization initiator>
The liquid for forming the hydrogel may be cured using a polymerization initiator. In this case, the polymerization initiator is used by being added to the hydrogel-forming liquid. A photoinitiator is illustrated as a polymerization initiator.

  As the photopolymerization initiator, any substance that generates radicals by irradiation with light, for example, ultraviolet rays having a wavelength of 220 nm to 400 nm can be used.

  As photopolymerization initiators, acetophenone, 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-dichlorobenzophenone, p, p-bisdiethylaminobenzophenone, Michler's ketone, benzyl, Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin n-propyl ether, benzoin isobutyl ether, benzoin n-butyl ether, benzyl methyl ketal, thioxanthone, 2-chlorothioxanthone, 2-hydroxy-2-methyl- 1-phenyl-1-one, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, methylbenzoyl formate, Examples include 1-hydroxycyclohexyl phenyl ketone, azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, and the like. These may be used individually by 1 type and may use 2 or more types together.

<< Method for producing hydrogel body >>
The production method of the hydrogel body is appropriately selected according to the purpose, but the mold is manufactured by a method of coating the liquid for forming the hydrogel with a certain thickness on a flat plate or the like, or by a suitable processing method. , A method of injecting a hydrogel-forming liquid into a mold and curing it (hereinafter referred to as “molding with a mold”), a head unit in which an inkjet head is arranged, and after discharging the hydrogel-forming liquid, There is a method of laminating while curing the hydrogel-forming liquid by irradiating with ultraviolet light (hereinafter referred to as “material jet molding”).

  Since the biological tissue contains a complex shape and a plurality of parts having different properties, when reproducing the biological tissue using a hydrogel body, molding by a mold or material jet molding is preferable, and the shape is accurately formed. From the viewpoint, material jet molding is more preferable.

<Molding by mold>
A mold in which an internal cavity having a desired shape is formed in advance is used. The mold may be used alone or as a set with a core. The hydrogel-forming liquid is cured while being injected into the mold. Thereby, the hydrogel body of the shape according to the type | mold is obtained as hardened | cured material. The mold may be disposable for single use or reusable. Examples of the reusable mold include those that are used in combination with a plurality of parts and that are decomposed into a plurality of parts when the hydrogel body is taken out. The mold may be manufactured by cutting metal or resin or using a modeling apparatus called a three-dimensional printer.

<Material jet molding>
In material jet molding, the hydrogel-forming liquid is mounted on a modeling apparatus as a model material. Moreover, arbitrary model materials are mounted in a modeling apparatus as needed. Hereinafter, a general material jet type modeling apparatus equipped with a UV curable model material and a support material will be described as a modeling apparatus suitably used in the manufacturing method of the present embodiment. At least one of two or more hydrogel bodies can be formed by the following modeling apparatus. Moreover, the modeling apparatus can make the liquid containing a polymer on the surface of the formed hydrogel body.

  FIG. 1 is a schematic view showing a modeling apparatus according to an embodiment of the present invention. The modeling apparatus 30 includes head units 31 and 32, an ultraviolet irradiator 33, a roller 34, a carriage 35, and a stage 37. The head unit 31 discharges the model material 1. The head unit 32 discharges the support material 2. The ultraviolet irradiator 33 irradiates the discharged model material 1 and support material 2 with ultraviolet rays and cures them. The roller 34 smoothes the liquid film of the model material 1 and the support material 2. The carriage 35 reciprocates each unit such as the head units 31 and 32 in the X direction in FIG. The stage 37 moves the substrate 36 in the Z direction shown in FIG. 1 and the Y direction which is the depth direction in FIG.

  When there are a plurality of model materials for each color, the modeling apparatus 30 may be provided with a plurality of head units 31 for discharging the model material of each color.

  As nozzles in the head units 31 and 32, nozzles in known ink jet printers can be suitably used.

  Examples of the metal that can be used for the roller 34 include SUS300 series, 400 series, 600 series, hexavalent chromium, silicon nitride, and tungsten carbide. Further, a metal in which any of these is coated with fluorine or silicone may be used for the roller 34. Among these metals, 600 series is preferable from the viewpoint of strength and workability. In the case where the roller 34 is used, the effect of smoothing can be further exerted by rotating the roller 34 in the reverse direction with respect to the scanning direction of the carriage 35.

  When the roller 34 is used, the modeling apparatus 30 performs stacking while lowering the stage 37 in accordance with the number of stacking times in order to keep the gap between the roller 34 and the surface of the modeled object constant. It is preferable that the roller 34 is adjacent to the ultraviolet irradiator 33.

  Further, in order to prevent the ink from drying during the pause, the modeling apparatus 30 may be provided with means such as a cap for closing the nozzles in the head units 31 and 32. In order to prevent nozzle clogging during continuous use for a long time, the modeling apparatus 30 may be provided with a maintenance mechanism for maintaining the head.

  The modeling apparatus 30 may include a mechanism for collecting or recycling the model material 1 and the support material 2. The modeling apparatus 30 may have a mechanism for detecting a model material 1 attached to the nozzle surfaces of the head units 31 and 32, a blade for removing the support material 2, or a non-ejection nozzle. Furthermore, the modeling apparatus 30 may have a mechanism for controlling the environment in the apparatus such as the temperature during modeling.

  There is no restriction | limiting in particular as the ultraviolet irradiation machine 33 used for hardening of the model material 1 and the support material 2, According to the objective, it selects suitably, A high pressure mercury lamp, an ultrahigh pressure mercury lamp, LED, a metal halide, etc. are illustrated. The ultra-high pressure mercury lamp is a point light source, but the Deep UV type, which has high light utilization efficiency in combination with an optical system, can irradiate in a short wavelength region. Since the metal halide has a wide wavelength region, it is selected according to the absorption spectrum of the photopolymerization initiator. Specific examples of the ultraviolet irradiator 33 include commercially available products such as an H lamp, D lamp, or V lamp manufactured by Fusion System.

