JP2020139118A - Production method of gel film and gel film - Google Patents

Abstract

To provide a production method of a gel film capable of improving strength of a gel film after film formation and capable of producing a gel film excellent in smoothness.SOLUTION: The production method of a gel film 2c comprises: a step of forming a film of a liquid film 2a by using a dispersion of a polymer gel, which is a gel comprising at least one selected from the group consisting of hyaluronic acid, a hyaluronate and a hyaluronic acid derivative, and at least one selected from the group consisting of carboxymethylcellulose, a carboxymethylcellulose salt and a carboxymethylcellulose derivative, or a copolymer of at least one selected from the group consisting of hyaluronic acid, a hyaluronate and a hyaluronic acid derivative, and at least one selected from the group consisting of carboxymethylcellulose, a carboxymethylcellulose salt and a carboxymethylcellulose derivative; and a heating step of hot pressing a gel film 2b obtained by drying the liquid film.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a method for producing a gel film and a gel film produced thereby.

In recent years, materials using various polymer gels have been developed, and are applied to, for example, medical products, cosmetics, foods, and the like. The polymer gel is used in a film-like form such as a film or a sheet.

Examples of the polymer material used for the polymer gel include hyaluronic acid, alginic acid, chitosan, cellulose, chemically modified cellulose, natural polysaccharides such as salts thereof, proteins such as collagen and fibroin, polyesters, polyamides and polyvinyl compounds. , Polyvinylidene compounds, polystyrene compounds, polystyrenes, polyurethanes, polypropylenes and the like are known.

As a method for forming a film-like polymer gel, for example, a method of pouring the polymer gel into a flat container and drying it at room temperature, or a method of arranging the polymer gel between two members whose at least one is porous is arranged. Therefore, a method of compressing and dehydrating, a method of freeze-drying the polymer gel, a method of freeze-drying the polymer gel and then compressing, and the like have been proposed (see, for example, Patent Documents 1 and 2). Generally, a method is known in which a polymer gel is poured into a flat container and dried at room temperature.

Further, it has been reported that the strength is increased by heat-treating a film-like polymer gel (see, for example, Patent Document 1).

Japanese Patent No. 3399526 Japanese Unexamined Patent Publication No. 8-208706 JP-A-2017-113938

However, when the film-like polymer gel is heat-treated in order to increase its strength, deformation such as wrinkles, swells, and curls occurs, resulting in poor handleability of the gel film and adhesion to the target to which the gel film is applied. It may be inferior.

Further, as another method for increasing the strength of the film-shaped polymer gel, for example, a method of promoting the intermolecular or intramolecular cross-linking reaction of the polymer gel before forming the film-like structure can be considered. However, if the cross-linking reaction is excessively promoted before the film is formed, the number of cross-linkable sites existing in the polymer gel is reduced, so that the cross-linking reaction is present in the film at the stage of forming the film. Cross-linking between polymer gels is less likely to occur. As a result, even if the strength of the obtained gel film is sufficient, the flexibility of the gel film is impaired and the handleability at the time of use becomes inferior.

Therefore, it is important that the strength of the gel film can be adjusted at the stage of forming the polymer gel into a film.

The present disclosure has been made in view of the above problems, and is a method for producing a gel film, which can improve the strength after forming the gel film and can produce a gel film having excellent smoothness. The purpose is to provide.

In order to achieve the above object, the present disclosure comprises a film forming step of forming a gel film containing a polymer gel and a heating step of hot pressing the gel film using a hot plate. Provide a manufacturing method.

Further, the present disclosure is a gel film containing a polymer gel, wherein the polymer gel is at least one selected from the group consisting of hyaluronic acid, hyaluronate and hyaluronic acid derivatives, and carboxymethyl cellulose and carboxymethyl cellulose salt. And a gel containing at least one selected from the group consisting of carboxymethyl cellulose derivatives, or at least one selected from the group consisting of hyaluronic acid, hyaluronate and hyaluronic acid derivatives, and carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose. A gel that is a copolymer with at least one selected from the group consisting of derivatives, the gel film having a first surface and a second surface, and the arithmetic average roughness of the first surface. (Ra1) is smaller than the arithmetic average roughness (Ra2) of the second surface, and the arithmetic average roughness (Ra1) of the first surface is within the range of 10 nm or more and 1000 nm or less. A gel film having a value Ra1 / Ra2 obtained by dividing the arithmetic average roughness (Ra1) of the surface by the arithmetic average roughness (Ra2) of the second surface within the range of 0.05 or more and 1.0 or less. provide.

According to the present disclosure, it is possible to provide a method for producing a gel film, which can improve the strength after film formation and can produce a gel film having excellent smoothness.

It is a process drawing which shows an example of the manufacturing method of the gel film of this disclosure. It is a process drawing which shows another example of the manufacturing method of the gel film of this disclosure. It is a process diagram which shows an example of the film forming process in the manufacturing method of the gel film of this disclosure. It is a schematic diagram which shows an example of the heating process in the manufacturing method of the gel film of this disclosure. It is a photograph of the gel film of Examples 2-10-2-11. It is a photograph of the gel film of Comparative Examples 3 to 6.

Hereinafter, the method for producing a gel film of the present disclosure and the gel film produced by the method will be described in detail.

As used herein, the term "gel film" refers to a polymer gel formed into a thin film. The gel film may be a dry one or a water-containing one. The gel film also includes what is generally called a "sheet", a "film", or the like.

A. Method for Producing Gel Membrane The method for producing a gel film of the present disclosure includes a film-forming step of forming a gel film containing a polymer gel and a heating step of hot-pressing the gel film using a hot plate. The method.

Hereinafter, the method for producing the gel film of the present disclosure will be described with reference to the drawings.

1 (a) to 1 (e) are process diagrams showing an example of the method for producing a gel film of the present disclosure. First, as shown in FIG. 1A, a polymer gel dispersion liquid film 2a containing a polymer gel and a dispersion medium is formed on one surface of the base material 1. Next, as shown in FIG. 1B, the polymer gel dispersion film 2a is dried to remove the dispersion medium contained in the polymer gel dispersion, and the dried gel film 2b is obtained. Subsequently, as shown in FIG. 1 (c), the dried gel film 2b is peeled off from the base material 1. Next, as shown in FIG. 1D, the dried gel film 2b is sandwiched between the pair of hot plates 11 and heat-pressed. In this way, as shown in FIG. 1 (e), the gel film 2c after hot pressing can be obtained.

In the present disclosure, the strength of the gel film can be improved by performing a heating step of hot-pressing the gel film using a hot plate after forming the gel film. The strength of the gel film can be adjusted by the heating temperature and heating time during hot pressing. Therefore, the gel film produced by the method for producing a gel film of the present disclosure can be applied to various applications because the strength of the gel film can be adjusted according to the application. When the gel film is a biocompatible gel film, it may be used for, for example, medical materials, cosmetics, beauty materials, etc., and it is desirable that the gel film has strength suitable for the required application. For example, when a biocompatible gel film is used as an anti-adhesion material as a medical material, a gel film that does not have sufficient strength may be damaged during a procedure by a doctor, or after application to an organ. It may be damaged.

