JP6414193B2 - Polymer gel and method for producing the same - Google Patents

Description

  The present invention relates to a polymer gel and a method for producing the same, and more particularly to a water-containing polymer gel material for molding a medical material having both the properties of each of two or more polymers and a method for producing the same.

A polymer gel is a material that forms a three-dimensional network structure by cross-linking polymers, and can hold a solvent several hundreds or thousands of times its own weight. This is called hydrogel.
Such a hydrogel is a useful material that has been attracting attention because of its excellent water retention properties as described above, and has been conventionally used in fields such as medicine / medicine, food, civil engineering, and bioengineering. For example, it is used for highly water-absorbing resin, paper diapers, sanitary products, soft contact lenses, water-containing sheets for indoor greening and the like. In addition, it has sustained drug release properties and is applied to medical materials such as drug delivery systems and wound dressings. It is also used for shock absorbing materials, vibration control / soundproof materials, etc., and its uses are diverse.

  However, hydrogels generally have low strength, and there is a problem that the structure breaks down with a small stress, and it has been a problem to improve mechanical strength. As a method for improving the mechanical strength of the hydrogel, the inventors polymerize the first monomer component in a mold to form a gel having a first network structure, and then use this gel to form a second gel. After immersing in the solution containing the monomer component and diffusing the solution in the gel, the gel is taken out and the second monomer component in the gel is polymerized to polymerize each other having a crosslinked network structure, or to crosslink A method for producing a hydrogel having a structure (interpenetrating network structure or semi-interpenetrating network structure) in which a polymer having a network structure and a linear polymer are entangled with each other is disclosed (Patent Document 1). In addition, the inventors introduced the first monomer into the physical crosslinking gel, polymerized and crosslinked the first monomer to form the first network structure, and then introduced the second monomer. Discloses a method for producing a polymer gel in which a second network is formed by polymerizing and crosslinking a second monomer (Patent Document 2).

International Publication No. 03/093337 Pamphlet JP 2009-298971 A

However, the polymer gel obtained by the method disclosed in Patent Document 1 has an extremely weak gel having the first network structure obtained in an intermediate stage, and is difficult to maintain in a desired shape. Large and complex shapes are difficult to mold. There is also a problem that the gel having the first network structure is weak and difficult to handle.
The polymer gel obtained by the method disclosed in Patent Document 2 has good strength, has a high degree of freedom in molding shape, and can be continuously produced. The polymer gel obtained by this method has two types. The properties of the entire gel are determined by any one of the polymers used, and not the properties of both of the two polymers used. It was difficult to obtain a gel having the following properties.
Accordingly, an object of the present invention is to provide a polymer gel having the properties of two kinds of polymers constituting a polymer gel having a network structure, and a method for producing the same.

In order to achieve the above object, the present inventors have intensively studied and found that the above problem can be solved by forming a network structure by crosslinking using a specific first polymer and a second polymer. Got.
The present invention has been made on the basis of the above findings, and the molding is characterized in that the first polymer and the second polymer form a network structure by cross-linking between different polymers. The first polymer and the second polymer are cross-linked by a first monomer, and the amount of the first monomer is the composition of the first polymer. The present invention provides a water-containing polymer gel material for a medical material molded product, which is 0.2 to 1.0 mol per monomer unit.
Moreover, this invention is a medical-materials molded article of Claim 1 by which the said 1st polymer and 2nd polymer were bridge | crosslinked by the (meth) acrylic acid derivative or vinyl derivative which has an isocyanate group. A hydrous polymer gel material is provided.
Further, in the present invention, the first polymer is a polymer having reactivity with an isocyanate group, and the second polymer is a polymer copolymerizable with a (meth) acryl group or a vinyl group. A hydrous polymer gel material for medical material moldings is provided.
In the present invention, a polymer having reactivity with an isocyanate group and a polymer copolymerizable with a (meth) acrylic group or a vinyl group are crosslinked by a (meth) acrylic acid derivative or a vinyl derivative having an isocyanate group. The amount of the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is 0.2 to 1 per constituent monomer unit of the polymer having reactivity with the isocyanate group. Provided is a hydrous polymer gel material for medical material moldings, which is 0.0 mol.
Examples of the polymer having reactivity with the isocyanate group include cellulose derivatives.

The polymer copolymerizable with the (meth) acrylic group or vinyl group is at least one selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers. And a polymer obtained by polymerizing the second monomer.
Further, the present invention is a method for producing a hydrous polymer gel material for a medical material molded article in which an intercrosslinking network structure is formed between a second polymer composed of a second monomer and the first polymer, The polymerization reactive group is introduced by reacting the first polymer with a first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group to introduce a polymerization reactive group into the first polymer. By copolymerizing a second monomer having a functional group copolymerizable with the polymerization reactive group in the presence of the first polymer having the polymerization reactive group. In the method, an inter-crosslinking network structure is formed between the second polymer composed of two monomers and the first polymer, and the amount of the first monomer used is the composition of the first polymer. 0.2 per monomer unit The process is provided which is ˜1.0 mol.
Examples of the polymerization reactive group include a (meth) acryl group and a vinyl group.
Examples of the polymer reactive group include an isocyanate group.
Examples of the first monomer include (meth) acrylic acid derivatives or vinyl derivatives having an isocyanate group, and the first polymer is a polymer having reactivity with an isocyanate group.
Examples of the polymer having reactivity with the isocyanate group include cellulose derivatives.

Examples of the second monomer include monomers selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers.
The present invention also introduces an acrylic group or vinyl group into the first polymer by polymerizing a (meth) acrylic acid derivative or vinyl derivative having an isocyanate group with a first polymer having reactivity with the isocyanate group. To obtain a first polymer having an acrylic group or a vinyl group, and then, in the presence of the first polymer having an acrylic group or a vinyl group, a first polymer having a functional group copolymerizable with the acrylic group or the vinyl group. 2 is a method of forming a cross-linked network structure between a second polymer composed of a second monomer and the first polymer by copolymerizing two monomers, and having the isocyanate group (meta ) The acrylic acid derivative or vinyl derivative is 0.2 to 1.0 mol per monomer unit of the first polymer. To provide a method of manufacturing a medical material for a molded article hydrous polymer gel material.
Examples of the first polymer include cellulose derivatives.
Examples of the second monomer include monomers selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers.