  The modeling apparatus 30 discharges the hydrogel forming liquid as the model material 1 from the head unit 31, discharges the support material 2 from the head unit 32, and laminates the hydrogel forming liquid while curing with the ultraviolet irradiation machine 33. .

  That is, the modeling apparatus 30 discharges and hardens the support material 2 from the head unit 32 to form the first layer support portion 20 having a reservoir, and forms a hydrogel in the reservoir of the first layer support portion 20. The liquid for use is discharged from the head unit 31 and cured to form the first layer model portion 10. Further, the modeling apparatus 40 uses the roller 34 to smooth the surfaces of the model unit 10 and the support unit 20 to form a first modeling layer.

  Subsequently, the modeling apparatus 30 discharges and hardens the support material 2 on the first modeling layer, and stacks the second support portion 20 having a reservoir portion on the reservoir portion of the second layer support portion 20. The hydrogel-forming liquid is discharged and cured, and the second model part 10 is laminated on the first modeling layer. Furthermore, the modeling apparatus 40 uses the roller 34 to smooth the surfaces of the model unit 10 and the support unit 20 to form a second modeling layer. The modeling apparatus 30 obtains a three-dimensional modeled object in which the model unit 10 and the support unit 20 are integrated by repeating the above-described stacking.

  The modeling apparatus 30 can form, for example, a hydrogel body whose composition distribution and shape are controlled in accordance with the state of the treatment site of the individual patient. In this case, the modeling apparatus 30 uses personal data such as the shape of the patient's blood vessel and the hardness of the affected part, for example, to model a three-dimensionally shaped object of the blood vessel shape of the affected part to be a catheter treatment target, and for each part as necessary. A hardness distribution can be provided.

  In this case, the modeling apparatus 30 uses a plurality of types of hydrogel-forming liquids having different hardnesses of the cured products, and separates the hydrogel-forming liquids to be arranged for each part based on personal data. It is possible to provide a distribution in the hardness of the. In particular, a hardness distribution can be provided in accordance with the affected area of the patient to be treated.

  The amounts of the plurality of types of hydrogel-forming liquids may be different. Alternatively, the modeling apparatus 30 may have a mechanism for discharging each composition of the hydrogel-forming liquid, and may adjust the amount of the solvent by changing the ratio of the composition discharged from each mechanism.

  As a mechanism for discharging each composition of the hydrogel-forming liquid, as a first head for discharging the hydrogel-forming liquid, as a liquid for diluting the hydrogel-forming liquid, for example, water and a water-soluble solvent A second head for discharging the diluted liquid consisting of is exemplified. The hydrogel-forming liquid and the diluting liquid are ejected from the respective heads to the same location by a predetermined amount. Thereby, each liquid is mixed in each location, and the quantity ratio of the hydrogel-forming liquid and the diluted liquid is precisely controlled. Furthermore, the modeling apparatus 30 may have a head unit for discharging the polymer A.

<< Composite >>
The composite is formed by adhering two or more hydrogel bodies in a separable manner. As a method of adhering two or more hydrogel bodies, a method of interposing an arbitrary substance containing the polymer A between the two hydrogel bodies, or after shaping the hydrogel body, at least the surface of the hydrogel body Examples thereof include a method in which a part of the hydrogel-forming liquid is brought into contact and cured, and a method in which two hydrogel-forming liquids are simultaneously cured in a state where an arbitrary substance including the polymer A is interposed.

  When bonding the two hydrogel bodies, each may be housed in a mold or a frame to adjust the shape, or may be pressurized or depressurized from outside, or heated or cooled as necessary. Further, after bonding, unnecessary portions of the obtained composite may be excised, or the surface may be modified such as coloring or glossing.

When the composite is separated into two or more hydrogel bodies, the adhesive interface has a polymer A having a weight average molecular weight of 8000 or more. Although it does not specifically limit as a method of adhere | attaching a 1st hydrogel body and a 2nd hydrogel body so that isolation | separation is possible, The following method is illustrated.
-After the liquid containing the polymer A is attached to at least a part of the surface of the hydrogel body (an example of the first hydrogel body), another hydrogel body (second hydrogel) Example of body) Contacting a liquid containing polymer A to at least a part of the surface of the hydrogel body, and then forming a hydrogel to form another hydrogel body on the surface to which the liquid has adhered A method of contacting the liquid for curing and curing the hydrogel-forming liquid, a method of arranging the polymer A and two or more hydrogel bodies, and discharging each of the polymer A and two or more hydrogel-forming liquids Method of forming a liquid film and curing-Method of injecting polymer A or a mixture containing polymer A into the hydrogel body or composite-Method of polymer A inside the hydrogel body or composite Precursor, or A method of injecting a mixture containing the precursor of the monomer A with a syringe or the like and generating the weight body A therein. The precursor a1 of the polymer A on one hydrogel body, and the polymer A on the other hydrogel body The precursor a2 is added, and when one hydrogel body and the other hydrogel body are bonded, the precursor a1 and the precursor a2 are reacted to generate the weight body A.

  By the above method, a liquid in which the polymer A is dissolved or dispersed in an organic solvent may be attached to the hydrogel body. In this case, the process which removes an organic solvent from the liquid adhering to the hydrogel body may be performed.

<< Fracture surface extract >>
When the polymer A is soluble in methanol, the polymer A present at the adhesive interface of the composite can be extracted with methanol from the fracture surface when the composite is peeled off at the adhesive interface. Hereinafter, unless otherwise specified, the fracture surface extract represents one extracted from the fracture surface with methanol.

As a condition for obtaining the fracture surface extract, the hydrogel body peeled from the composite was washed by stirring for 10 minutes in 0.5 g of methanol per 1 cm ^{2 of the} fracture surface area, and the extract was washed at 50 ° C. A method of removing methanol under reduced pressure with an evaporator or the like while heating in a warm bath is exemplified. The molecular weight of the obtained extract is measured using gel permeation chromatography (GPC) or high performance liquid chromatography (HPLC).