Further, in the present disclosure, it is possible to prevent deformation such as wrinkles, wrinkles, and curls from remaining on the gel film by performing heat pressing with a hot plate in the heating step. That is, it is possible to prevent macroscopic unevenness from remaining on the gel film. Therefore, a gel film having excellent smoothness can be obtained. Therefore, when a gel film having good handleability and biocompatibility, for example, can be obtained, a gel film having good adhesion to an application target such as a living body can be obtained. As a result, when the gel film is used, the performance of the gel film can be fully exhibited.

In the film forming step of forming the gel film, it is also conceivable to perform pressing at the time of forming the polymer gel dispersion liquid film. However, after the formation of the polymer gel dispersion film, it is usual to perform drying in order to remove the dispersion medium contained in the polymer gel dispersion film, and when the polymer gel dispersion film is dried, it is dried. Deformation such as wrinkles due to shrinkage of the polymer gel dispersion liquid film with progress or bending of the edge of the gel film remains on the gel film. Therefore, it is difficult to obtain a gel film having excellent smoothness even when pressing is performed at the time of forming the polymer gel dispersion liquid film.
Further, as a method of heat-pressing the gel film, for example, a method of heat-rolling can be considered in addition to the heat-pressing of a hot plate. However, in the method using a thermal roll, since the gel film is heated on the circumferential surface of the cylindrical thermal roll, deformation such as curl tends to remain on the gel film, and the gel film is wrinkled during heating by the thermal roll. May occur and remain even after heating. Therefore, it is difficult to obtain a gel film having excellent smoothness by the method using a thermal roll. In addition, when the gel film is heated with a heat roll, it may be necessary to reduce the processing speed or increase the number of heat rolls in order to obtain sufficient strength of the gel film, which is a disadvantage in manufacturing. May be.

The example shown in FIG. 1 is an example of a single-wafer manufacturing method, but the gel film manufacturing method of the present disclosure can be a roll-to-sheet manufacturing method.

2 (a) to 2 (c) are process diagrams showing another example of the gel film manufacturing method of the present disclosure, and are examples of a roll-to-sheet manufacturing method. In FIG. 2A, the base material 1 is unwound from the unwinding roll 21, and the polymer gel dispersion is poured from the die 22 onto the surface of the base material 1 supported by the backup roll 23, and the polymer gel is formed. A dispersion liquid film 2a is obtained. Next, the base material 1 on which the polymer gel dispersion liquid film 2a is formed is conveyed by the guide roll 31, and is contained in the polymer gel dispersion liquid by drying the polymer gel dispersion liquid film 2a by the drying means 24. The dispersion medium is removed to obtain a dried gel film 2b. Next, the base material 1 on which the dried gel film 2b is formed is separated into the base material 1 and the gel film 2b by the separator 32, and then the transport direction of the base material 1 and the dried gel film 2b is changed. The base material 1 is wound around the base material winding roll 25, and the dried gel film 2b is conveyed by the guide roll 33, so that the dried gel film 2b is peeled off from the base material 1. Next, the dried gel film 2b is cut by the cutting means 26. Then, as shown in FIG. 2B, the cut and dried gel film 2b is hot-pressed. At this time, the dried gel films 2b may be heat-pressed one by one, or a plurality of gel films 2b may be heat-pressed at once. When a plurality of dried gel films 2b are stacked, a plurality of dried gel films 2b and a plurality of release sheets 12 are alternately laminated, and the laminated body is sandwiched between a pair of hot plates 11 and collectively. And heat press. In this way, as shown in FIG. 2C, the gel film 2c after hot pressing can be obtained.

In the present disclosure, it is possible to produce a gel film having excellent smoothness by either the single-wafer method or the roll-to-sheet method.

Hereinafter, each step of the gel film manufacturing method of the present disclosure will be described.

1. 1. Membrane-forming process In the present disclosure, first, a film-forming step of forming a gel film containing a polymer gel is performed.

(1) Polymer gel The polymer gel is not particularly limited, and a known polymer gel can be used. The polymer gel may be a polymer gel having biocompatibility.
Here, "biocompatibility" refers to a property that does not have a medically unacceptable toxic or harmful effect with respect to biological function.

Further, the polymer gel having biocompatibility is preferably bioabsorbable. The gel membrane produced by the production method of the present disclosure can also be applied to applications in which bioabsorbability is desired.
Here, "bioabsorbable" refers to the property of being decomposed, excreted or metabolized in the living body.

Further, the polymer gel may be either a chemical gel or a physical gel. Above all, the polymer gel is preferably a chemical gel. This is because the strength and stability of the obtained gel film can be improved.

In the case of a chemical gel, a known cross-linking method can be applied as the cross-linking method. For example, heating, electron beam irradiation, gamma ray irradiation, ultraviolet irradiation and the like can be mentioned. Further, in order to facilitate the reaction, a cross-linking agent (also referred to as a condensing agent) may be used, or a polymerizable functional group may be introduced. The polymer gel may be crosslinked by any method.

The polymer gel preferably contains at least one selected from the group consisting of polyanionic polysaccharides and salts thereof, and derivatives thereof. Polyanionic polysaccharides are known to exhibit high biocompatibility, gel swelling property, viscoelasticity and the like, and are widely used as raw materials for, for example, medical products, foods and cosmetics.

Hereinafter, "polyanionic polysaccharides and salts thereof, and derivatives thereof" may be abbreviated as "polyanionic polysaccharides and the like".

Examples of the polyanionic polysaccharide include natural polysaccharides such as hyaluronic acid, alginic acid, pectin, and polygalacturonic acid, carboxymethyl cellulose, carboxyethyl cellulose, carboxymethyl amylose, carboxymethyl pullulan, carboxymethyl chitin, carboxymethyl chitosan, and carboxy. Examples thereof include carboxyalkyl polysaccharides such as methylmannan, and polysaccharides having a sulfate group such as dermatane sulfate, heparin, heparan sulfate, and heparan sulfate.

Examples of the salt of the polyanionic polysaccharide include the above-mentioned salt of the polyanionic polysaccharide, for example, an alkali metal salt such as a sodium salt and a potassium salt, an alkaline earth metal salt such as a calcium salt and a magnesium salt, and the like. Can be mentioned.

Derivatives of polyanionic polysaccharides are chemically modified polyanionic polysaccharides and salts thereof. Examples of the derivative of the polyanionic polysaccharide include the above-mentioned derivatives of the polyanionic polysaccharide and its salt, and examples thereof include the polyanionic polysaccharide into which a functional group has been introduced and a salt thereof.

The polyanionic polysaccharides and the like can be used alone or in combination of two or more.