  The hydrous polymer gel material for medical material molded articles of the present invention has improved mechanical strength and has the characteristics of two or more kinds of polymers. Further, according to the method for producing a hydrous polymer gel material for molded medical material of the present invention, the mechanical strength is improved, and a polymer gel material having the characteristics of two or more polymers can be easily produced. .

It is a graph which shows the result (stress-strain curve, SS curve) of a tension test. It is a graph which shows the maximum distortion of the polymer gel obtained by the Example and the comparative example. It is a graph which shows the relationship between a crosslinking point density | concentration and a maximum distortion. It is a graph which shows the measurement result of a moisture content. It is a graph which shows the result (stress-strain curve, SS curve) of a tension test. It is a graph which shows the result (stress-strain curve, SS curve) of a tension test. It is a graph which shows the result (stress-strain curve, SS curve) of a tension test. It is a graph which shows the result (stress-strain curve, SS curve) of a tension test.

Hereinafter, the water-containing polymer gel material for a medical material molded product of the present invention will be described first. In the following description, the water-containing polymer gel material for medical material molded products is also simply referred to as a polymer gel.
In the polymer gel of the present invention, the first polymer and the second polymer form a network structure by cross-linking between different polymers. The network structure in the polymer gel of the present invention will be described.
Conventionally, a gel having an interpenetrating network (IPN) is known as a gel having a three-dimensional network structure. The interpenetrating network structure is formed by polymerizing the first monomer component to form a gel having the first network structure, and then immersing the gel in a solution containing the second monomer component to thereby store the solution in the gel. After the gel is diffused, the gel is taken out and the second monomer component of the gel is polymerized, whereby a polymer having a crosslinked network structure or a structure in which a polymer having a crosslinked network structure and a linear polymer are entangled with each other (mutually) It is a gel having an intrusion network structure (full IPN) or a semi-interpenetrating network structure (semi-IPN).
In addition, a cross-linked network structure in which a cross-linked structure (Internet Cross-linking (INC)) of a polymer chain composed of a first monomer and a polymer chain composed of a second monomer exists is also known. (Macromolecules 2009, 42, 2184-2189 True Chemical Structure of Double Network Hydrogels)

  The polymer gel of the present invention has a network structure not conventionally known. That is, in the polymer gel of the present invention, there is no cross-linking between the first polymers and no cross-linking between the second polymers, and cross-linking between the first polymer and the second polymer is formed, thereby A network structure is formed. In the present specification, this network structure is also referred to as an intercross linked network (ICN). The polymer gel having such a network structure has not been known so far and has been found for the first time by the present inventors. In the polymer gel of the present invention, since there is no cross-linking between the first polymers and cross-linking between the second polymers, the properties of both the first polymer and the second polymer affect the overall properties. It is a polymer gel that has the properties of two types of polymers.

The polymer gel of the present invention will be described. In the polymer gel of the present invention, the first polymer and the second polymer form a network structure by cross-linking between different polymers.
The 1st polymer and 2nd polymer which comprise the polymer gel of this invention are demonstrated. The polymer gel of the present invention is formed by crosslinking a first polymer and a second polymer by forming a network structure by crosslinking between different polymers. Therefore, a combination of a compound that crosslinks the first polymer and the second polymer is important. In the present specification, “cross-linking between different types of polymers” means that the same types of polymers are not cross-linked, and cross-linking with different types of polymers is formed. That is, in the present invention, the first polymer and the second polymer are crosslinked with an arbitrary compound (hereinafter also referred to as a first monomer), for example, a compound as described later.

  As a specific example of the polymer gel of the present invention, for example, a first polymer and a second polymer are crosslinked by a first monomer. Examples of the first monomer include compounds having a reactivity with the first polymer and a polymerization reactive group. Having reactivity with the first polymer means having a functional group capable of crosslinking with the first polymer. For example, when a cellulose derivative is used as the first polymer, a compound having an isocyanate group Is applicable. Examples of the polymerization reactive group include a (meth) acryl group and a vinyl group. Accordingly, examples of the first monomer include (meth) acrylic acid derivatives having an isocyanate group and vinyl derivatives having an isocyanate group. That is, the polymer gel of the present invention includes one in which the first polymer and the second polymer are cross-linked by a (meth) acrylic acid derivative or a vinyl derivative having an isocyanate group. In this case, a polymer having reactivity with an isocyanate group is used as the first polymer, and a monomer copolymerizable with a (meth) acryl group or a vinyl group is used as the monomer constituting the second polymer. It is done.

The (meth) acrylic acid derivative or vinyl derivative having an isocyanate group will be described.
Examples of the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group include compounds represented by the following general formulas (1) to (3).
R ¹ —O—R ² —NCO (1)
(In the formula, R ¹ is an acryl group, a methacryl group or a vinyl group, and R ² is an alkylene group)
R ¹ —O—R ³ —O—R ⁴ —NCO (2)
(In the formula, R ¹ is an acryl group, a methacryl group or a vinyl group, and R ³ and R ⁴ may be the same or different, and each is an alkylene group)

(In the formula, R ¹ is an acryl group, a methacryl group or a vinyl group, and R ⁵ is an alkyl group)
Examples of the compound represented by the general formula (1) include compounds represented by the following formulas (4) and (5).

  Moreover, as a compound represented by the said 1 group formula (2), the compound represented by following formula (6) is mentioned.

  Moreover, as a compound represented by the said General formula (3), the compound represented by following formula (7) is mentioned.

  As the compounds represented by the above formulas (4), (5), (6) and (7), commercially available compounds can be used. For example, Karenz MOI (registered trademark) manufactured by Showa Denko KK Examples include Karenz AOI (registered trademark), Karenz MOI-EG (registered trademark), Karenz BEI (registered trademark), and the like. Moreover, the compound deblocked by heat processing and reproducing | regenerating an active isocyanate group can also be used, For example, the compound represented by following formula (8) and (9) is mentioned as such a compound.