<< Use of composite >>
The use of the complex is not particularly limited, and examples thereof include a biological tissue model and an organ model. The biological tissue model and the organ model may be a blood vessel model inclusion structure. These are suitably used as part of a practice kit for the purpose of practicing procedures such as endoscopic operation and catheter intubation.

<< Vessel model inclusion structure >>
In the present embodiment, the blood vessel model inclusion structure indicates a complex including a cylindrical hollow tube that imitates a blood vessel (hereinafter, referred to as “blood vessel model”). In the blood vessel model inclusion complex of the present embodiment, at least a part of the hollow blood vessel model formed of the hydrogel body is covered with the living tissue model formed of the hydrogel body via the polymer A. Yes. Alternatively, in the blood vessel model inclusion complex of the present embodiment, at least a part of the biological tissue model formed of the hydrogel body is covered with the hollow blood vessel model formed of the hydrogel body via the polymer A. It may be broken. Further, a medium simulating blood may be allowed to flow inside the hollow tube of the blood vessel model. Thereby, the tactile sensation and texture of the blood vessel model inclusion structure can be brought close to an actual organ. This also allows the medium flowing in the hollow tube when the blood vessel model is incised to flow out of the blood vessel model as if blood flows out. Moreover, handling property and preservation property can be improved by covering the blood vessel model with the biological tissue model.

  The blood vessel model may be bonded so as to be covered with a living tissue model such as a simple rectangular parallelepiped, but may be bonded so as to be covered with a living tissue model having a shape imitating an organ, for example. An organ model in which a blood vessel model is arranged in a biological tissue model simulating an organ is suitably used for technique training and preoperative simulation.

<< Biological tissue model >>
The biological tissue model is a hydrogel body or a composite covering the blood vessel model. The biological tissue model fixes the blood vessel model and improves the handleability when performing catheter intubation, improves the storage stability of the blood vessel model, and brings the tactile sensation when performing catheter intubation close to an actual blood vessel. A more realistic biological tissue model and organ model can be obtained by forming a biological tissue model using a hydrogel that is similar in composition and touch to the actual biological tissue.

<< Hard body cover >>
In order to improve the handleability, the hydrogel body or the composite of the present embodiment is preferably attached with a transparent hard body that transmits light as a cover. By attaching this, the following three functions can be improved.
(1) The shape of the hydrogel body or the composite is maintained, and the handleability in the practice of the technique is improved.
(2) The preservability, drying resistance, and antiseptic properties of the hydrogel body or composite are improved.
(3) The appearance of the hydrogel body or composite is improved.

  There is no restriction | limiting in particular as a material which forms a hard body, Although it selects suitably according to the objective, Transparent plastic materials, such as an acrylic resin and a polycarbonate resin, Transparent inorganic materials, such as glass, etc. are illustrated. . There is no restriction | limiting in particular as a shape and thickness of a hard body, According to the objective, it selects suitably.

By improving the drying resistance and antiseptic properties of the composite, the storage stability of the composite is improved. For example, in order to improve the antiseptic property of the blood vessel model, the blood vessel model may be covered with a cover formed of a hard body so as not to come into contact with the outside air. At this time, the drought resistance of the blood vessel model is improved by using a hard body having low water vapor permeability and oxygen permeability. The water vapor permeability (JIS K7129) of the hard body is preferably 500 g / m ² · d or less. The oxygen permeability (JIS Z1702) of the hard body is preferably 100,000 cc / m ² / hr / atm or less.

<< Organ model for technique practice >>
The above organ model can be used as an organ model for practice. There are no particular limitations on the organ model for practicing the technique, but a model that reproduces any part of the human body, such as the brain, heart, esophagus, stomach, bladder, small intestine, large intestine, liver, kidney, pancreas, spleen, or uterus. Illustrated.

  The organ model for practicing the technique of the present embodiment faithfully reproduces internal structures such as blood vessels and diseased parts, the tactile sensation and sharpness of the organ are very close to those of an actual organ, and can be opened with a scalpel. For this reason, the organ model for practicing practice is suitably used for practicing a technique by a doctor, a resident, a medical student, or the like, for example, in a medical department or a hospital of a university. Moreover, the organ model for procedure practice is suitably used for sharpness inspection by a manufacturer of a surgical knife.

  A liver model will be described as an example of an organ model for practice. The liver is the largest organ on the right side of the upper abdomen and below the ribs. The weight of an adult liver is 1.2 kg to 1.5 kg. Liver is a form of bile that helps the body to use, store and supply nutrients taken from food, detoxify to detoxify harmful substances, or help break down or absorb fat, etc. It works as a secretor.

  The liver is divided into a left lobe and a right lobe by a main dividing plane connecting the gallbladder and the inferior vena cava. Surgery to remove a part of the liver is hepatectomy. Most of the diseases for which hepatectomy is indicated are liver cancer (primary liver cancer), and other diseases include metastatic liver cancer, liver benign tumor, and liver trauma.

  There are various types of hepatectomy, such as partial excision, subsegmental excision, segmental excision, lobe excision, enlarged lobe excision, and three-segment excision depending on the cutting method. Since the liver is not marked, at the time of surgery, the boundaries between the above parts are identified by color changes by tying up the portal vein or hepatic artery or injecting pigment into the blood vessels. For excision of the liver, various machines such as an electric scalpel, harmonic scalpel (ultrasonic vibration surgical instrument), CUSA (ultrasonic surgical suction device), and microtase (microwave surgical instrument) are used.

  The organ model for practicing the technique of the present embodiment faithfully reproduces the inclusions such as blood vessels and diseased parts, has a tactile sensation and sharpness that is close to the real thing, and can be incised with a surgical knife. And is preferably used.

<< Endoscope practice kit, catheter tube kit >>
The blood vessel model inclusion structure and the technique training organ model are preferably used for endoscope insertion training, catheter intubation technique training, or simulation before surgery.

  Endoscope insertion training is for training an operation, an inspection by an inserted endoscope, or a treatment until an endoscope is inserted into an organ model for operation practice and reaches a target location. A set having an organ model for practicing practice and an endoscope that can be inserted into a catheter that can be hollowly inserted into a hollow in the organ model for practicing practice, that is, a blood vessel model, is suitably used as an endoscopic practice kit. The endoscope may be any commercially available product.

