JP2018158973A - Method for producing thin polymer film dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer thin film dispersion having high production efficiency and suitable for mass production. In the method for producing a polymer thin film dispersion of the present invention, (a) a film-like laminate 10 including a process film 2 and a polymer thin film 1 and a water-permeable sheet 3 are combined with a polymer thin film 1. A step of laminating the water-permeable sheet 3 so as to face each other, a step of (b) a step of peeling the process film 2 from the polymer thin film 3, and (c) a step of winding the film into a roll to form the polymer thin film 1 and water. A step of obtaining a wound body in which the permeable sheet 3 is wound together in a roll shape, (d) a step of immersing the wound body in a liquid medium, and (e) water permeability peeled from a polymer thin film. This method includes a step of removing the sheet 3 from the liquid medium and (f) a step of shredding and dispersing the polymer thin film 1 in the liquid medium to obtain a polymer thin film dispersion. [Selection diagram] Fig. 4

Description

  The present invention relates to a method for producing a polymer thin film dispersion.

Conventionally, a technique for producing a biocompatible polymer thin film having a thickness of several tens to several hundreds of nanometers made of a polymer such as poly-L-lactic acid is known (for example, Patent Document 1).
Since such a polymer thin film has bioabsorbability, biodegradability, tissue repairability, and the like, it is excellent in applicability to living tissue.
In addition, such polymer thin films are known to adhere firmly to living tissues due to electrostatic force and wettability when applied to living tissues such as healthy skin, skin wound surfaces, organ wound surfaces, and corneas. Yes.
Therefore, since the polymer thin film has such properties, it has been studied as a covering material for living tissue such as healthy skin, skin wound surface, organ wound surface and cornea.

For example, Patent Document 1 discloses a thin film structure obtained by the following steps.
(A) adsorbing a multifunctional molecule in an arbitrarily shaped region at the interface with the liquid phase of the substrate;
(B) polymerizing and / or crosslinking the adsorbed polyfunctionality to form a polymer thin film;
(C) The formed thin film is peeled off from the substrate.

International Publication No. 2006/025592

  However, the polymer thin film described in Patent Document 1 must adsorb polyfunctional molecules to a substrate and polymerize it. Therefore, the polymer thin film described in Patent Document 1 is compared with a method of forming a polymer thin film by continuously applying a polymer thin film forming solution to a long release sheet and drying it. There was a problem that the production efficiency was low and it was difficult to shift to mass production. The polymer thin film dispersion is produced by chopping and dispersing the polymer thin film in a liquid medium. Therefore, the polymer thin film dispersion has the same problem that the production efficiency is low and it is difficult to shift to mass production. On the other hand, a polymer thin film obtained by a method of forming a polymer thin film on a release sheet cannot be easily released from the release sheet in a liquid medium, and it is difficult to produce a polymer thin film dispersion. There was a problem.

  An object of the present invention is to provide a method for producing a polymer thin film dispersion having high production efficiency and suitable for mass production.

According to one aspect of the invention,
(A) a step of laminating a film-like laminate comprising a process film and a polymer thin film, and a water permeable sheet so that the polymer thin film and the water permeable sheet face each other;
(B) peeling the process film from the polymer thin film;
(C) The process of winding in roll shape and obtaining the wound body by which the said polymer thin film and the said water-permeable sheet were wound together in roll shape,
(D) immersing the wound body in a liquid medium;
(E) removing the water-permeable sheet peeled from the polymer thin film from the liquid medium;
(F) chopping and dispersing the polymer thin film in the liquid medium to obtain a polymer thin film dispersion;
A method for producing a polymer thin film dispersion is provided.

In one aspect of the present invention described above, the water permeable sheet is preferably at least one selected from the group consisting of a nonwoven fabric and paper.
In the above-described embodiment of the present invention, the polymer thin film preferably has a thickness of 5 nm to 1000 nm.
In one embodiment of the present invention, the polymer constituting the polymer thin film is at least one selected from the group consisting of polylactic acid, lactic acid copolymer, polylactone, lactone copolymer, and polypeptide. preferable.
In one embodiment of the present invention described above, the air permeability of the water permeable sheet is preferably 100,000 seconds or less.
In one aspect of the present invention described above, the water permeable sheet preferably has a thickness of 25 μm or more.