  As the compounds represented by the above formulas (8) and (9), commercially available compounds can be used. For example, Karenz MOI-BP (registered trademark), Karenz MOI-BM (registered trademark) manufactured by Showa Denko KK Trademark) and the like.

Next, the first polymer will be described. The first polymer forms a network structure by cross-linking between a second polymer described later and different polymers. As a specific example, since it can be cross-linked by the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group described above, a polymer having reactivity with an isocyanate group can be used.
As the polymer having reactivity with an isocyanate group, a polymer into which a functional group having reactivity with an isocyanate group is introduced is preferable. Examples of such functional groups include a hydroxyl group, a carboxyl group, an amino group, an amide group, a mercapto group, and the like. That is, examples of the first polymer include a polymer having a hydroxyl group, a polymer having a carboxyl group, a polymer having an amino group, a polymer having an amide group, and a polymer having a mercapto group.

  Examples of the polymer having a hydroxyl group include cellulose derivatives such as methyl cellulose, ethyl cellulose, acetyl cellulose, cellulose acetate, and cellulose triacetate; acidic cellulose derivatives having a carboxyl group in the side chain; polyvinyl alcohol, dextran, alkyl cellulose, agarose, pullulan, Inulin, chitosan, poly 2-hydroxypropyl (meth) acrylate and the like can be mentioned.

  As a polymer which has a carboxyl group, the copolymer etc. which use (meth) acrylic acid ester and (meth) acrylic acid as a copolymerization component are mentioned, for example.

  Examples of the polymer having an amino group include polyallylamine, polyethyleneimine, poly-3-aminopropyl (meth) acrylate, poly-3-aminopropyl (meth) acrylamide, chitosan, diallylamine acetate / sulfur dioxide copolymer, acrylamide Examples include diallyldimethylammonium chloride copolymer.

  Examples of the polymer having an amide group include polyvinyl pyrrolidone, polyvinyl caprolactam, polyvinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone / vinyl caprolactam copolymer, vinyl pyrrolidone / vinyl imidazole copolymer, vinyl pyrrolidone / acrylic acid copolymer. , Vinylpyrrolidone / methacrylic acid copolymer, vinylpyrrolidone / 3-methyl-1-vinylimidazolium salt copolymer, N-vinylpyrrolidone, N-vinylpiperidone, N-vinylcaprolactam, protein, polypeptide, oligopeptide Etc.

Examples of the polymer having a mercapto group include HS- (A-S _x ) _m -ASH (1)
(Wherein A is a substituent that reacts with an isocyanate group, x is an integer of 1 to 5, and m is an integer of 1 to 50). Examples of the substituent that reacts with the isocyanate group in the formula include a hydroxyl group.

Next, the second polymer will be described. A 2nd polymer forms a network structure by bridge | crosslinking between the 1st polymer mentioned above and a mutually different polymer, As a specific example, the (meth) acrylic acid derivative which has the isocyanate group mentioned above is mentioned. Alternatively, a polymer that can be crosslinked with a vinyl derivative and can be copolymerized with a (meth) acryl group or a vinyl group can be used.
Examples of the polymer copolymerizable with the (meth) acrylic group or vinyl group include monomers selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers. A polymer obtained by polymerization may be mentioned. Other (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. Acrylic acid esters, aromatic vinyl compounds such as styrene, α-styrene, methoxystyrene, divinylbenzene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, malein Aliases such as diallyl acid, diallyl fumarate, diallyl itaconate, diallyl trimelliate, triallyl cyanurate, triallyl isocyanurate, diallyl carbonate, diethylene glycol bisallyl carbonate Compound, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, maleic acid, fumaric acid, maleic anhydride, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, and derivatives thereof, ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Poly (poly) obtained by polymerizing polyfunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Chromatography may also be a second polymer in the present invention.

The content ratio of the first polymer, the second polymer and the first monomer constituting the polymer gel of the present invention is not particularly limited, but depending on the properties of the polymer gel to be obtained, The ratio with the second polymer can be adjusted, and the ratio is about 1: 10000 to 10000: 1 (0.01 mol% to 99.99 mol%) in terms of the molar ratio of the constituent monomer units. When the characteristics of the first polymer are to be increased, the ratio of the first polymer is increased, and when the characteristics of the second polymer are to be increased, the ratio of the second polymer is increased.
The first monomer is preferably used in an amount of about 0.2 to 1.0 mol per monomer unit of the first polymer. If the amount of the first monomer used is less than 0.2 mol per unit monomer unit of the first polymer, a network structure may not be formed. Since the first monomer becomes excessive and the formation of the network structure does not proceed any further, the amount of the first monomer used may be less than 1.0 mol per constituent monomer unit of the first polymer. When the amount of the first monomer used is less than the above range, for example, the first monomer is bonded only to both ends of the first polymer, and is bonded to the second polymer together with it to form a ladder type. May form a gel. Therefore, unless a certain amount of the first monomer is used, a network structure is not formed. Accordingly, the amount of the first monomer used is preferably 0.2 mol or more per constituent monomer unit of the first polymer.

  There is no restriction | limiting in particular in the shape of the polymer gel of this invention, Various gel-like molded products can be obtained by designing suitably. Specific examples include industrial materials such as various shock absorbing / damping materials, biomaterials such as artificial joints, various electronic parts, OA equipment expansion / contraction parts or drive parts, various intermediate films, ship bottom paints, pipe antifouling agents, etc. Alternative materials for living tissues such as joints, cartilage and blood vessels; cell culture sheets, soft contact lenses, water-containing sheets for indoor greening, medical materials such as drug delivery systems and wound dressings.

The polymer gel of the present invention may contain additives such as known colorants, plasticizers, stabilizers, reinforcing agents, inorganic fillers, impact modifiers, and flame retardants as necessary. Also good. As a method for incorporating these additives into the polymer gel, for example, a high molecular weight additive can be added to the solution at the time of production, and a low molecular weight additive is finally obtained. It can be contained in the polymer gel by free diffusion.
The polymer gel of this invention can be manufactured with the manufacturing method of the polymer gel of this invention mentioned later.