  In the catheter intubation technique training, a catheter is intubated into a blood vessel model inclusion structure and training is performed until a target location is reached. Catheter intubation technique training includes training such as changing the thickness of the catheter to be used according to the purpose, or providing a stent, wire, balloon, etc. at the tip, treating it at the affected site, or installing it . That is, selecting an optimal catheter according to the blood vessel shape is part of the training. For this reason, a set having a blood vessel model inclusion structure and a catheter that can be hollowly inserted into the blood vessel model inclusion structure is suitably used as a catheter tube delivery kit (an example of a practice kit). The catheter may be any commercially available product.

  The state in the blood vessel model of the blood vessel model inclusion structure is preferably similar to the state in the actual blood vessel. The blood vessel model inclusion structure of the present embodiment is formed of hydrogel, and its tactile sensation is very similar to that of a living body, and thus is suitably used for the training described above. In addition, a mechanism for flowing a liquid may be provided in the blood vessel model inclusion structure, and training may be performed in a state where blood flow is generated.

  Conventionally, since there were few transparent blood vessel models, training was performed by irradiating the blood vessel model with X-rays and visualizing it. The blood vessel model inclusion structure of the present embodiment may be formed of a permeable material. In this case, training can be performed without exposure to X-rays.

  The blood vessel model inclusion structure or the organ model as the complex may be modeled based on the affected area data of the patient by the three-dimensional modeling technique. As a result, a vascular model inclusion structure or an organ model in which the affected area of the patient is reproduced is suitable for a simulation before difficult surgery.

  In a conventional operation by inserting a stent into an aneurysm, the shape of the aneurysm is read from an X-ray image of the affected area, and a stent that seems to have an appropriate shape is selected during the operation. However, this selection is made based on the experience of a doctor, and it may take time to make a decision. By using the above-mentioned vascular model inclusion structure, it is possible to examine preoperatively, so what kind of member (stent etc.) should be selected according to the shape and physical properties of the aneurysm It becomes possible to identify and is expected to improve the success rate of surgery.

  EXAMPLES Hereinafter, although an Example and a comparative example are shown and this invention is demonstrated concretely, this invention is not limited by these Examples.

[Example 1]
(Method for producing polyvinyl alcohol solution 1)
A mixed solution of 45 parts of dimethyl sulfoxide and 135 parts of ion-purified water was heated to 90 ° C., and PVA117 (manufactured by Kuraray Co., Ltd., polyvinyl alcohol, saponification degree of 99.0 to 99.0 mol%, polymerization degree of 1700). ) 20 parts were added and stirred for 3 hours while maintaining 90 ° C. to obtain a polyvinyl alcohol solution 1.

(Method for producing hydrogel bodies 1 and 2)
The polyvinyl alcohol solution 1 was placed in a rectangular parallelepiped mold 1 having an internal shape of 100 mm × 100 mm in size and 8 mm in thickness, and cooled to 25 ° C. to obtain a rectangular parallelepiped polyvinyl alcohol gel. The gel was placed in a container having an internal size of 120 mm × 120 mm × 50 mm containing 250 g of methanol and left for 2 hours. After the gel was taken out and the methanol in the container was discarded, 250 g of ion-purified water was placed in the container, and the gel was placed again and left for 2 hours. Thereby, the hydrogel body 1 by which the dimethylsulfoxide in polyvinyl alcohol gel was substituted by methanol and also water was obtained. The obtained rectangular parallelepiped hydrogel body 1 was taken out of the container. In the same manner, a rectangular parallelepiped hydrogel body 2 having the same composition was also obtained.

(Method for producing composite 1)
9000 g of vinyl acetate (polymer) (50% by mass ethyl acetate solution, average molecular weight 42000, Showa Chemical) 9000 g is put in a container having an inner size of 173 mm × 173 mm × 400 mm, and the suspended hydrogel body 1 is put into the solution in the container. Soaked. Subsequently, the suspended hydrogel body 1 was pulled up and dried to remove ethyl acetate, which is a solvent for vinyl acetate (polymer), from the surface film, whereby a coated hydrogel body 1 was obtained.

The coated hydrogel body 1 is overlaid with the hydrogel body 2, and a compressive load of 1.2 kg (0.12 N / cm ² ) is applied in a direction perpendicular to the contact surface between the coated hydrogel body 1 and the hydrogel body 2. After storage for 1 hour, the obtained gel was cooled at −18 ° C. for 1 hour with a freezer (GS-1356HC, manufactured by Yamato Scientific Co., Ltd.) to obtain Complex 1.

  About the obtained composite 1, the tensile strength after peeling start, the tensile strength before peeling start, re-adhesiveness, modeled object hardness, and the methanol extraction result of the adhesion interface were evaluated with the following evaluation methods.

Result of methanol extraction of fracture surface:
The composite is pulled in a direction perpendicular to the bonding surface, the hydrogel body is peeled off at the bonding surface, the fracture surface is washed with methanol by the method described in the above embodiment, and the extract is removed under reduced pressure to obtain an extract. It was. The obtained extract was measured by GPC (Gel permeation chromatography), and it was evaluated whether the detected substance appeared at a weight average molecular weight of 8000 or more.
○: Detected ×: Not detected

  Heuristic evaluation by a surgeon was performed on the tensile strength after the start of peeling, the tensile strength before the start of peeling, the re-adhesiveness, and the hardness of the molded article.

Tensile strength after starting peeling, tensile strength before starting peeling:
After the composite 1 is peeled off using Metzenbaum (MZS-1, manufactured by ASONE), the hardness (tensile strength) until the peeling starts and the peeling starts (while peeling) The hardness was evaluated on a five-point scale from the viewpoint of whether it was similar to the kidney fiber membrane.
▲▲: Compared with kidney fiber membrane, it is clearly difficult to peel.
▲: Slightly less peelable than kidney fiber membranes.
○: Almost equivalent to kidney fiber membrane.
▼: Slightly easier to peel than the kidney fiber membrane.
▼▼: Easily peeled off compared with kidney fiber membrane.