In the above-described aspect of the present invention, it is preferable that the peeling force of the step film from the polymer thin film in the step (b) is 10 mN / 100 mm or more and 1000 mN / 100 mm or less.
1 aspect of the above-mentioned this invention WHEREIN: It is preferable that the said film-like laminated body and the said water-permeable sheet are strip | belt shape.
1 aspect of the above-mentioned this invention WHEREIN: It is preferable that the width dimension in planar view of the said water-permeable sheet | seat is 1200 mm or less.
In one aspect of the present invention described above, the water-permeable sheet is partially provided with an adhesive layer on one side, and in the step (a), the polymer thin film and the adhesive layer are pasted. By combining, it is preferable to laminate | stack the said film-like laminated body and the said water-permeable sheet.
In the above-described aspect of the present invention, it is preferable that the water-permeable sheet is provided with the pressure-sensitive adhesive layer at a front end portion in a length direction in a plan view.

  According to the present invention, it is possible to provide a method for producing a polymer thin film dispersion having high production efficiency and suitable for mass production.

It is the schematic which shows the film-form laminated body which concerns on embodiment of this invention. It is the schematic which shows the adhesive sheet which concerns on embodiment of this invention. It is the schematic which shows the state which laminated | stacked the film-form laminated body and the adhesive sheet in the process (a) which concerns on embodiment of this invention. It is the schematic which shows the state which peeled the process film from the polymer thin film in the process (b) which concerns on embodiment of this invention. It is the schematic which shows the wound body obtained at the process (c) which concerns on embodiment of this invention. It is the schematic which shows the state which immersed the winding body in the liquid medium in the process (d) which concerns on embodiment of this invention. It is the schematic which shows the state which the water-permeable sheet peeled from the polymer thin film in the liquid medium in the process (e) which concerns on embodiment of this invention. It is the schematic which shows the state which removed the water-permeable sheet from the liquid medium in the process (e) which concerns on embodiment of this invention. It is the schematic which shows the state which cut and disperse | distributed the polymer thin film in a liquid medium in the process (f) which concerns on embodiment of this invention.

  Hereinafter, the present invention will be described with reference to the drawings, taking an embodiment as an example. The present invention is not limited to the contents of the embodiment. In the drawings, there are portions enlarged or reduced for easy explanation.

The method for producing a polymer thin film dispersion according to this embodiment is as follows.
(A) a step of laminating a film-like laminate comprising a process film and a polymer thin film, and a water permeable sheet so that the polymer thin film and the water permeable sheet face each other;
(B) peeling the process film from the polymer thin film;
(C) The process of winding in roll shape and obtaining the wound body by which the said polymer thin film and the said water-permeable sheet were wound together in roll shape,
(D) immersing the wound body in a liquid medium;
(E) removing the water-permeable sheet peeled from the polymer thin film from the liquid medium;
(F) chopping and dispersing the polymer thin film in the liquid medium to obtain a polymer thin film dispersion.

  First, the film-like laminate and the water permeable sheet used in this embodiment will be described.

(Film laminate)
As shown in FIG. 1, the film-like laminate 10 used in the present embodiment includes a polymer thin film 1 and a process film 2. This film-like laminate 10 is obtained by applying a polymer thin film forming solution to the process film 2 to form the polymer thin film 1. The film-like laminate 10 is preferably strip-shaped.

(Polymer thin film)
The polymer thin film 1 preferably contains a water-insoluble polymer.
This is because the main application target of the polymer thin film in the present embodiment is a living tissue such as an organ wound surface or cornea, epidermis, etc., and basically has a mucus derived from a living body, sweat, etc. on its surface. Therefore, the polymer thin film is prevented from being dissolved by moisture contained in the mucus or the like.
Therefore, the material substance of the polymer thin film in the present embodiment is not particularly limited as long as it can form a water-insoluble polymer thin film, and a conventionally known material substance can be used. More preferably, a material substance is used.
Further, in order to make the polymer thin film water-insoluble in this embodiment, the material substance does not necessarily need to be water-insoluble. Finally, the material substance is subjected to heat drying, crosslinking reaction, polymerization, etc. Any water-insoluble polymer thin film can be used.

Further, the specific material is preferably at least one selected from the group consisting of polylactic acid, lactic acid copolymer, polylactone, lactone copolymer and polypeptide.
This is because a polymer thin film having a more uniform thickness can be obtained more stably by including these material substances.

Moreover, when using polylactic acid as a material substance, the polymer of L-lactic acid, the polymer of D-lactic acid, and the polymer of lactic acid containing L-lactic acid and D-lactic acid can be used, for example.
A polymer of lactide which is a cyclic dimer of lactic acid such as L-lactide, D-lactide, and meso-lactide may be used as a material substance.