Next, the manufacturing method of the polymer gel of this invention is demonstrated.
The method for producing the polymer gel of the present invention in the first embodiment comprises:
A method for producing a polymer gel in which an inter-crosslinked network structure is formed between a second polymer composed of a second monomer and the first polymer,
The polymerization reactive group is introduced by reacting the first polymer with a first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group to introduce a polymerization reactive group into the first polymer. By copolymerizing a second monomer having a functional group copolymerizable with the polymerization reactive group in the presence of the first polymer having the polymerization reactive group. Forming a cross-linked network structure between the second polymer composed of two monomers and the first polymer.

In the method for producing a polymer gel of the present invention in the first embodiment, first, a first polymer, a first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group are included. By reacting, a polymerization reactive group is introduced into the first polymer to obtain a first polymer having a polymerization reactive group. Here, the first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group is a compound that has a polymer reactive group that reacts with the first polymer and a polymerization reactive group. Although it can use without a restriction | limiting in particular, For example, the (meth) acrylic acid derivative which has an isocyanate group as mentioned above, and the vinyl derivative which has an isocyanate group can be used. In this case, a polymer having a functional group that reacts with an isocyanate group is used as the first polymer. Examples of such a polymer include functional groups such as a hydroxyl group, a carboxyl group, an amino group, an amide group, and a mercapto group. The polymer which has is mentioned. These examples are as described above.
For the step of reacting the first polymer with the first monomer and introducing the polymerization reactive group into the first polymer to obtain the first polymer having the polymerization reactive group, a conventionally known method is used. That is, the first polymer and the first monomer are dissolved or suspended in a solvent such as DMF, DMSO, DMAC, or NMP, and stirred at a temperature of room temperature to about 80 ° C. for several minutes to several hours. Can be implemented. The reaction can be stopped to any degree by adding water or alcohol.

In the method for producing a polymer gel of the present invention, the shape can be appropriately designed depending on the intended use, and a gel-like molded product can be obtained.
The first monomer is preferably used in an amount of about 0.2 to 1.0 mol per monomer unit of the first polymer. If the amount of the first monomer used is less than 0.2 mol per unit monomer unit of the first polymer, a network structure may not be formed. Since the first monomer becomes excessive and the formation of the network structure does not proceed any more, the amount of the first monomer used may be 1.0 mol or less per constituent monomer unit of the first polymer. In general, when the amount of the first monomer used is small, a polymer gel having a low elastic modulus and high ductility can be obtained because the crosslinking density is low. On the other hand, when the amount of the first monomer used is increased, the crosslink density is increased, so that a gel having a high elastic modulus and brittleness can be formed. When the amount of the first monomer used is less than the above range, for example, the first monomer is bonded only to both ends of the first polymer, and is bonded to the second polymer together with it to form a ladder type. May form a gel. Therefore, unless a certain amount of the first monomer is used, a network structure is not formed. Accordingly, the amount of the first monomer used is preferably 0.2 mol or more per constituent monomer unit of the first polymer.

  Next, by copolymerizing a second monomer having a functional group copolymerizable with the polymerization reactive group in the presence of the obtained first polymer having a polymerization reactive group, a second monomer comprising the second monomer is obtained. A cross-linked network structure is formed between the two polymers and the first polymer. When the (meth) acrylic acid derivative having an isocyanate group as described above or the vinyl derivative having an isocyanate group is used as the first monomer, examples of the second monomer include N, N-dimethylacrylamide, acrylamide. , Monomers selected from the group consisting of alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers. Other (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. Acrylic acid esters, aromatic vinyl compounds such as styrene, α-styrene, methoxystyrene, divinylbenzene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, malein Aliases such as diallyl acid, diallyl fumarate, diallyl itaconate, diallyl trimelliate, triallyl cyanurate, triallyl isocyanurate, diallyl carbonate, diethylene glycol bisallyl carbonate Compounds, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, maleic acid, fumaric acid, maleic anhydride, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, etc. Can be used. In the present invention, N, N-dimethylacrylamide is preferably used. N, N-dimethylacrylamide can be used as a solvent in the step of reacting the first polymer with the first monomer.

  The second monomer is polymerized by copolymerizing the second monomer having a functional group copolymerizable with the polymerization reactive group in the presence of the first polymer having the polymerization reactive group. Since the first polymer having a polymerizable reactive group is copolymerized with the second monomer at the same time, the resulting product is composed of the second polymer composed of the second monomer and the first polymer. A cross-linked network structure is formed between the two. The reaction conditions for copolymerizing the second monomer in the presence of the first polymer having a polymerization reactive group can be carried out with stirring at a temperature of room temperature to about 80 ° C. for about several minutes to several hours. . In the reaction, it is preferable to add a photo radical initiator to the reaction system and irradiate ultraviolet rays to initiate copolymerization. Examples of such photo radical initiators include α-ketoglutaric acid, benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone. , Diphenyl disulfite, methyl orthobenzoylbenzoate, ethyl 4-dimethylaminobenzoate, 2,4-diethylthioxanthone, 2-methyl-1- [4- (methyl) phenyl] -2-morpholinopropanone- 1, tetra (t-butylperoxycarbonyl) benzophenone, benzyl, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, 4,4-bisdiethylaminoben Phenone, 2,2'-bis (2-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2' Biimi Dazo - le, and the like. As thermal radical initiators, azo compounds such as azobisisobutyronitrile (AIBN), persulfates such as potassium persulfate, sodium persulfate, and ammonium persulfate, benzoyl peroxide, halogen benzoyl peroxide, Examples thereof include organic peroxides such as lauroyl peroxide, acetyl peroxide, dibutyl peroxide, cumene hydroperoxide, and butyl hydroperoxide, and inorganic peroxides such as hydrogen peroxide, ammonium persulfate, and potassium persulfate.

The use ratio of the first polymer having a polymerization reactive group and the second monomer depends on the properties of the polymer gel to be obtained, and the first monomer and the second polymer composed of the second monomer. The ratio can be adjusted, and the ratio is about 1: 10000 to 10,000: 1 in terms of the molar ratio of the constituent monomer units. (0.01 mol% to 99.99 mol%) When trying to increase the characteristics of the first polymer, the ratio of the first polymer is increased, and when trying to increase the characteristics of the second polymer, What is necessary is just to enlarge the ratio of a polymer.
In the method for producing a polymer gel of the present invention, since a crosslinking agent is not used, crosslinking between the first polymers and crosslinking between the second polymers are not formed, and the first polymer and the second polymer However, they form crosslinks between different polymers and form a network structure.