Retackiness:
After the composite 1 was peeled off, the fracture surface of each hydrogel body was brought into close contact, and a compression load of 1.2 kg (0.12 N / cm ² ) was applied in the direction perpendicular to the interface for 1 minute. Thereafter, the interface was peeled again, and the hardness during peeling was evaluated from the viewpoint of whether it was similar to the kidney fiber membrane.
▲▲: Compared with kidney fiber membrane, it is clearly difficult to peel.
▲: Slightly less peelable than kidney fiber membranes.
○: Almost equivalent to kidney fiber membrane.
▼: Slightly easier to peel than the kidney fiber membrane.

Model hardness:
The hardness of the complex 1 was evaluated from the viewpoint of whether it was similar to the kidney.
▲▲: Harder than kidney.
○: Almost the same as kidney hardness.

[Example 2]
(Method for producing composite 2)
The hydrogel body 1 is superposed on the hydrogel body 1, and a compressive load of 1.2 kg (0.12 N / cm ² ) is applied in the direction perpendicular to the contact surface of the hydrogel body 1 and the hydrogel body 2 to 1 After time storage, the obtained gel was cooled at −18 ° C. for 1 hour using a freezer (GS-1356HC, manufactured by Yamato Scientific Co., Ltd.). 1.0 g of vinyl acetate (polymer) (50 wt% ethyl acetate solution, average molecular weight 42000, manufactured by Showa Chemical Co., Ltd.) was added to the interface between the hydrogel body 1 and the hydrogel body 2 in the obtained gel adhesive. UNFX00 (manufactured by ASONE) and stored at room temperature for 30 minutes to obtain composite 2. The composite 2 was evaluated in the same manner as in Example 1.

[Example 3]
(Preparation of hydrogel-forming liquid 1)
First, while stirring high-purity water, Laponite XLG was added little by little as a layered clay mineral and stirred to prepare a dispersion. Next, etidronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a dispersant for Laponite XLG.

  Next, acryloylmorpholine from which the polymerization inhibitor was removed by passing through an activated alumina column was added as a monomer to the obtained dispersion. Further, N, N'-methylenebisacrylamide as an organic crosslinking agent was added to the dispersion, and LS106 was added as a surfactant and mixed. Subsequently, N, N, N ′, N′-tetramethylethylenediamine was added to the mixed solution as a polymerization accelerator and mixed with stirring. After stirring and mixing, vacuum degassing was performed for 10 minutes. Subsequently, the liquid mixture was filtered to remove impurities and the like to obtain a homogeneous hydrogel-forming liquid 1.

(Components of hydrogel-forming liquid 1)
The components of the hydrogel-forming liquid 1 are as follows.
High purity water 70.2% by mass, as a layered clay mineral _{[Mg 5.34 Li 0.66 Si 8 O} 2 0 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, manufactured by RockWood Co.) 6% by mass, 22% by mass of acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd.) as a curable material, 0.2% by mass of N, N′-methylenebisacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.), Laponite XLG Etidronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3 mass% as a dispersant, N, N, N ′, N′-tetramethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 4 mass% as a polymerization accelerator, interface It contains 0.3% by mass of LS106 (Kao Corporation) as an activator.

(Production method of hydrogel bodies 3 and 4)
2 parts by mass of potassium peroxodisulfate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added to 98 parts by mass of ion-purified water and sufficiently dissolved to obtain a 2% by mass aqueous potassium peroxodisulfate solution. While 100 parts by mass of the hydrogel-forming liquid 1 is being stirred, 12 parts by mass of a potassium peroxodisulfate aqueous solution (2% by mass aqueous solution) is added and stirred for 10 seconds. When placed in a rectangular parallelepiped mold 1 having an internal shape of 100 mm and a thickness of 8 mm, sealed from above with a vinylidene chloride film (New Kurelap, manufactured by Kureha Co., Ltd.) and stored at 25 ° C. for 12 hours, the liquid hardened. The cured hydrogel body 3 was taken out and obtained. A hydrogel body 4 having the same composition was obtained in the same manner.

(Method for producing composite 3)
9000 g of vinyl acetate (polymer) (50 mass% ethyl acetate solution, average molecular weight 42000, Showa Chemical) 9000 g is put in a container having an inner size of 173 mm × 173 mm × 400 mm, and the suspended hydrogel body 3 is put into the solution in the container. Soaked. Subsequently, the suspended hydrogel body 3 was pulled up and dried to remove ethyl acetate, which is a solvent for vinyl acetate (polymer), from the surface film, whereby a coated hydrogel body 3 was obtained.

The coated hydrogel body 3 is overlaid with the hydrogel body 4, and a compressive load of 1.2 kg (0.12 N / cm ² ) is applied in a direction perpendicular to the contact surface between the coated hydrogel body 3 and the hydrogel body 4. And stored for 1 hour to obtain a composite 3. The composite 3 was evaluated in the same manner as in Example 1.

[Example 4]
(Preparation of coating solution 1)
In a mixed solvent of 45 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) and 45 parts by mass of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), VINNOL E15 / A48 (molecular weight: 22000, vinyl chloride: hydroxypropyl acrylate = 83. 5: 16.5 [mass%], manufactured by Sakai Chemical Industry Co., Ltd.) 10 parts by mass were added little by little with stirring and stirred at 25 ° C. for 2 hours. The obtained solution was filtered with a filter paper (No. 5C, manufactured by Advantech) and degassed under reduced pressure to obtain a colorless and transparent coating solution 1.

(Method for producing composite 4)
The composite 4 was obtained by the same method as the composite 3 except that the vinyl acetate (polymer) was replaced with the coating liquid 1 in the production method of the composite 3. The composite 4 was evaluated in the same manner as in Example 1.