Moreover, when using a lactic acid copolymer as a material substance, the polymer of lactic acid and another monomer component can be used.
Examples of the other monomer components described above include hydroxycarboxylic acids (for example, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, and 6-hydroxycaproic acid), Compounds containing a hydroxyl group or derivatives thereof (for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, polyethylene glycol, glycerin, pentaerythritol, etc.) and compounds having a plurality of carboxylic acid groups in the molecule or Derivatives thereof (for example, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulfoisophthalic acid. ), And the like.
Further, the mass ratio (lactic acid / other monomer components) when copolymerizing lactic acid and other monomer components constituting the lactic acid copolymer is 50/50 or more and 99/1 or less. preferable.

  When polylactone is used as a material substance, for example, lactone polymers such as ε-prolactone, δ-butyrolactone, β-methyl-δ valerolactone, and β-propiolactone can be used.

Moreover, when using a lactone copolymer as a material substance, the polymer of a lactone and another monomer component can be used, for example.
Examples of the other monomer components described above include hydroxycarboxylic acids (for example, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 4-hydroxyvaleric acid, and 6-hydroxycaproic acid), Compounds containing a hydroxyl group or derivatives thereof (for example, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, polyethylene glycol, glycerin, pentaerythritol, etc.) and compounds having a plurality of carboxylic acid groups in the molecule or Derivatives thereof (for example, succinic acid, adipic acid, sebacic acid, fumaric acid, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulfoisophthalic acid. ), And the like. Moreover, you may use the lactic acid or lactide mentioned above as another monomer component.
In addition, the mass ratio (lactone / other monomer component) when copolymerizing the lactone constituting the lactone copolymer with other monomer components is 50/50 or more and 99/1 or less. preferable.

  When using a polypeptide as a material substance, for example, polylysine, polyglutamine, polyasparagine, polyarginine, polyglutamic acid, polyaspartic acid, polyglycine, polyphenylalanine, polyalanine, polyleucine, polyisoleucine, polyvaline, Polyproline, polyserine, polythreonine, polytyrosine and the like can be used.

In addition, a polymer electrolyte (polycation and polyanion) having opposite charges can also be used as a material substance. By alternately applying a dilute solution containing a polycation and a dilute solution containing a polyanion to a substrate, a polymer thin film in which the polycation and the polyanion are laminated can be formed. In addition, as a laminated body of a polycation and a polyanion, it is good also as a 2 layer laminated body which laminated | stacked the polycation layer and the polyanion layer 1 layer at a time, but it is further laminated | stacked alternately and is 4 layers-20 layers It is good also as a laminated body of a grade.
Examples of such polycations include polylysine, polyglutamine, polyasparagine, and polyarginine. Examples of polyanions include polyglutamic acid and polyaspartic acid.

Moreover, it is preferable to make the weight average molecular weight of a material substance into the value within the range of 10,000 or more and 2,000,000 or less.
This is because the polymer thin film having a more uniform thickness can be obtained more stably by setting the weight average molecular weight of the material substance within this range, and the strength of the polymer thin film can be increased. This is because it can be further improved.
If the weight average molecular weight of the material substance is 10,000 or more, it can be suppressed that the strength of the polymer thin film becomes insufficient. On the other hand, if the weight average molecular weight of the material substance is 2,000,000 or less, it is possible to suppress the non-uniform thickness of the polymer thin film.
Therefore, the weight average molecular weight of the material substance is more preferably set to a value within the range of 30,000 to 1,000,000, and further preferably set to a value within the range of 50,000 to 500,000. . The weight average molecular weight in this specification is a standard polystyrene conversion value measured by a gel permeation chromatography (GPC) method.

Further, the material substance may be not only a polymer as described above but also a polyfunctional monomer.
However, when forming a polymer thin film using these polyfunctional monomers, it is necessary to polymerize or further crosslink the polyfunctional monomer.
Examples of such polyfunctional monomers include amino acids, saccharides, functional groups in the molecule (for example, amino group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, aldehyde group, epoxy group, and cyanur group). And a monomer having a plurality of vinyl groups in the molecule (for example, divinylbenzene, divinyl ether, divinylsulfone, bismaleimide, etc.).

In addition, the thickness of the polymer thin film 1 is preferably set to a value within the range of 5 nm to 1000 nm.
The reason for this is that by setting the thickness of the polymer thin film within such a range, when the polymer thin film is applied to a living tissue such as an organ wound surface or cornea as an application target, the film strength is kept moderate. This is because the polymer thin film can be firmly adhered to the living tissue.
If the thickness of the polymer thin film is 5 nm or more, the film strength can be prevented from excessively decreasing, and the polymer thin film tends to break excessively when the polymer thin film is applied to the application target. This can be suppressed. On the other hand, if the thickness of the polymer thin film is 1000 nm or less, it is possible to suppress an excessive decrease in the adhesion to the application object.
Therefore, the thickness of the polymer thin film 1 is more preferably set to a value within the range of 10 nm to 700 nm, and further preferably set to a value within the range of 20 nm to 400 nm.