Among them, the polyanionic polysaccharide and the like are preferably one or more selected from the group consisting of carboxymethyl cellulose, carboxymethyl amylose, hyaluronic acid, salts thereof, and derivatives thereof. Further, polyanionic polysaccharides and the like are hyaluronic acid or a salt thereof or a derivative thereof and carboxymethyl cellulose or a salt thereof or a derivative thereof, or hyaluronic acid or a salt thereof or a derivative thereof and heparin or a salt thereof. Alternatively, it is preferably a derivative thereof.

In particular, the polyanionic polysaccharide and the like are at least one selected from the group consisting of hyaluronic acid, hyaluronic acid and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. Is preferable. That is, the high molecular weight gel contains at least one selected from the group consisting of hyaluronic acid, hyaluronic acid salt and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. In a gel or in a copolymer of at least one selected from the group consisting of hyaluronic acid, hyaluronic acid and hyaluronic acid derivatives and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose derivatives. It is preferably a certain gel. These polyanionic polysaccharides and the like are used for various purposes such as medical products, foods and cosmetics because of their high safety and biocompatibility. For example, in the medical field, they are used as raw materials for adhesion preventive materials and the like. ing.

In addition, the polymer gel contains at least one selected from the group consisting of hyaluronic acid, hyaluronate and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. A gel or a copolymer of at least one selected from the group consisting of hyaluronic acid, hyaluronate and hyaluronic acid derivatives and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose derivatives. In the case of a certain gel, it is preferably a chemical gel, and more preferably one crosslinked using a cross-linking agent (condensing agent).

(2) Method for forming a gel film The method for forming a gel film is not particularly limited as long as it is a method capable of forming a polymer gel, and a general polymer gel film forming method is not limited. The method can be applied. For example, casting method, method of injecting polymer gel into a mold and drying, method of compressing polymer gel into a film, method of freeze-drying polymer gel, method of freeze-drying polymer gel, and then compressing. Examples thereof include a method in which a polymer gel is placed between two members whose at least one is porous, and compression and dehydration are performed. Further, a method of applying a polymer gel dispersion liquid containing a polymer gel and a dispersion medium to one surface of the base material and drying it can also be used.

Further, the film forming step is a polymer gel dispersion liquid film forming step of forming a polymer gel dispersion liquid film on one surface of the substrate by using a polymer gel dispersion liquid containing a polymer gel and a dispersion medium. By drying the polymer gel dispersion liquid film, it is possible to have a drying step of removing the dispersion medium contained in the polymer gel dispersion liquid to obtain a gel film.
Hereinafter, each step will be described.

(I) Polymer gel dispersion liquid film forming step In the film formation step, first, a polymer gel dispersion liquid film containing a polymer gel and a dispersion medium is used to form a polymer gel dispersion liquid film on one surface of a substrate. The polymer gel dispersion liquid film forming step to be formed can be performed.

The base material is particularly limited as long as it can form a polymer gel dispersion film on one surface of the base material and can peel off the gel film from the base material after the drying step. Instead, it can be appropriately selected according to the use of the gel film, the process order and method of the gel film manufacturing method of the present disclosure, and the like.

The form of the base material may be single-wafer-shaped or long-shaped. When it is a long base material, the base material may be rolled into a roll. For example, when the method for producing a gel film of the present disclosure is carried out by a single-wafer method, a single-wafer-shaped base material is used. Further, when the gel film manufacturing method of the present disclosure is carried out by a roll-to-sheet method, a long base material is used.

In the case of a single-wafer-shaped base material, the base material can be, for example, a flat mold, that is, a flat container. For example, the base material 1 shown in FIG. 3A is a flat container 10. In this case, as shown in FIG. 3 (b), the polymer gel dispersion 2a'is supplied to the end portion in the container 10, and as shown in FIGS. 3 (c) to 3 (d), the developing means 15 is used. The polymer gel dispersion liquid film 2a can be obtained by spreading the polymer gel dispersion liquid 2a'on the surface of the bottom portion 10a in the container 10. At this time, the wall portion 10b of the container 10 can keep the distance G between the surface of the bottom portion 10a in the container 10 and the developing means 15 constant, and the polymer gel dispersion liquid film 2a having a uniform thickness can be formed. Obtainable.

The depth of the container is appropriately adjusted according to the thickness of the target polymer gel dispersion film and the like.

Further, the base material may or may not have flexibility. For example, when the method for producing a gel film of the present disclosure is carried out by a roll-to-sheet method, it is preferable that the base material has flexibility.

Examples of the material of the base material include plastic, metal, glass and the like. Among them, when used for producing a biocompatible gel film, plastic is preferable, and medical plastic is more preferable. Specifically, acrylic resin, ABS resin (acrylonitrile-butadiene-styrene copolymer resin), acrylonitrile styrene, polyethylene terephthalate, polybutylene terephthalate, polypropylene, polyethylene, polyacetal, polystyrene, polyvinyl chloride, polyamide, polycarbonate, poly. Examples thereof include allylate, polysulfone, polyether ether ketone, cyclic polyolefin and the like. Further, as the medical plastic, a commercially available medical grade plastic can be used.

Moreover, it is preferable that the base material has hydrophilicity. This is because when the base material has hydrophilicity, a polymer gel dispersion liquid film can be satisfactorily formed on one surface of the base material.

On the other hand, if the hydrophilicity of the base material is too high, it becomes difficult to peel off the gel film when the gel film is peeled off from the base material. Therefore, as the hydrophilicity of the base material, for example, the contact angle of the base material surface with water is determined. , 30 ° or more and 95 ° or less, and above all, 30 ° or more and 85 ° or less, particularly preferably 30 ° or more and 60 ° or less. When the contact angle is within the above range, the polymer gel dispersion liquid film can be uniformly formed on one surface of the base material. Further, in the drying step, the adhesion between the base material and the polymer gel dispersion film can be improved, and peeling of the film can be suppressed. Further, when the gel film is peeled from the base material, the gel film can be easily peeled from the base material.

Here, for the contact angle with water, a contact angle measuring device Drop Master-700 manufactured by Kyowa Interface Science Co., Ltd. was used, and a droplet of 1.5 mL of pure water was prepared using a 22 G stainless needle to prepare a base material. The contact angle with water 1000 milliseconds after the droplet is brought into contact with the surface is measured.

Further, the base material may be surface-treated in order to adjust the contact angle of the surface with water. That is, the base material may have a hydrophilic treated surface on the surface. The surface treatment is not particularly limited as long as it can increase the hydrophilicity of the surface of the plastic, and for example, corona discharge treatment, plasma treatment, UV ozone treatment, excimer UV treatment, electron beam irradiation treatment, etc. Laser processing and the like can be mentioned.

Further, as will be described later, when the heating step is performed before the peeling step of peeling the gel film from the base material, the base material preferably has heat resistance. As for the heat resistance of the base material, it is preferable that the base material has heat resistance to the heating temperature in the heating step. Above all, the deflection temperature under load of the material of the base material is preferably higher than the heating temperature in the heating step, for example, it can be 100 ° C. or higher, preferably 130 ° C. or higher, and more preferably 150 ° C. or higher. Is.
The upper limit of the deflection temperature under load is not particularly limited.