Next, the manufacturing method of the polymer gel of this invention in a 2nd embodiment is demonstrated. The method for producing a polymer gel of the present invention in the second embodiment is a method for producing a polymer gel in which an intercrosslinking network structure is formed between the second polymer composed of the second monomer and the first polymer. Because
A first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group is copolymerized with a second monomer having a functional group that can be copolymerized with the polymerization reactive group, to obtain a polymer reactive group And a second polymer having the polymer reactive group is reacted with the first polymer to form an intercrosslinking network between the second polymer and the first polymer. Form a structure.

In the method for producing a polymer gel of the present invention in the second embodiment of the present invention, first, the first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group is used as the polymerization reaction. Copolymerization with a second monomer having a functional group copolymerizable with the group yields a second polymer having a polymer reactive group. Here, the first monomer and the second monomer are as described in the first embodiment. Reaction conditions, usage ratios, and the like are the same as in the first embodiment. Also in this second embodiment, N, N-dimethylacrylamide is preferable because it can be used as a solvent.
Next, the obtained second polymer having a polymer reactive group is reacted with the first polymer. The first polymer used here is the same as that described in the first embodiment, and the reaction conditions and the like are also the same.
In the method for producing a polymer gel of the present invention in the second embodiment, the above-mentioned (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is used as the first monomer. Among the (meth) acrylic acid derivatives or vinyl derivatives having an isocyanate group described above, it is preferable to use the compounds represented by the formulas (8) and (9). In the compounds represented by the formulas (8) and (9), a protecting group is bonded to the isocyanate group, so that the reaction with the first polymer does not occur as it is, and the reaction system is heated to a high temperature (for example, 70 ° C. or higher). Since the protecting group is removed, a (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is formed, and the isocyanate group of this compound reacts with the first polymer. A first monomer having a polymer reactive group and a polymerization reactive group that reacts with the first polymer at a temperature of about -30 ° C., and a second monomer having a functional group copolymerizable with the polymerization reactive group (For example, by irradiating ultraviolet rays in the presence of a photoradical initiator as described above), and then raising the reaction system to a temperature of about 70 to 90 ° C. to react with the first polymer. By, there is an advantage that can be omitted the step of adding the reagent in the middle of the reaction. The polymer gel produced by the method for producing a polymer gel of the present invention in the second embodiment is particularly excellent in producing a film-like gel.

Next, the manufacturing method of the polymer gel of this invention in a 3rd embodiment is demonstrated. The method for producing a polymer gel of the present invention in a fifth embodiment is the production of a polymer gel in which an interconnected network structure is formed between the second polymer composed of the second monomer and the first polymer. A method comprising: a first monomer having a polymer reactive group that reacts with the first polymer and a polymerization reactive group; a first polymer; and a second monomer having a functional group copolymerizable with the polymerization reactive group. And the first monomer and the second monomer are copolymerized, and the polymer reactive group in the first monomer is reacted with the first polymer, whereby the second polymer and the An cross-linked network structure is formed with the first polymer.
That is, in the method for producing the polymer gel of the present invention in the fifth embodiment, the first polymer, the first monomer, and the second monomer are all mixed and reacted. About the raw material used, reaction conditions, etc., it is the same as that of the manufacturing method of the polymer gel in other embodiment.

  As a 1st monomer used in the manufacturing method of the polymer gel of this invention in the 1st-3rd embodiment mentioned above, the compound which has a reactivity with a 1st polymer and has a polymerization reaction group is mentioned. Can be mentioned. Having reactivity with the first polymer means having a functional group capable of crosslinking with the first polymer. For example, when a cellulose derivative is used as the first polymer, a compound having an isocyanate group Is applicable. Examples of the polymerization reactive group include a (meth) acryl group and a vinyl group. Accordingly, examples of the first monomer include (meth) acrylic acid derivatives having an isocyanate group and vinyl derivatives having an isocyanate group, and specific examples are as described above.

Next, the 1st polymer used in the manufacturing method of the polymer gel of this invention in the 1st-3rd embodiment is demonstrated. The first polymer forms a network structure by cross-linking between a second polymer described later and different polymers. As a specific example, since it can be cross-linked by the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group described above, a polymer having reactivity with an isocyanate group can be used.
As the polymer having reactivity with an isocyanate group, a polymer into which a functional group having reactivity with an isocyanate group is introduced is preferable. Examples of such functional groups include a hydroxyl group, a carboxyl group, an amino group, an amide group, a mercapto group, and the like. That is, examples of the first polymer include a polymer having a hydroxyl group, a polymer having a carboxyl group, a polymer having an amino group, a polymer having an amide group, and a polymer having a mercapto group. Such a polymer is as described above.

Next, the 2nd polymer used in the manufacturing method of the polymer gel of this invention in the 1st-3rd embodiment is demonstrated. A 2nd polymer forms a network structure by bridge | crosslinking between the 1st polymer mentioned above and a mutually different polymer, As a specific example, the (meth) acrylic acid derivative which has the isocyanate group mentioned above is mentioned. Alternatively, a polymer that can be crosslinked with a vinyl derivative and can be copolymerized with a (meth) acryl group or a vinyl group can be used, and specific examples are as described above.
Examples of the polymer copolymerizable with the (meth) acrylic group or vinyl group include monomers selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomers, alkyl methacrylate monomers, and vinyl compound monomers. A polymer obtained by polymerization may be mentioned. Other (meth) such as methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, isobornyl (meth) acrylate, etc. Acrylic acid esters, aromatic vinyl compounds such as styrene, α-styrene, methoxystyrene, divinylbenzene, vinyl esters such as vinyl acetate, vinyl propionate, vinyl benzoate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, malein Aliases such as diallyl acid, diallyl fumarate, diallyl itaconate, diallyl trimelliate, triallyl cyanurate, triallyl isocyanurate, diallyl carbonate, diethylene glycol bisallyl carbonate Compound, N-methylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, maleic acid, fumaric acid, maleic anhydride, dimethyl maleate, dimethyl fumarate, dimethyl itaconate, and derivatives thereof, ethylene Glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, glycerin di (meth) acrylate, trimethylolethane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol Poly (poly) obtained by polymerizing polyfunctional (meth) acrylates such as tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. Chromatography may also be a second polymer in the present invention.