[Example 5]
(Preparation of coating solution 2)
In a mixed solvent of 45 parts by mass of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) and 45 parts by mass of toluene (manufactured by Wako Pure Chemical Industries, Ltd.), Solvain TA5R (molecular weight: 18000, vinyl chloride: vinyl acetate: vinyl alcohol = 88: 1:11 [mass%] (manufactured by Nissin Chemical Industry Co., Ltd.) 10 parts by mass were added little by little with stirring and stirred at 25 ° C. for 2 hours. The obtained solution was filtered with a filter paper (No. 5C, manufactured by Advantech) and degassed under reduced pressure to obtain a light yellow transparent coating solution 2.

(Method for producing composite 5)
The composite 5 was obtained by the same method as the composite 3 except that the vinyl acetate (polymer) was replaced with the coating liquid 2 in the composite 3 production method. The composite 5 was evaluated in the same manner as in Example 1.

[Example 6]
(Preparation of coating solution 3)
To 90 parts of methanol (manufactured by Wako Pure Chemical Industries, Ltd.), 10 parts by mass of JMR-8M (molecular weight: 8000, saponification degree 68 (mol%), manufactured by Nihon Vinegar Bipoval Co., Ltd.) was added little by little at 25 ° C. For 2 hours. The obtained solution was filtered with a filter paper (No. 5C, manufactured by Advantech) and degassed under reduced pressure to obtain a colorless and transparent coating solution 3.

(Method for producing composite 6)
A composite 6 was obtained by the same method as the composite 3 except that the vinyl acetate (polymer) was replaced with the coating liquid 3 in the method of preparing the composite 3. The composite 6 was evaluated in the same manner as in Example 1.

[Example 7]
(Preparation of coating solution 4)
Preparation similar to coating liquid 3 except that JMR-8M is changed to JMR-150L (molecular weight: 120,000, saponification degree: 22 (mol%), manufactured by Nihon Vinegar Bipoval Co., Ltd.) in the method for preparing coating liquid 3. A colorless and transparent coating solution 4 was obtained by this method.

(Method for producing composite 7)
A composite 7 was obtained by the same method as the composite 3 except that the vinyl acetate (polymer) was replaced with the coating liquid 4 in the composite 3 production method. The composite 7 was evaluated in the same manner as in Example 1.

[Example 8]
(Preparation method of coating liquid 5)
Except for changing JMR-8M to JMR-8L (molecular weight: 14000, saponification degree: 1.5 (mol%), manufactured by Nihon Vinegar Bipoval Co., Ltd.) in the preparation method of coating liquid 3, the same as coating liquid 3 A colorless and transparent coating solution 5 was obtained by the above production method.

(Production method of composite 8)
The composite 8 was obtained by the same method as the composite 3 except that the vinyl acetate (polymer) was replaced with the coating solution 5 in the production method of the composite 3. The composite 8 was evaluated in the same manner as in Example 1.

[Example 9]
(Preparation method of coating liquid 6)
Preparation similar to coating liquid 3 except that JMR-8M in the preparation method of coating liquid 3 is changed to JMR-10L (molecular weight: 18000, saponification degree: 37 (mol%), manufactured by Nihon Vinegar Bipoval Co., Ltd.) A colorless and transparent coating solution 6 was obtained by this method.

(Method for producing composite 9)
A composite 9 was obtained by the same method as the composite 3 except that vinyl acetate (polymer) was replaced with the coating liquid 6 in the composite 3 production method. The composite 9 was evaluated in the same manner as in Example 1.

[Example 10]
(Method for producing composite 10)
In the production method of the composite 3, except that the hydrogel body 3 is replaced with the hydrogel body 1, vinyl acetate (polymer) is replaced with the coating liquid 6, and the hydrogel body 4 is replaced with the hydrogel body 2. The composite 10 was obtained by the same method. The composite 10 was evaluated in the same manner as in Example 1.

[Example 11]
(Hydrogel body 5)
When 70 g of the hydrogel-forming liquid 1 was stirred, 8.4 g of 2% by mass potassium peroxodisulfate was added and stirred for 10 seconds. FIG. 2A is a perspective view of a mold used in the eleventh embodiment. FIG. 2B is a perspective view of a hydrogel body obtained by a mold. The liquid obtained by stirring was put into a mold 51 having an inner dimension of 105 mm × 105 mm and a thickness of 13 mm, and further, a core 52 having an outer dimension of 100 mm × 100 mm and a thickness of 8 mm was combined and sealed. After sealing, the liquid was cured when stored at 25 ° C. for 12 hours. The hydrogel body 5 was obtained by taking out the cured hydrogel body 5.

(Method for producing composite 11)
In the production method of the composite 3, the composite 11 is obtained by the same method as the production of the composite 3, except that the vinyl acetate (polymer) is replaced with the coating liquid 6 and the hydrogel body 4 is replaced with the hydrogel body 5. It was. The composite 11 was evaluated in the same manner as in Example 1.

[Example 12]
(Hydrogel body 6)
When 10 g of the hydrogel-forming liquid 1 was stirred, 1.22 g of 2% by mass potassium peroxodisulfate was added and stirred for 10 seconds. FIG. 3A is a perspective view of a mold used in Example 12. FIG. FIG. 3B is a perspective view of the gel. The liquid obtained by stirring was placed in a mold 61, and a core 62 was disposed and sealed. After sealing, when stored at 25 ° C. for 12 hours, the liquid hardened, and a cylindrical gel having an inner diameter of 5 mm, an outer diameter of 7.5 mm, and a length of 100 mm was obtained. The hydrogel body 6 was obtained by taking out the cured hydrogel body 6.

(Hydrogel body 7)
When 900 g of the hydrogel-forming liquid 1 was stirred, 108 g of 2% by mass potassium peroxodisulfate was added and stirred for 15 seconds. 4A is a perspective view of a mold used in Example 12. FIG. FIG. 4B is a perspective view of the gel. The obtained liquid was put into a container 71 having an inner dimension of 100 mm, and a cylindrical core 72 having an outer diameter of 7.5 mm and a length of 100 mm was further sealed, and the liquid was cured when stored at 25 ° C. for 12 hours. The cured gel was taken out to obtain a hydrogel body 7.