Here, the deflection temperature under load can be measured by complying with JIS-K7191.

Examples of the material of the base material having heat resistance include polypropylene, polycarbonate and the like.

The thickness of the base material can be appropriately selected depending on the form of the base material, the process order and method of the gel film manufacturing method of the present disclosure, and the like.

The polymer gel dispersion liquid contains a polymer gel and a dispersion medium. The polymer gel dispersion is a dispersion in which the polymer gel is dispersed in a dispersion medium.

The dispersion medium is not particularly limited as long as it is a dispersion medium capable of dispersing the polymer gel, and is appropriately selected depending on the type of the polymer gel and the like. As the dispersion medium, for example, water or a dispersion medium miscible with water is preferably used. Specific examples of the dispersion medium to be mixed with water include lower alcohols such as methanol, ethanol, 1-propanol and 2-propanol; ketones such as acetone and methyl ethyl ketone; tetrahydrofuran, acetonitrile, dimethyl sulfoxide (DMSO) and dimethylformamide (DMSO). DMF) and the like. These dispersion media can be used alone or in combination of two or more.

The viscosity of the polymer gel dispersion at 23 ° C. can be, for example, in the range of 3 Pa · s or more and 10 Pa · s or less, and in particular, in the range of 4 Pa · s or more and 8 Pa · s or less. Is preferable. When the polymer gel dispersion is applied to one surface of the base material, for example, when the viscosity is within the above range, the polymer gel dispersion can be easily uniformly applied to one surface of the base material. The thickness of the polymer gel dispersion film can be easily made uniform. Further, when the polymer gel dispersion liquid is defoamed as described later, the bubbles can be easily removed.

Here, the viscosity of the polymer gel dispersion is measured with a B-type viscometer. Specifically, the measurement is performed at a rotation speed of 6 rpm using a TVB10M manufactured by Toki Sangyo Co., Ltd. and a spindle type rotor M3.

The polymer gel dispersion may contain a cross-linking agent (condensing agent), a pharmaceutically active substance, a coloring agent, a bacteriostatic agent, a pH adjusting agent, and the like. Examples of the pH adjuster include hydrochloric acid.

The method of forming the polymer gel dispersion liquid film on one surface of the base material is not particularly limited, and for example, a method of supplying and developing the polymer gel dispersion liquid on one surface of the base material. Examples thereof include a method of using a mold as a base material and injecting a polymer gel dispersion into the mold, and a method of using a mold as a base material and injecting a polymer gel dispersion into a mold and then shaking. A polymer gel dispersion film having a uniform thickness can be obtained by a method of supplying a polymer gel dispersion liquid to one surface of a base material and developing it, or a method of injecting the polymer gel into a mold and then shaking it. be able to. As a result, it is possible to obtain a gel film having a uniform thickness.

In the case of the method of supplying the polymer gel dispersion liquid to one surface of the base material and developing it, as the method of supplying the polymer gel dispersion liquid to one surface of the base material, a predetermined amount of the polymer gel dispersion liquid is used. The method is not particularly limited as long as it can be supplied. The method of supplying the polymer gel dispersion liquid to one surface of the base material may be a single-wafer method or a continuous method.

Further, the supply means for supplying the polymer gel dispersion liquid to one surface of the base material may be different from the developing means for developing the polymer gel dispersion liquid on one surface of the base material, and may be developed. It may also serve as a means.

When the supplying means is different from the developing means, as a method of supplying the polymer gel dispersion liquid to one surface of the base material, for example, a method using a dispenser can be mentioned.
When the supply means is different from the developing means, the polymer gel dispersion liquid is supplied to one surface of the base material and developed, for example, the polymer gel dispersion liquid is supplied to one surface of the base material. After supplying the above, a method of scraping off the excess polymer gel dispersion liquid can be mentioned. Specifically, a bar coating method, a reverse coating method, a comma direct coating method, a blade coating method, a knife coating method, a method using an applicator, or the like can be used.

When the supplying means also serves as a developing means, as a method of supplying the polymer gel dispersion liquid to one surface of the base material and developing it, for example, a die coating method, a microgravure method or the like can be used.

When the polymer gel dispersion is developed on one surface of the base material, the developing means may be moved or the base material may be moved with respect to one surface of the base material. Both substrates may be moved.

As a method of developing the polymer gel dispersion liquid on one surface of the base material, the polymer gel is spread on one surface of the base material by moving the developing means or the base material with respect to one surface of the base material. The method is not particularly limited as long as it can develop the dispersion liquid. The method of developing the polymer gel dispersion liquid on one surface of the base material may be a single-wafer method or a continuous method.

When the method of developing the polymer gel dispersion liquid on one surface of the base material is the single-wafer method, usually by moving the developing means or the base material in a direction parallel to one surface of the base material. , A polymer gel dispersion is developed on one surface of the substrate.

The direction parallel to one surface of the base material means a direction within ± 1 ° with respect to one surface of the base material.

Further, as described above, the deploying means may be different from the supply means, or may also serve as the supply means.

When the deploying means is different from the supply means, the deploying means may include, for example, a rod-shaped or plate-shaped member, and specifically, a blade such as a doctor blade, a squeegee, a wire bar, a wireless bar, or the like. Examples include coating bars and applicators.

When the developing means is different from the supplying means, as a method of supplying the polymer gel dispersion liquid to one surface of the base material and developing it, for example, the polymer gel dispersion liquid is supplied to one surface of the base material. After supplying the above, a method of scraping off the excess polymer gel dispersion liquid can be mentioned. In this case, the developing means can be a means for scraping off the excess polymer gel dispersion from one surface of the base material. Further, in this case, the deploying means may or may not rotate by itself, for example. The specific method is as described above.

When the developing means also serves as a supplying means, the method of supplying the polymer gel dispersion liquid to one surface of the base material and developing it is as described above.

When deploying the polymer gel dispersion on one surface of the substrate, it is preferable that the deploying means is arranged at a constant height from one surface of the substrate. This is because the thickness of the polymer gel dispersion film can be easily determined by the distance between the developing means and the base material, and a polymer gel dispersion film having a uniform thickness can be obtained. .. As a result, a gel film having a uniform thickness can be obtained.

In the case of the method of shaking after injecting the polymer gel dispersion into the mold, the shaking method is not particularly limited, and a known shaking method can be applied. For example, a method using a shaker can be mentioned, and a shake method such as a horizontal reciprocating type, a swivel type, a seesaw type, and a figure eight motion type can be applied.

(Ii) Drying step In the film forming step, after the polymer gel dispersion film forming step, the polymer gel dispersion film is dried to remove the dispersion medium contained in the polymer gel dispersion, and the gel film is formed. The resulting drying step can be performed.

The method for drying the polymer gel dispersion film is not particularly limited as long as it can remove the dispersion medium contained in the polymer gel dispersion, and a general method for drying the polymer gel can be used. Can be applied. For example, normal temperature drying, heat drying, vacuum drying and the like can be mentioned. In the case of heat drying or vacuum drying, the drying time can be shortened and the production efficiency can be improved. Further, the drying method may be a single-wafer method or a continuous method.