Although there is no restriction | limiting in particular in the content rate of the 1st polymer used in the manufacturing method of the polymer gel of this invention in the 1st-3rd embodiment, a 2nd polymer, and a 1st monomer, The high which it is going to obtain The ratio between the first polymer and the second polymer can be adjusted according to the characteristics of the molecular gel, and the ratio is about 1: 10000 to 10,000: 1 in terms of the molar ratio of the constituent monomer units (0.01 mol). % To 99.99 mol%). When the characteristics of the first polymer are to be increased, the ratio of the first polymer is increased, and when the characteristics of the second polymer are to be increased, the ratio of the second polymer is increased.
The first monomer is preferably used in an amount of about 0.2 to 1.0 mol per monomer unit of the first polymer. If the amount of the first monomer used is less than 0.2 mol per unit monomer unit of the first polymer, a network structure may not be formed. Since the first monomer becomes excessive and the formation of the network structure does not proceed any further, the amount of the first monomer used may be less than 1.0 mol per constituent monomer unit of the first polymer. When the amount of the first monomer used is less than the above range, for example, the first monomer is bonded only to both ends of the first polymer, and is bonded to the second polymer together with it to form a ladder type. May form a gel. Therefore, unless a certain amount of the first monomer is used, a network structure is not formed. Accordingly, the amount of the first monomer used is preferably 0.2 mol or more per constituent monomer unit of the first polymer.

  In addition, in the manufacturing method of the polymer gel of the present invention in the first to third embodiments, known colorants, plasticizers, stabilizers, reinforcing agents, inorganic fillers, impact resistance modification are performed as necessary. You may contain additives, such as an agent and a flame retardant. As a method for incorporating these additives into the polymer gel, for example, a high molecular weight additive can be added to the solution at the time of production, and a low molecular weight additive is finally obtained. It can be contained in the polymer gel by free diffusion.

As apparent from the above, the present invention provides the following method for producing a polymer gel.
A (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is polymerized with a first polymer having reactivity with an isocyanate group to introduce an acrylic group or vinyl group into the first polymer, thereby producing an acrylic group or vinyl. A first polymer having a group is obtained, and then a second monomer having a functional group copolymerizable with the acrylic group or the vinyl group is copolymerized in the presence of the first polymer having the acrylic group or the vinyl group. By doing so, an inter-crosslinked network structure is formed between the second polymer composed of the second monomer and the first polymer, and a method for producing a polymer gel.
A (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is copolymerized with a second monomer having a functional group copolymerizable with the acrylic group or the vinyl group to obtain a second polymer having an isocyanate group, and The second polymer having the isocyanate group is reacted with the first polymer having reactivity with the isocyanate group, so that the second polymer comprising the second monomer and the first polymer are cross-linked. A method for producing a polymer gel, comprising forming a network structure.
A (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is reacted with a second monomer having a functional group copolymerizable with the acrylic group or the vinyl group, and the first polymer having reactivity with the isocyanate group. And copolymerizing the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group with the second monomer, and reacting the isocyanate group in the (meth) acrylic acid derivative or vinyl derivative with the first polymer, An intercrosslinking network structure was formed between the second polymer and the first polymer, forming an intercrosslinking network structure between the second polymer composed of the second monomer and the first polymer. A method for producing a polymer gel.

Hereinafter, the present invention will be described in more detail with reference to examples. Needless to say, the scope of the present invention is not limited to such examples.
In the following examples, the polymer gel was evaluated by the following method.
(1) Tensile test A sample prepared by immersing the prepared gel in a large amount of pure for 24 hours or more to swell was used as a sample. A test piece was prepared with a dumbbell-shaped die cutter (JIS K6251 tension No. 8), and a sample having a thickness of 3 mm and a distance between scores of 16 mm was prepared. In the test, a desktop material testing machine STA-1150 (manufactured by Orientec Co., Ltd.) was used, and measurement was performed at a crosshead speed of 100 mm / min.

(2) Crosslinking point concentration The crosslinking point concentration was determined from the following equation.
Crosslinking point concentration (mol / L) = number of crosslinking points (mol) / volume after swelling (L)
The number of crosslinking points and the volume after swelling were determined as follows.
The number of cross-linking points was determined from the following formula.
Number of crosslinking points (mol) = mass of added Karenz MOI-EG (g) / molecular weight of Karenz MOI-EG (g / mole) × introduction rate of Karenz MOI-EG to HPC (mol%)
The introduction rate (mol%) of Karenz MOI-EG to HPC represents the ratio of the number of molecules of Karenz MOI-EG to one pyranose ring constituting HPC.
The volume after swelling was determined by the following formula.
Volume after swelling (L) = Volume after swelling (mm ³ ) / 10 ⁻⁶
Volume after swelling (mm ³ ) = length (mm) × width (mm) × thickness (mm)
The length, width, and thickness are the size of the gel after swelling.

(3) Moisture content A part of the polymer gel was collected as a sample, and the moisture content was measured using a drying method. The drying method is a method in which a solid sample is heated to a temperature equal to or higher than the transpiration temperature of water and kept for a certain period of time to evaporate and dry the water from the sample, and the amount of decrease in the sample mass before and after heat drying is obtained as moisture. The moisture content is expressed in weight percent (wt%).
It measured using Moisture Analyzers MS-70 (made by AND (A & D)).

Example 1
To 0.293 g of N, N-dimethylacrylamide, 0.102 g of cellulose derivative (hydroxypropylcellulose, HPC, 20 g / L in water, viscosity at 25 ° C .: 2.0 to 2.9 mPa · s) is added, and HPC is dissolved. Until stirred. Next, Karenz MOI-EG (compound represented by the general formula (6)) is added in an amount of 0.3 mol to 1 mol of the pyranose ring which is a constitutional unit monomer of HPC, and stirred at a temperature of 60 ° C. for 1 hour. did. Subsequently, 2.16 mL of pure water was added to react unreacted isocyanate groups of Karenz MOI-EG with water molecules so that no erroneous reaction occurred during gelation. Next, 0.012 g of α-ketoglutaric acid as a photo radical initiator was added and stirred, and then the solution was poured into a mold with a 1 mm silicone spacer sandwiched between two glass plates, and ultraviolet light (wavelength: 352 nm) was applied. A polymer gel was prepared by irradiation for 9 hours. The obtained polymer gel was evaluated as described above.