(Method for producing composite 12)
In the preparation method of the composite body 3, the hydrogel body 3 is replaced with the hydrogel body 6, the vinyl acetate (polymer) is replaced with the coating liquid 6, and the hydrogel body 4 is replaced with the hydrogel body 7. The composite 12 was obtained by the same method. FIG. 5 is a perspective view of the composite 12 obtained in Example 12. FIG. The composite 12 was evaluated in the same manner as in Example 1.

[Example 13]
(Method for producing composite 13)
9000 g of coating liquid 6 is put in a container having an inner size of 173 mm × 173 mm × 400 mm, and a hydrogel body 6 containing a cylindrical core having an outer diameter of 5 mm and a length of 100 mm is suspended and immersed in the solution in the container. After pulling up, the film hydrogel body 6 'was obtained by drying. By drying, methanol as a solvent of JMR-10L was removed from the coating on the surface of the coating hydrogel body 6 '.

  FIG. 6 is a conceptual diagram for explaining a process for producing a composite in Example 13. A solution obtained by fixing the coated hydrogel body 6 'containing the core 83 to a container 71 having an inner size of 100 mm and stirring the hydrogel-forming liquid 1 and 900 g of 2 mass% potassium peroxodisulfate for 15 seconds. 1 'was put in the container 71 and sealed. After sealing, the liquid was cured when stored at 25 ° C. for 12 hours. After curing, the core 83 was removed, and the cured gel was taken out from the cube to obtain a composite 13. The composite 13 was evaluated in the same manner as in Example 1.

[Example 14]
-Preparation of hydrogel-forming liquid 2-
First, while stirring pure water, Laponite XLG was added little by little as a layered clay mineral and stirred to prepare a dispersion. Next, etidronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) was added as a dispersant for Laponite XLG.

  Next, acryloylmorpholine from which the polymerization inhibitor was removed by passing through an activated alumina column was added as a monomer to the obtained dispersion. Furthermore, N, N'-methylenebisacrylamide was added as an organic crosslinking agent. LS106 was added as a surfactant and mixed. Next, N, N, N ′, N′-tetramethylethylenediamine was added as a polymerization accelerator, and then Irgacure 184 was added as a photopolymerization initiator in a 4% by mass methanol solution and mixed with stirring. After stirring and mixing, vacuum degassing was performed for 10 minutes. Subsequently, the dispersion liquid was filtered using a filter paper (No. 5C, manufactured by Advantech) to remove impurities and the like to obtain a homogeneous hydrogel-forming liquid 2.

<Constituent components of hydrogel-forming liquid 2>
The components of the hydrogel-forming liquid 2 are as follows.
High purity water 60 wt%, as a layered clay mineral _{[Mg 5.34 Li 0.66 Si 8 O} 20 (OH) 4] Na - 0.66 synthetic hectorite having a composition of (Laponite XLG, manufactured by RockWood Ltd.) 6 wt% Glycerin (manufactured by Sakamoto Yakuhin Kogyo Co., Ltd.) 10.2% by mass as an anti-drying agent, acryloylmorpholine (manufactured by KJ Chemicals Co., Ltd.) 22% by mass as a curable material, and N, N′-methylenebisacrylamide (as an organic crosslinking agent) 0.2% by mass (manufactured by Tokyo Chemical Industry Co., Ltd.), etidronic acid (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.3% by mass as a dispersant for Laponite XLG, and Irgacure 184 (manufactured by BASF) (4% by mass) as a photopolymerization initiator. Methanol solution) 0.6% by mass, N, N, N ′, N′-tetramethylethylenediamine as a polymerization accelerator Tokyo Chemical Industry Co., Ltd.) 0.4 wt%, including LS106 a (Kao Corporation) 0.3 mass% as a surfactant.

(Method for producing composite 14)
<Layered modeling>
The hydrogel-forming liquid 2 and the coating liquid 6 were filled in and discharged from two inkjet heads (GEN4 manufactured by Ricoh Industry Co., Ltd.) of the modeling apparatus. The hydrogel-forming liquid 2 discharged, the ultraviolet ray irradiation device (manufactured by Ushio Inc., SPOT CURE SP5-250DB) curing the hydrogel-forming liquid 2 was irradiated with light intensity of 350 mJ / cm ^2, the model unit And a support part was formed.

  FIG. 7 is a diagram for explaining a modeling process in the fourteenth embodiment. As shown in FIG. 7A, the modeling apparatus first discharges and cures the hydrogel-forming liquid 2 to form a hydrogel body 8 having a size of 100 mm × 100 mm and a thickness of 5 mm. Then, as shown to (B) of FIG. 7, a modeling apparatus discharges the coating liquid 6 by 100 mm x 100 mm and thickness 0.1mm on a hydrogel body, and makes it dry. As shown in FIG. 7C, the modeling apparatus discharges the hydrogel-forming liquid 2 onto the dried product D of the coating liquid 6 and cures it to have a size of 100 mm × 100 mm and a thickness of 5 mm. A hydrogel body 9 was formed to obtain a composite 14 having a size of 100 × 100 mm and a thickness of 10 mm. The composite 14 was evaluated in the same manner as in Example 1.

[Example 15]
(Method for producing composite 15)
FIG. 8 is a perspective view of the composite 15 manufactured in Example 15. FIG. In the method for producing the composite 14, the hydrogel forming liquid 2 and the coating liquid 6 are discharged in the same pass as shown in FIG. 8, and the hydrogel forming liquid 2 is cured after discharging. A composite 15 was prepared in the same manner as the composite 14 was prepared. The composite 15 has an interface of the coating liquid 6 in the stacking direction, and the size is 10 mm × 10 mm and the thickness is 50 mm. The composite 15 was evaluated in the same manner as in Example 1.