Above all, it is preferable that the drying conditions are such that the gel film is not deformed or cracked such as wrinkles. This is because the yield can be improved.

For example, the drying temperature is preferably a temperature at which the base material has heat resistance. Specifically, the drying temperature is preferably lower than the deflection temperature under load of the substrate material.

Above all, the drying temperature is preferably normal temperature. This is because if the drying temperature is high, as a result of the rapid progress of drying, the gel film may be deformed or cracked due to the shrinkage stress of the polymer gel dispersion film. The normal temperature means 23 ° C. ± 5 ° C. In particular, the drying temperature is preferably in the range of 20 ° C. or higher and 26 ° C. or lower.

Further, for example, by adjusting the humidity, wind speed, etc., it is possible to suppress deformation or cracking of the polymer gel dispersion liquid film during drying, such as wrinkles.
Specifically, when the humidity is low, the gel film may be deformed or cracked due to shrinkage of the polymer gel dispersion film during drying. Moreover, when the humidity is high, it may take a long time to dry.
Further, if the wind speed is high, the gel film may be deformed or cracked such as wrinkles. Further, if the wind speed is low, it may take a long time to dry.

2. 2. Peeling Step In the present disclosure, as described above, when the film-forming step includes a polymer gel dispersion liquid film forming step and a drying step, the gel film is removed from the substrate after the film-forming step. A peeling step for peeling can be performed.

The method of peeling the gel film from the base material is not particularly limited, and examples thereof include a method of peeling the base material by a physical method.

3. 3. Heating step In the present disclosure, after the film forming step, a heating step of hot pressing the gel film using a hot plate is performed. By performing the heating step, the strength of the gel film can be increased.
The heat press referred to here refers to applying pressure to the entire gel film in a heating atmosphere, and the heating source and the pressure source may be the same or different. An example in which the heating source and the pressure source are the same is a hot plate.

The hot plate is a flat plate. Since the hot plate is a flat plate, a gel film having less macroscopic unevenness and excellent smoothness can be obtained.

In a hot press using a hot plate, it is preferable that the gel film is arranged so as not to come into direct contact with the hot plate. That is, it is preferable that a release sheet, a cushioning sheet, or the like is arranged between the gel film and the hot plate.
In general, in a hot press using a hot plate, for example, as shown in FIG. 4, heat and pressure are uniformly applied to the object, so that the object can be further protected and the object can be easily peeled from the hot plate. As described above, the cushioning sheet 13, the stainless steel plate 14, and the release sheet 12 are arranged between the object (here, the gel film 2b after drying) and the hot plate 11. In the example shown in FIG. 4, the release sheet 12 is also arranged between the dried gel films 2b in order to prevent the gel films 2b from sticking to each other after drying.
As the release sheet, cushioning sheet and the like, those generally used for heat pressing can be used. Examples of materials such as the release sheet and the cushioning sheet include rubber such as silicone rubber and fluororubber, and paper.

When the gel film is heat-pressed, the gel film may be heat-pressed one by one, or a plurality of gel films may be laminated and heat-pressed at once. When a plurality of gel films are laminated and heat-pressed at once, manufacturing efficiency and work efficiency can be improved.

When a plurality of gel films are laminated and heat-pressed at once, it is preferable to arrange a release sheet between the gel films in order to prevent the gel films from adhering to each other. That is, it is preferable to heat-press the laminated body in which a plurality of gel films and a plurality of release sheets are alternately laminated.
As described above, examples of the material of the release sheet include rubber such as silicone rubber and fluororubber, and paper. Specifically, dust-free paper or the like can be used as the paper.

The heating temperature is not particularly limited as long as it can increase the strength of the gel film, and is appropriately determined according to the type of polymer gel, the process order and method of the gel film manufacturing method of the present disclosure, and the like. Can be set.

For example, when the heating step and the peeling step are performed in this order, the heating temperature is preferably a temperature at which the base material has heat resistance. Specifically, the heating temperature is preferably lower than the deflection temperature under load of the material of the base material.

Further, for example, the polymer gel has at least one selected from the group consisting of hyaluronic acid, hyaluronic acid salt and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. Gel containing, or a copolymer of at least one selected from the group consisting of hyaluronic acid, hyaluronic acid salt and hyaluronic acid derivatives and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. In the case of the gel, the heating temperature can be in the range of 100 ° C. or higher and lower than 200 ° C., and more preferably in the range of 120 ° C. or higher and 160 ° C. or lower. If the heating temperature is too low, the strength of the gel film may not be sufficiently increased. Further, if the heating temperature is too high, the polymer gel may deteriorate.

It is preferable to cool the gel film after hot pressing.
The temperature of the cooling environment is not particularly limited as long as the temperature of the gel film after heating can be cooled to the heating temperature or lower.
The relative humidity of the cooling environment is preferably 40% RH or more and 60% RH or less. Above all, it is preferable to leave the product in an environment with a relative humidity of 40% RH or more and 60% RH or less for 1 hour or more. This is because the water content of the gel film after heating is lowered, and the gel film is easily damaged when a force is applied to the gel film. If the relative humidity of the cooling environment is too low, the gel film cannot sufficiently contain water, and if a force is applied to the gel film, the gel film may remain in a easily damaged state. Further, if the relative humidity is too high, the gel film may contain too much water, which may cause wrinkles or waviness in the gel film. By allowing the gel film to stand for the above time or longer in an environment with a relative humidity within the above range, the water content of the gel film is kept within an appropriate range, so that the gel film is easily damaged or wrinkles occur. Can be suppressed.

The peeling step and the heating step can be performed in any order. The order of the peeling step and the heating step can be appropriately determined according to the method of the gel film manufacturing method of the present disclosure, the type of the base material, the heat resistance, and the like.

When the peeling step and the heating step are performed in this order, for example, in the heating step, a plurality of gel films can be laminated and heat-pressed at once, and the production efficiency can be improved.
Further, for example, when the heat resistance of the base material is relatively low, it is preferable to carry out the peeling step and the heating step in this order. Even when the heat resistance of the base material is relatively low, the heating temperature can be set regardless of the heat resistance of the base material because the base material has already been peeled off in the heating step.
Further, for example, when the film forming step is a single-wafer method and a flat container is used as the base material, it is preferable to carry out the peeling step and the heating step in this order. This is because when a gel film is formed in the container, it becomes difficult to heat-press the gel film.

On the other hand, when the heating step and the peeling step are performed in this order, the gel film may be hot-pressed in the heating step in a state where the gel film is supported by the base material, that is, in a state where the gel film is in close contact with the base material. it can. When a plurality of gel films in close contact with a base material are heat-pressed at once, the base material functions as a release sheet, so that the release sheet is not always required and the gel film is deformed by heating. Can be suppressed.
Further, for example, in the case where the film forming process is a continuous method, when the heating step and the peeling step are performed in this order, the heat pressing can be performed while tension is applied to the base material in the heating step, and the gel film can be formed. There is no need to apply tension directly. Therefore, it is possible to prevent deformation such as wrinkles caused by directly applying tension to the gel film from remaining on the gel film or cracking.