Example 2
A polymer gel was obtained in the same manner as in Example 1 except that a cellulose derivative having a viscosity at 20 g / L · 25 ° C. in water of 1000 to 5000 mPa · s was used. The obtained polymer gel was evaluated as described above.

Example 3
A polymer gel was obtained in the same manner as in Example 1 except that the amount of Karenz MOI-EG was 1.0 mol per mol of pyranose ring which is a constituent unit monomer of HPC. The obtained polymer gel was evaluated as described above.

Example 4
A cellulose derivative having a viscosity of 1000 to 5000 mPa · s in water at 20 g / L · 25 ° C. is used, and the amount of Karenz MOI-EG used is 1.0 with respect to 1 mol of pyranose ring which is a constitutional unit monomer of HPC. A polymer gel was obtained in the same manner as in Example 1 except that the molar amount was changed. The obtained polymer gel was evaluated as described above.

Example 5
A cellulose derivative having a viscosity of 1000 to 5000 mPa · s in water at 20 g / L · 25 ° C. is used, and the amount of Karenz MOI-EG used is 0.1 per mol of pyranose ring as a constituent unit monomer of HPC. A polymer gel was obtained in the same manner as in Example 1 except that the molar amount was changed. The obtained polymer gel was evaluated as described above.
The HPC used as a raw material in the polymer gels obtained in Examples 1 to 5 is used as a thickener, has LCST type (lower critical solution temperature) temperature dependency, and is usually It is a substance that becomes insoluble in water at a temperature of 32 ° C. or higher. On the other hand, N, N-dimethylacrylamide has a high solubility in water and dissolves well even when the water temperature rises. Each of the polymer gels obtained in Examples 1 to 5 has high ductility as compared with a polymer composed only of N, N-dimethylacrylamide even if the crosslink density is the same by adding HPC. It becomes a molecular gel. Moreover, by adding N, N-dimethylacrylamide, it becomes a gel that maintains transparency even when the temperature is increased in water.

Comparative Example 1
A polymer gel was obtained in the same manner as in Example 1 except that 0.05 mol% of N, N′-methylenebisacrylamide as a crosslinking agent was added to N, N-dimethylacrylamide. . The obtained polymer gel was evaluated as described above.

Comparative Example 2
A polymer gel was obtained in the same manner as in Example 2 except that 0.05 mol% of N, N′-methylenebisacrylamide as a crosslinking agent was added to N, N-dimethylacrylamide. . The obtained polymer gel was evaluated as described above.

Comparative Example 3
A polymer gel was obtained in the same manner as in Example 3 except that 0.05 mol% of N, N′-methylenebisacrylamide as a crosslinking agent was added to N, N-dimethylacrylamide. . The obtained polymer gel was evaluated as described above.

Comparative Example 4
A polymer gel was obtained in the same manner as in Example 4 except that 0.05 mol% of N, N′-methylenebisacrylamide as a crosslinking agent was added to N, N-dimethylacrylamide. . The obtained polymer gel was evaluated as described above.
In Comparative Examples 1 to 4, a crosslinking agent is added, whereby cellulose derivative molecules are crosslinked to each other, and polymers formed by copolymerization of N, N-dimethylacrylamide are crosslinked to each other. Is not formed.

The results of the tensile test (stress-strain curve, SS curve) are shown in FIG.
The polymer gel of Example 5 stretched best and exhibited a maximum strain of 10.63 (1063%). Further, it was found that the maximum strain was larger when N, N′-methylenebisacrylamide as a crosslinking agent was added and when it was not added (that is, the polymer gel of the present invention). Example 1 for Comparative Example 1, Example 2 for Comparative Example 2, Example 3 for Comparative Example 3, Example 4 for Comparative Example 4). Moreover, since the tensile test was possible also in the polymer gel obtained in Examples 1-4, by adding Karenz MOI-EG, gel was added without adding the crosslinking agent N, N′-methylenebisacrylamide. It was found that can be prepared.
Moreover, the maximum distortion of the polymer gel obtained in Examples 1-5 and Comparative Examples 1-4 is shown in FIG. It was found that the viscosity of the polymer gel obtained was higher when the amount of Karenz MOI-EG was smaller.

  FIG. 3 is a graph showing the relationship between the crosslinking point concentration and the maximum strain. As is clear from FIG. 3, it can be seen that HPC having higher viscosity has a larger maximum strain. Further, the number of cross-linking points along the main chain of HPC is proportional to the length of the main chain of HPC. Therefore, when HPC having higher viscosity is used, the number of cross-linking points increases. It is thought that the ductility is improved.

The measurement result of the moisture content is shown in FIG. As is clear from FIG. 4, it was found that the polymer gel obtained in Example 5 showed the highest water content. Further, it was found that the moisture content was higher when N, N′-methylenebisacrylamide as a crosslinking agent was added and when it was not added (that is, the polymer gel of the present invention). Example 1 for Comparative Example 1, Example 2 for Comparative Example 2, Example 3 for Comparative Example 3, Example 4 for Comparative Example 4). It was also found that the moisture content was higher when the amount of Karenz MOI-EG was less and the viscosity of HPC was higher. This is a tendency similar to the relationship between the concentration of crosslinking and the maximum strain. Under the condition that the water content is high, the number of cross-linking points is reduced, so that the space between the gel meshes is increased, the volume for storing water is increased, and therefore the water content is considered to be high.
As described above, the polymer gel of the present invention has both the high water content of polydimethylacrylamide and the high viscosity of cellulose.

Example 6
The same procedure as in Example 1 was carried out except that methylcellulose 15 (20 g / L in water, average molecular weight 50,000, average polymerization degree: 260, manufactured by Wako Pure Chemical Industries, Ltd.) was used as the cellulose derivative, and the polymer A gel was obtained. The obtained polymer gel was evaluated as described above.