[Comparative Example 1]
(Method for Manufacturing Composite 101)
The hydrogel body 1 is superposed on the hydrogel body 1, and a compressive load of 1.2 kg (0.12 N / cm ² ) is applied in the direction perpendicular to the contact surface of the hydrogel body 1 and the hydrogel body 2 to 1 After storage for a period of time, the obtained gel was cooled at −18 ° C. for 1 hour using a freezer (GS-1356HC, manufactured by Yamato Scientific Co., Ltd.) to obtain a composite 101. The composite 101 was evaluated in the same manner as in Example 1.

  The hydrogel body 1 does not go through the step of immersing in vinyl acetate (polymer) as in Example 1. Therefore, in the composite 101, the peel strength has increased due to the excessive adhesion of the hydrogel body 1 and the hydrogel body 2.

[Comparative Example 2]
(Method for manufacturing composite 102)
The hydrogel body 4 is superposed on the hydrogel body 3, and a compressive load of 1.2 kg (0.12 N / cm ² ) is applied in a direction perpendicular to the contact surface between the hydrogel body 3 and the hydrogel body 4 to 1 The composite 102 was obtained by storing for a while. The composite 101 was evaluated in the same manner as in Example 1.

  The hydrogel body 2 has not gone through the step of immersing in vinyl acetate (polymer) as in Example 3. Therefore, the composite 102 has increased peel strength due to excessive adhesion between the hydrogel body 3 and the hydrogel body 4.

[Comparative Example 3]
(Method for manufacturing composite 103)
A composite 103 was obtained in the same manner as the composite 1 except that vinyl acetate (monomer) was used instead of vinyl acetate (polymer) in the method of manufacturing the composite 1 in Example 1. The composite 101 was evaluated in the same manner as in Example 1.

  Since the hydrogel body 103 uses vinyl acetate (monomer) instead of vinyl acetate (polymer), the adhesion between the hydrogel body 1 and the hydrogel body 2 is inhibited. Therefore, the composite 103 has weak peel strength between the hydrogel body 1 and the hydrogel body 2.

[Comparative Example 4]
(Method for manufacturing composite 104)
A composite 104 was obtained by the same method as the composite 1 except that ethyl acetate was used in place of vinyl acetate (polymer) in the method of manufacturing the composite 1 in Example 1.

  Since the hydrogel body 104 uses ethyl acetate instead of vinyl acetate (polymer), all ethyl acetate has been removed during drying. Therefore, the composite 104 had a strong peel strength between the hydrogel body 1 and the hydrogel body 2 as in Comparative Example 1.

[Comparative Example 5]
(Method for Manufacturing Composite 105)
In the manufacturing method of the composite 1 in Example 1, 10 mass% polyvinyl alcohol (PVA117, the Kuraray Co., Ltd. make, molecular weight 75000, saponification degree, 98.5 (mol%)) is used instead of vinyl acetate (polymer). Obtained the composite 105 by the method similar to the preparation method of the composite 1.

  The composite 105 is made of saponified polyvinyl alcohol instead of vinyl acetate (polymer). The fully saponified polyvinyl alcohol was not sufficiently dried because of its high affinity with water, and adhesion between the hydrogel body 1 and the hydrogel body 2 was inhibited. Therefore, in the composite 105, the peel strength between the hydrogel body 1 and the hydrogel body 2 was weakened. Further, since completely saponified polyvinyl alcohol has low solubility in methanol at room temperature, polyvinyl alcohol was not detected from the cleaning solution when the fracture surface was washed with methanol.

  The production methods of the composites in each Example and Comparative Example are shown in Table 1. Table 2 shows the evaluation results of the composites in each Example and Comparative Example.

DESCRIPTION OF SYMBOLS 1 Model material 2 Support material 10 Model part 20 Support part 30 Modeling apparatus 31 Head unit 32 Head unit 33 Ultraviolet irradiation machine 34 Roller 35 Carriage 36 Substrate 37 Stage 100 Three-dimensional model

Japanese Patent No. 5759055

Claims (12)

  A composite having two or more hydrogel bodies bonded in a peelable manner and having a polymer having a weight average molecular weight of 8000 or more on the fracture surface when peeled at the bonding interface.   The composite according to claim 1, wherein the polymer is soluble in methanol. The polymer has a hydroxyl group and a substituent other than a hydroxyl group that is more hydrophobic than the hydroxyl group,
The composite according to claim 1 or 2, wherein a ratio of the hydroxyl group to a substituent other than the hydroxyl group is in the range of 1.0: 99.0 to 90.0: 10.0. Peeling The composite according to any one of claims 1 to 3, wherein the polymer contains polyvinyl alcohol having a saponification degree of 90 mol% or less. The at least one part of the 1st hydrogel body in the said 2 or more hydrogel bodies is covered with the 2nd hydrogel body in the said 2 or more hydrogel bodies. The complex described. The composite according to claim 1, wherein at least one of the first hydrogel body and the second hydrogel body in the two or more hydrogel bodies has a hollow shape. The first hydrogel body is a blood vessel model,
The composite according to claim 6, wherein the second hydrogel body is a biological tissue model.   The composite according to claim 7, wherein the composite is covered with a transparent covering member that transmits light. A complex according to claim 6;
Endoscope that can be inserted into the hollow in the hydrogel body, or catheter,
Having a practice kit. Attaching a liquid containing a polymer having a weight average molecular weight of 8000 or more to the surface of the first hydrogel body;
The surface of the first hydrogel body to which the liquid is attached is brought into contact with the second hydrogel body or the liquid for forming the second hydrogel body, the first hydrogel body, and Forming a complex in which the second hydrogel body is releasably bonded; and
The manufacturing method of the composite_body | complex which has. Discharging a curable liquid containing water, monomer and mineral to form a liquid film;
A step of curing the liquid film to form a layer, and laminating the layers to form at least one of the first hydrogel body and the second hydrogel body. Item 11. A method for producing the composite according to Item 10. In the step of attaching a liquid containing a polymer having a weight average molecular weight of 8000 or more to the surface of the first hydrogel body, the liquid containing the polymer having a weight average molecular weight of 8000 or more is used as the surface of the first hydrogel body. The method for producing a composite according to claim 10 or 11.

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