4. Defoaming Step In the present disclosure, a defoaming step of defoaming the polymer gel dispersion may be performed before the film forming step. This is because a gel film with few bubbles can be obtained macroscopically. As a result, it is possible to obtain a gel film having excellent smoothness with less unevenness due to air bubbles.

The method for defoaming the polymer gel dispersion is not particularly limited as long as it can remove air bubbles in the polymer gel dispersion, and for example, vacuum defoaming can be used. .. Further, a method of adding an antifoaming agent to the polymer gel dispersion in advance can also be used.

5. Other Steps The method for producing a gel film of the present disclosure may include other steps in addition to the above steps. Other steps include, for example, a packing step for cutting the gel film after the peeling step, a packing step for packing the gel film after the peeling step and the heating step, or after the cutting step when the cutting step is performed. Examples thereof include a sterilization step of sterilizing the gel film after the step and the packing step. In particular, when the gel membrane is a biocompatible gel membrane, it is preferable to carry out a sterilization step.

In the cutting step, the method for cutting the gel film is not particularly limited as long as the gel film can be cut out to a predetermined size, and a general cutting method can be applied.
When cutting the gel film, it is preferable that the humidity is relatively high so that the gel film is not cracked.
The cutting step may be performed after the drying step, before the heating step, or after the heating step.

In the packing step, the method for packing the gel film is not particularly limited, and a general packing method can be applied.

Further, in the sterilization step, the method for sterilizing the gel membrane is not particularly limited, and a general sterilization method can be applied. For example, gamma sterilization and the like can be used.

6. Gel film The gel film produced by the method for producing a gel film of the present disclosure is preferably a single layer. In the present disclosure, a single-layer gel film having excellent smoothness can be obtained.

The thickness of the gel film produced by the method for producing a gel film of the present disclosure can be appropriately set according to the type of polymer gel, the use of the gel film, and the like. For example, the thickness of the gel film can be about 40 μm or more and 80 μm or less.

In the present disclosure, the strength of the gel film can be increased by performing a heating step after the film forming step. As the strength of the gel film, for example, the swelling rate of the gel film or the thermal decomposition time of the gel film can be used as an index.

The swelling rate of the gel membrane is preferably in the range of 100% or more and 130% or less, and more preferably in the range of 100% or more and 125% or less when the gel membrane is gamma-sterilized. preferable. When the swelling rate is within the above range, it is possible to suppress the embrittlement of the gel film due to swelling and improve the handleability. On the other hand, if the swelling rate is too high, the gel film may become brittle due to swelling, and the gel film may be easily broken. The swelling rate of the gel membrane correlates with the crosslinked structure of the gel membrane. For example, when the crosslink density is high, the swelling rate of the gel membrane is low, and when the crosslink density is low, the swelling rate of the gel membrane is high. Become. Therefore, if the swelling rate of the gel film is high, the crosslink density is low and the desired strength may not be obtained.

Here, the swelling rate of the gel film can be determined by the following method. First, a gel film having a predetermined size is prepared. The size of the gel film is preferably a strip shape having a length in the short side direction of 1 cm and a length in the long side direction of 5 cm. The gel membrane is then immersed in saline or phosphate buffered solution (PBS) at room temperature for 30 minutes. When PBS is used, it may be PBS having a pH of 7.2 to 7.6. After that, the swelling rate is determined by the change in the dimensions of the gel film before and after immersion, that is, by the following formula.
Swelling rate [%] = (Dimensional fluctuation rate in the short side direction + Dimensional fluctuation rate in the long side direction) / 2
Dimensional variation rate in the short side direction [%] = L2 / L1 × 100
Dimensional variation rate in the long side direction [%] = L4 / L3 × 100
(L1 is the length in the short side direction of the gel film before immersion, L2 is the length in the short side direction of the gel film after immersion, L3 is the length in the long side direction of the gel film before immersion, and L4 is the length in the long side direction after immersion. Represents the length of the gel film in the long side direction.)
The swelling rate of 100% means that the size of the gel film does not change before and after immersion.

The thermal decomposition time of the gel film is preferably in the range of, for example, 150 minutes or more and 240 minutes or less, and more preferably 170 minutes or more and 220 minutes or less. Here, the thermal decomposition time of the gel film is an index of the decomposition time of the gel film in the living body. The gel membrane exists in the living body for a certain period of time, and then is decomposed, excreted or metabolized in the living body. When the thermal decomposition time of the gel film is within the above range, the decomposition time of the gel film in the living body can be set to a desired time. Further, the heat decomposition time of the gel film has a correlation with the crosslinked structure of the gel film. For example, when the crosslink density is high, the heat decomposition time is long, and when the crosslink density is low, the heat decomposition time is short. Therefore, if the heat decomposition time of the gel film is short, the crosslink density becomes low, and the desired strength may not be obtained.

Here, the thermal decomposition time of the gel film can be obtained by the following method. First, a gel film is cut into a size of 1 cm × 2 cm, and a test piece is prepared. The test piece is then immersed in phosphate buffered solution (PBS) and heated to 90 ° C. The time required for the test piece in the phosphate buffer solution to become invisible is defined as the thermal decomposition time.

Further, a protective sheet may be arranged on one side or both sides of the gel film. This is because the gel film can be easily handled.

7. Applications The gel film produced by the method for producing a gel film of the present disclosure can be used for a desired purpose. When the gel film is a biocompatible gel film, it can be used for, for example, medical materials, cosmetics, beauty materials and the like. Above all, when the gel film has biocompatibility, it is suitable for medical materials. Specific examples of the medical material include an adhesion preventive material, a wound dressing, a surface covering material for medical equipment, a scaffolding material for regenerative medicine, a carrier for a sustained-release drug, a hemostatic material, artificial skin and the like.

B. Gel film The gel film of the present disclosure includes a polymer gel, wherein the polymer gel is at least one selected from the group consisting of hyaluronic acid, hyaluronic acid acid and hyaluronic acid derivatives, and carboxymethyl cellulose, carboxymethyl cellulose salt and carboxy. From a gel containing at least one selected from the group consisting of methylcellulose derivatives, or from at least one selected from the group consisting of hyaluronic acid, hyaluronic acid and hyaluronic acid derivatives, from carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose derivatives. A gel which is a copolymer with at least one selected from the group, the gel film has a first surface and a second surface, and the arithmetic average roughness (Ra1) of the first surface. ) Is smaller than the arithmetic average roughness (Ra2) of the second surface, and the arithmetic average roughness (Ra1) of the first surface is within the range of 10 nm or more and 1000 nm or less. A gel film in which the value Ra1 / Ra2 obtained by dividing the arithmetic average roughness (Ra1) by the arithmetic average roughness (Ra2) of the second surface is in the range of 0.05 or more and 1.0 or less.