It is also preferable to modify the surface of the polymer thin film 1 with a functional substance.
Here, the “functional substance” means a recognition protein on the cell membrane and its ligand, a substance having molecular recognition ability such as an antigen or an antibody, a substance that promotes a specific reaction such as a catalyst or an enzyme, an antioxidant or a radical. It means a substance involved in a specific reaction such as an erasing agent, or a group or ligand involved in charge or reaction such as carboxyl group, amino group, mercapto group, maleimide group.
Moreover, the substance which makes a function express using the charge (electrostatic interaction) of a polymer electrolyte is also contained in a functional substance.
For example, the functional substance includes at least one selected from the group consisting of polymer compounds such as polyethylene glycol and sugar chains, proteins, peptides, sugar chains, biotin derivatives, polycations and polyanion polymer electrolytes. The functional substance is not limited to these.
In addition, as a bonding method of the functional substance, there is a method of chemically or physically bonding.
First, as a method of chemically bonding, amino group, carboxyl group, hydroxyl group, mercapto group, isocyanate group, aldehyde group, epoxy group, cyanuric group, or vinyl introduced into the polymer constituting the polymer thin film. It can be attached to the group via a functional group that can be attached.
For example, as a binding reaction between a functional substance and a polymer thin film, a urethane bond or a urea bond by a reaction between a hydroxyl group or an amino group and an isocyanate group, formation of a Schiff base by a reaction between an amino group and an aldehyde group, mercapto A reaction between a disulfide bond between groups, a mercapto group, a pyridyl disulfide group or a maleimide group, a reaction between a carbonyl group and a succinimide group, or the like can be used.

In addition, as a physical bonding method, electrostatic interaction, hydrophobic interaction, hydrogen bonding, intermolecular force, or the like between the functional substance side and the polymer thin film side can be used.
Alternatively, a functional substance can be immobilized on a polymer thin film by introducing a ligand into one of the polymer thin film and the functional substance, introducing an acceptor into the other, and utilizing a complex of the ligand and the acceptor.
Specific combinations include biotin and avidin, sugar chain and lectin, antigen and antibody, drug and receptor, enzyme and substrate, and the like.
Examples of enzymes include catalase, chymotrypsin, cytochrome, α-amylase, β-amylase, galactosidase, glycocerebrosidase, blood coagulation factor, peroxidase, protease, cellulase, hemicellulase, xylanase, lipase, pullulanase, isomerase, glucoamylase, Examples of the enzyme include, but are not limited to, glucose isomerase, glutaminase, β-glucanase, and serine protease.

(Process film)
The process film 2 is not particularly limited. For example, from the viewpoint of ease of handling, the process film 2 preferably includes a release substrate and a release agent layer formed by applying a release agent on at least one surface of the release substrate. Examples of the release substrate include a paper substrate, a laminated paper obtained by laminating a thermoplastic resin such as polyethylene on the paper substrate, and a plastic film.
Examples of the paper substrate include glassine paper, high-quality paper, coated paper, and cast coated paper. Examples of the plastic film include polyester films (for example, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate), and polyolefin films (for example, polypropylene and polyethylene).
Examples of the release agent include olefin resins, rubber elastomers (eg, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, fluorine resins, and silicone resins. Among these, the release agent is any selected from the group consisting of olefin resins, rubber elastomers (for example, butadiene resins, isoprene resins, etc.), long chain alkyl resins, alkyd resins, and fluorine resins. Such a release agent is preferable. The release agent layer may further contain an antistatic agent or may not contain an antistatic agent.

The thickness of the process film 2 is not particularly limited. The thickness of the process film 2 is usually 20 μm or more and 200 μm or less, and preferably 25 μm or more and 150 μm or less.
The thickness of the release agent layer is not particularly limited. When a release agent layer is formed by applying a solution containing a release agent on a release substrate, the thickness of the release agent layer is preferably 0.01 μm or more and 2.0 μm or less, and 0.03 μm or more and 1 More preferably, it is 0.0 μm or less.
When a plastic film is used as the release substrate, the thickness of the plastic film is preferably 3 μm or more and 50 μm or less, more preferably 5 μm or more and 90 μm or less, and particularly preferably 10 μm or more and 40 μm or less.

(Polymer thin film forming solution)
Since the material substance for polymer thin film formation as a solute in the polymer thin film formation solution has already been described, the description thereof is omitted.