Example 7
Except that cellulose acetate (20 g / L in water) was used as the cellulose derivative, the same operation as in Example 1 was performed to obtain a polymer raw material. The obtained polymer gel was evaluated as described above.

Example 8
The same procedure as in Example 1 was conducted except that cellulose triacetate (20 g / L in water) was used as the cellulose derivative, to obtain a polymer raw material. The obtained polymer gel was evaluated as described above.
The results of the tensile test (stress-strain curve, SS curve) are shown in FIG. 5 (Example 6), FIG. 6 (Example 7), and FIG. 7 (Example 8). The polymer gels obtained in Examples 6 to 8 are well stretched. For the polymer gels obtained in Example 6, Example 7 and Example 8, 9.12, 17.26 and A maximum strain of 14.58 was shown. Also in these examples, it was found that the gel can be prepared without adding a crosslinking agent. Moreover, the maximum stress was 11.39 kPa, 17.21 kPa, and 13.00 kPa about the polymer gel obtained in Example 6, Example 7, and Example 8, respectively. The water content was 97.29% by weight, 98.56% by weight and 99.99% by weight for the polymer gels obtained in Example 6, Example 7 and Example 8, respectively.
As is clear from the above description, the polymer gels obtained in Examples 6 to 8 had the same properties as those obtained in Examples 1 to 5. That is, it has both high viscosity and high water content.

Example 9
To 14.7711 g of N, N-dimethylacrylamide, 0.1892 g of a cellulose derivative (hydroxypropylcellulose, HPC, 20 g / L in water, viscosity at 25 ° C .: 1000 to 5000 mPa · s) was added and stirred until HPC was dissolved. Next, Karenz MOI-BM (compound represented by the general formula (8)) was added in an amount of 0.1 mol (0.0179 g) and A-KGA (one mol of pyranose ring as a constituent unit monomer of HPC). 0.001 equivalent, 0.0218 g) is added to 1 mol of N, N-dimethylacrylamide, and irradiation with ultraviolet light (wavelength: 352 nm) is performed for about 9 hours, so that N, N-dimethylacrylamide and Karenz MOI-BM A copolymer was obtained. Here, since the protecting group is bonded to the isocyanate group of Karenz MOI-BM, the cellulose derivative is not bonded to the copolymer.
Next, 100 g of DMSO was added and stirred for 5 days to obtain a viscous liquid. The obtained viscous liquid was heated at 100 ° C. for 24 hours to prepare a polymer gel. The obtained polymer gel was evaluated as described above.

FIG. 8 shows the results of the tensile test (stress-strain curve, SS curve). The polymer gel obtained in Example 9 extended well. Also in Example 9, it was found that the gel could be prepared without adding a crosslinking agent. The maximum stress is 42.38 kPa and the maximum strain is 4.
The water content was 90.02% by weight.
As is apparent from the above, the polymer gel obtained in Example 9 had the same properties as those obtained in Examples 1-5. That is, it has both high viscosity and high water content.

Claims (7)

A polymer gel for molded articles, wherein a cellulose derivative and a polymer copolymerizable with a (meth) acrylic group or a vinyl group form a network structure by crosslinking between different polymers. There,
The cellulose derivative and a polymer copolymerizable with a (meth) acrylic group or vinyl group are cross-linked with a (meth) acrylic acid derivative or vinyl derivative having an isocyanate group , and the amount of the cellulose derivative is A hydrous polymer gel material for molded medical material, which is 0.2 to 1.0 mol per monomer unit of the cellulose derivative . A polymer gel characterized in that a cellulose derivative and a polymer copolymerizable with a (meth) acrylic group or vinyl group are cross-linked by a (meth) acrylic acid derivative or vinyl derivative having an isocyanate group. A water-containing polymer gel material for molded medical material, wherein the amount of the cellulose derivative is 0.2 to 1.0 mol per constituent monomer unit of the polymer having reactivity with the isocyanate group. The polymer copolymerizable with (meth) acrylic group or vinyl group is at least one selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomer, alkyl methacrylate monomer and vinyl compound monomer. The water-containing polymer gel material for molded medical material according to claim 1 or 2 , which is a polymer obtained by polymerizing two monomers. A method for producing a water-containing polymer gel material for a medical material molded article in which a cross-linked network structure is formed between a second polymer composed of a second monomer and a cellulose derivative ,
And the cellulose derivative, an isocyanate group (meth) reacting an acrylic acid derivative or vinyl derivative by introducing a polymerizable reactive group in the cellulose derivative to obtain a cellulose derivative having a polymerization group, then the polymerization reaction group By copolymerizing a second monomer having a functional group copolymerizable with the polymerization reactive group in the presence of the cellulose derivative having, between the second polymer composed of the second monomer and the cellulose derivative In the above-described method for forming an inter-crosslinked network structure, the amount of the first monomer used is 0.2 to 1.0 mol per constituent monomer unit of the cellulose derivative . The water-containing polymer for molded medical materials according to claim 4 , wherein the second monomer is selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomer, alkyl methacrylate monomer and vinyl compound monomer. A method for producing a gel material. Having an isocyanate group with (meth) acrylic acid derivative or vinyl derivative, by a cellulose derivative and a polymer reaction to introduce an acryl group or a vinyl group in a cellulose derivative, to obtain a cellulose derivative having an acryl group or a vinyl group, then the A second polymer comprising a second monomer by copolymerizing a second monomer having a functional group copolymerizable with the acrylic group or vinyl group in the presence of a cellulose derivative having an acrylic group or vinyl group; In the method for forming a cross-linked network structure with the cellulose derivative , the (meth) acrylic acid derivative or vinyl derivative having an isocyanate group is 0.2 to 1. per unit monomer unit of the cellulose derivative . Hydrous polymer gel material for medical material molded product, characterized in that it is 0 mol Manufacturing method.
The water-containing polymer for molded medical material according to claim 6, wherein the second monomer is selected from the group consisting of N, N-dimethylacrylamide, acrylamide, alkyl acrylate monomer, alkyl methacrylate monomer and vinyl compound monomer. A method for producing a gel material.

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