In the present disclosure, since Ra1 / Ra2 of the gel film is within the above range, the difference in surface area between the first surface of the gel film and the second surface of the gel film is small, so that the first surface of the gel film is the first. The difference in the rate of moisture absorption and desorption between the surface and the second surface of the gel film can be reduced. Therefore, even if the gel film is temporarily curled in the process of manufacturing the gel film, the gel film is quickly smoothed and can be used for the next step. As a result, when producing the gel film, it is possible to quickly produce the gel film without requiring a long time to remove the curl of the gel film.

Further, in the gel film in the present disclosure, since Ra1 is within the above range and Ra1 / Ra2 is within the above range, it can be said that there are few irregularities, that is, there is little deformation such as wrinkles and waviness. That is, it can be said that the gel film in the present disclosure is obtained by hot-pressing the gel film using a hot plate as described in the above-mentioned "A. Method for producing gel film".

For example, in the method of drying the polymer gel dispersion liquid film to obtain a gel film or the method of obtaining a gel film by pressing at the time of forming the polymer gel dispersion liquid film, the gel film having Ra1 / Ra2 described above is used. It is difficult to obtain. This is because wrinkles and waviness occur in the gel film due to the shrinkage of the polymer gel dispersion film as the drying progresses.

Further, as a method for heating the gel film, for example, in addition to heat pressing with a hot plate, heating with a hot roll, infrared heating, oven heating, hot plate heating and the like can be considered. However, heating with a heat roll may leave roll marks on the gel film, or wrinkles may occur in the gel film when the gel film passes through the heat roll. Further, in infrared heating, oven heating, and hot plate heating, the gel film is liable to be deformed such as wrinkles and wrinkles. Therefore, it is difficult to obtain a smooth gel film by a heating method other than hot pressing with a hot plate, and it is difficult to obtain a gel film satisfying Ra1 and Ra1 / Ra2.

Hereinafter, the gel film of the present disclosure will be described.

The arithmetic mean roughness (Ra1) of the first surface of the gel film is in the range of 10 nm or more and 1000 nm or less, preferably in the range of 100 nm or more and 1000 nm or less, and more preferably 500 nm or more and 1000 nm or less. It is within the range.

Further, the value Ra1 / Ra2 obtained by dividing the arithmetic mean roughness (Ra1) of the first surface of the gel film by the arithmetic mean roughness (Ra2) of the second surface is in the range of 0.05 or more and 1.0 or less. Is inside.

Further, the arithmetic mean roughness (Ra2) of the second surface of the gel film is larger than the arithmetic average roughness (Ra1) of the first surface, and may satisfy the above Ra1 / Ra2, for example, 500 nm or more. It can be in the range of 1500 nm or less, preferably in the range of 500 nm or more and 1200 nm or less, and more preferably in the range of 500 nm or more and 1000 nm or less.

Here, the arithmetic mean roughness (Ra1) of the first surface of the gel film and the arithmetic mean roughness (Ra2) of the second surface are measured by a white interferometer (Zygo, manufactured by Canon Marketing Japan Co., Ltd.). A 50x objective lens is used to measure the range of 216.2 μm × 216.2 μm. The arithmetic average roughness (Ra1) of the first surface of the gel film and the arithmetic average roughness (Ra2) of the second surface are measured at nine points on each surface of the gel film and are the average value of the measured values. To do. Further, the measurement areas at each location shall be regions separated from each other by at least 30 mm or more.

The gel film of the present disclosure can be produced by the above-mentioned method for producing a gel film.

The polymer gel and other points such as the thickness and characteristics of the gel film have been described in the above-mentioned "A. Method for producing gel film", and thus the description thereof will be omitted here.

The present disclosure is not limited to the above embodiment. The above-described embodiment is an example, and any object having substantially the same structure as the technical idea described in the claims of the present disclosure and exhibiting the same action and effect is described in this invention. Included in the technical scope of disclosure.

Examples and comparative examples are shown below, and the present disclosure will be described in more detail.

[Examples 1-1 to 1-9]
A polymer gel obtained by copolymerizing carboxymethyl cellulose and hyaluronic acid using EDC (1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride) as a condensing agent is used as a dispersion medium (water) at a ratio of 2% by mass. The mixture was dispersed to prepare a polymer gel dispersion.

The obtained polymer gel dispersion is poured into an acrylic resin container having an inner size of 150 mm × 180 mm and a depth of 3 mm, and an applicator (SA-204 micrometer film applicator, manufactured by Tester Sangyo Co., Ltd.) is used. , A polymer gel dispersion film having a uniform thickness was obtained. The obtained polymer gel dispersion film is allowed to stand in a constant temperature and humidity chamber set at 20 ° C. and 55% RH for 20 hours to remove the dispersion medium contained in the polymer gel dispersion, thereby gelling. The membrane was formed. Then, the gel film was peeled off from the acrylic resin container. To peel off the gel film from the acrylic resin container, use a small punching machine type III (manufactured by Tester Sangyo Co., Ltd.) to make a cut in the gel film in close contact with the acrylic resin container to a size of 146 mm x 176 mm and gel. This was done by peeling the gel film from the acrylic container while supporting the cut end of the film.

Next, the gel film sandwiched between dust-free paper (clean room paper CP-01HA4, manufactured by Ostrich Diamond Co., Ltd.) is pressed with a heated parallel plate hot plate under the heat pressing conditions shown in Table 1 below. Therefore, a hot press was carried out. The gel film after hot pressing was allowed to stand in a constant temperature and humidity chamber at 20 ° C. and 55% RH for 2 hours to cool, and a gel film was obtained.

[Comparative Example 1]
A gel film was obtained in the same manner as in Examples 1-1 to 1-9 except that the hot pressing conditions shown in Table 1 below were used.

[Comparative Example 2]
A gel film was obtained in the same manner as in Examples 1-1 to 1-9 except that the heat pressing was not performed.

[Evaluation 1]
(Smoothness)
The smoothness of the obtained gel film was evaluated.
〇: There is no deformation such as wrinkles, swells, and curls on the gel film. ×: There is deformation such as wrinkles, swells, and curls on the gel film.

(Swelling rate)
The swelling rate was determined after irradiating the obtained gel film and the obtained gel film with gamma rays of 25 kGy. First, a strip-shaped test piece having a length of 1 cm in the short side direction and a length of 5 cm in the long side direction was cut out from the gel film. Next, the test piece was immersed in physiological saline at room temperature for 30 minutes. Then, the swelling rate was determined by the change in the dimensions of the test piece before and after immersion, that is, by the following formula.
Swelling rate [%] = (Dimensional fluctuation rate in the short side direction + Dimensional fluctuation rate in the long side direction) / 2
Dimensional variation rate in the short side direction [%] = L2 / L1 × 100
Dimensional variation rate in the long side direction [%] = L4 / L3 × 100
(L1 is the length of the test piece before immersion in the short side direction, L2 is the length of the test piece after immersion in the short side direction, L3 is the length of the test piece before immersion in the long side direction, and L4 is the length of the test piece after immersion. Indicates the length of the test piece in the long side direction.)

(Brittleness when swollen)
After irradiating the obtained gel membrane with gamma rays of 25 kGy, the brittleness of the gel membrane when immersed in physiological saline for 30 minutes was evaluated in the same manner as in the measurement of the swelling rate.
⊚: The gel film does not collapse even when the gel film being immersed is picked with tweezers and shaken lightly in physiological saline. 〇: The gel film does not collapse when the gel film being immersed is picked with tweezers ×: Immersion When the gel film inside is picked with tweezers, the gel film collapses

[Examples 2-1 to 2-21]
Twenty-five gel films were formed in the same manner as in Example 1-1, and each gel film was peeled off from the acrylic resin container.
Next, a laminate prepared by alternately stacking dust-free paper (clean room paper CP-01HA4, manufactured by Ostrich Diamond Co., Ltd.) and a gel film was further sandwiched between dust-free paper, and under the heat pressing conditions shown in Table 2 below. The heat press was carried out by applying pressure with a hot plate of a heated parallel flat plate. Then, it cooled in the same manner as in Example 1-1 to obtain a gel film.

[Evaluation 2]
In the same manner as in Example 1-1, the swelling rate of the obtained gel film was measured, and the smoothness and brittleness at the time of swelling were evaluated. In Table 2, the stacking order 1/25 is the gel film at the bottom of the laminated body, the stacking order 13/25 is the 13th gel film from the bottom of the laminated body, and the stacking order 25/25 is one of the laminated bodies. The top gel film is shown.

[Comparative Example 3]
A gel film was formed in the same manner as in Example 1-1, and the gel film was peeled off from the acrylic resin container.
Next, the heat treatment was performed by heating in an incubator at 100 ° C. for 1 hour. Then, it cooled in the same manner as in Example 1-1 to obtain a gel film.

[Comparative Example 4]
A gel film was formed in the same manner as in Example 1-1, and the gel film was peeled off from the acrylic resin container.
Next, the heat treatment was performed by heating in an incubator at 150 ° C. for 2 minutes. Then, it cooled in the same manner as in Example 1-1 to obtain a gel film.

[Comparative Example 5]
A gel film was formed in the same manner as in Example 1-1, and the gel film was peeled off from the acrylic resin container.
Next, a far-infrared heater (PU-2060A, manufactured by Noritake Company Limited) was installed so that the infrared source came at a distance where the surface temperature of the gel film was 120 ° C., and heated for 5 minutes. Heat treatment was performed. Then, it cooled in the same manner as in Example 1-1 to obtain a gel film.

[Comparative Example 6]
A gel film was formed in the same manner as in Example 1-1, and the gel film was peeled off from the acrylic resin container.
Next, the heat treatment was performed by passing a gel film through a heat roll (Lami Monkey LK-29, manufactured by Rummy Corporation) heated to 140 ° C. 20 times. Then, it cooled in the same manner as in Example 1-1 to obtain a gel film.

[Evaluation 3]
The smoothness of the gel membranes of Examples 2-10, 2-11 and Comparative Examples 3 to 6 was evaluated in the same manner as in Example 1-1. In addition, photographs of the appearance of the gel membranes of Examples 2-10 and 2-11 and Comparative Examples 3 to 6 are shown in FIGS. 5 (a) to 5 (b) and FIGS. 6 (a) to 6 (d), respectively.

[Examples 3-1 to 3-3]
A gel film was obtained in the same manner as in Example 1-5 except that the hot pressing time was 7 minutes.

The arithmetic mean roughness (Ra1) of the first surface and the arithmetic mean roughness (Ra2) of the second surface of the obtained gel film were measured with a white interferometer (Zygo, manufactured by Canon Marketing Japan Co., Ltd.). It was determined by measuring a range of 216.2 μm × 216.2 μm using a 50x objective lens. The arithmetic average roughness (Ra1) of the first surface of the gel film and the arithmetic average roughness (Ra2) of the second surface were measured at 9 points and used as the average value of the measured values. In addition, the measurement regions at each location were defined as regions separated from each other by at least 30 mm or more.

In addition, curl suppression was evaluated for the obtained gel film.
◯: In an atmosphere of 20 ° C. and 55% RH, even if the gel film is curled, it is quickly smoothed.

1 ... Base material 2a ... Polymer gel dispersion film 2b ... Gel film after drying 2c ... Gel film after hot pressing 11 ... Hot plate

Claims (9)

A film-forming process for forming a gel film containing a polymer gel,
A heating step of hot-pressing the gel film using a hot plate, and
A method for producing a gel film. The method for producing a gel film according to claim 1, wherein the gel film is a single layer. The method for producing a gel film according to claim 1 or 2, wherein the hot plate is a flat plate. The gel film according to any one of claims 1 to 3, wherein in the heating step, a laminate in which a plurality of the gel films and a plurality of release sheets are alternately laminated is collectively heat-pressed. Production method. The film forming process is
A polymer gel dispersion liquid film forming step of forming a polymer gel dispersion liquid film on one surface of a base material using the polymer gel dispersion liquid containing the polymer gel and a dispersion medium.
It has a drying step of removing the dispersion medium to obtain a gel film by drying the polymer gel dispersion liquid film.
The method for producing a gel film according to any one of claims 1 to 4, further comprising a peeling step of peeling the gel film from the substrate between the film forming step and the heating step. The polymer gel contains at least one selected from the group consisting of hyaluronic acid, hyaluronic acid salt and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. , Or a copolymer of at least one selected from the group consisting of hyaluronic acid, hyaluronic acid acid and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose derivatives. Is a gel
The method for producing a gel film according to any one of claims 1 to 5, wherein the heating temperature in the heating step is within the range of 100 ° C. or higher and lower than 200 ° C. The method for producing a gel film according to any one of claims 1 to 6, wherein the gel film is a biocompatible gel film. A gel membrane containing a polymer gel
The polymer gel contains at least one selected from the group consisting of hyaluronic acid, hyaluronic acid salt and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salt and carboxymethyl cellulose derivative. , Or a copolymer of at least one selected from the group consisting of hyaluronic acid, hyaluronic acid acid and hyaluronic acid derivatives, and at least one selected from the group consisting of carboxymethyl cellulose, carboxymethyl cellulose salts and carboxymethyl cellulose derivatives. Is a gel
The gel film has a first surface and a second surface, and the arithmetic mean roughness (Ra1) of the first surface is smaller than the arithmetic mean roughness (Ra2) of the second surface. The arithmetic mean roughness (Ra1) of the first surface is within the range of 10 nm or more and 1000 nm or less, and the arithmetic mean roughness (Ra1) of the first surface is set to the arithmetic mean roughness (Ra1) of the second surface. A gel film in which the value Ra1 / Ra2 divided by Ra2) is in the range of 0.05 or more and 1.0 or less. The gel film according to claim 8, which is a gel film having biocompatibility.