The type of the solvent in the polymer thin film forming solution is not particularly limited as long as it is a solvent that can dissolve or uniformly disperse the material substance for forming the polymer thin film and can be evaporated by heating. For example, the solvent is preferably ethanol, propanol, isopropyl alcohol, acetone, toluene, ethyl acetate, butyl acetate, tetrahydrofuran, methyl ethyl ketone, dichloromethane, or chloroform.
Moreover, as a boiling point of a solvent, it is preferable to set it as the value within the range of 30 to 120 degreeC, and it is more preferable to set it as the value within the range of 35 to 100 degreeC.

Moreover, it is preferable to make the density | concentration of the material substance in the polymer thin film formation solution into the value within the range of 0.1 mass% or more and 20 mass% or less.
If the concentration of the material substance in the polymer thin film forming solution is 0.1% by mass or more, it is possible to suppress a problem that a necessary thickness may not be obtained or a problem that the viscosity of the solution is not optimal. . On the other hand, when the concentration of the material substance in the polymer thin film forming solution is 20% by mass or less, it is possible to suppress a problem that a uniform coating film may not be obtained.
Therefore, the concentration of the material substance in the polymer thin film forming solution is more preferably set to a value within the range of 0.3% by mass to 15% by mass, and within the range of 0.5% by mass to 10% by mass. More preferably, the value of

Moreover, it is preferable to make the viscosity (measurement temperature: 25 degreeC) of the solution for polymer thin film formation into the value within the range of 1 mPa * s or more and 500 mPa * s or less.
If the viscosity of the solution for forming a polymer thin film is 1 mPa · s or more, it is possible to suppress a problem that the coating film is repelled. On the other hand, if the viscosity of the polymer thin film forming solution is 500 mPa · s or less, it is possible to suppress a problem that a uniform coating film cannot be obtained.
Therefore, the viscosity (measurement temperature: 25 ° C.) of the polymer thin film forming solution is more preferably set to a value in the range of 2 mPa · s to 400 mPa · s, and more preferably in the range of 3 mPa · s to 300 mPa · s. More preferably, it is a value.
The viscosity of the polymer thin film forming solution was measured according to JIS K7117-1 4.1 (Brookfield rotary viscometer).

Moreover, although it does not specifically limit as drying conditions for making the application layer of the solution for polymer thin film formation formed on the process film 2 into the polymer thin film 1, Usually, it is 40 to 120 degreeC temperature conditions. In addition, the drying time is preferably 6 seconds or more and 300 seconds or less.
If drying temperature is 40 degreeC or more, the malfunction that drying takes time too much or drying becomes insufficient can be suppressed. On the other hand, if the drying temperature is 120 ° C. or lower, problems such as wrinkles and curling can be suppressed.
Moreover, if the drying time is 6 seconds or more, the problem of insufficient drying can be prevented. On the other hand, if the drying time is 300 seconds or less, problems such as wrinkles and curling can be suppressed.
Therefore, it is more preferable that the drying conditions for forming the coating layer of the polymer thin film forming solution as the polymer thin film 1 are a temperature condition of 50 ° C. or higher and 110 ° C. or lower and a drying time of 12 seconds or longer and 180 seconds or shorter. More preferably, the temperature is 60 ° C. or higher and 100 ° C. or lower, and the drying time is 18 seconds or longer and 120 seconds or shorter.

Moreover, it is preferable to apply the polymer thin film forming solution by a roll-to-roll method.
The reason for this is that, if the roll-to-roll method is used, the polymer thin film 1 having a predetermined thickness can be formed more efficiently, so that the film-like laminate 10 can be mass-produced more efficiently. Because.
In carrying out the roll-to-roll method, it is particularly preferable to use a bar coater, a reverse gravure coater or a slot die coater as a coating apparatus.
The reason for this is that with these coating apparatuses, the polymer thin film 1 having a predetermined thickness can be formed more efficiently.
That is, if it is a bar coater, a reverse gravure coater and a slot die coater, the polymer thin film 1 having a thickness of nanometer order can be formed with a uniform thickness without generating wrinkles on the surface thereof. Moreover, the bar coater, reverse gravure coater and slot die coater have a simple structure and are excellent in economic efficiency.

(Water-permeable sheet)
As shown in FIG. 2, the water-permeable sheet 3 used in the present embodiment preferably has a pressure-sensitive adhesive layer 4 partially provided on one side. The water permeable sheet 3 is a sheet that allows a liquid medium to pass from one side of the sheet to the other side.
Moreover, it is preferable that the shape of the water-permeable sheet 3 is a strip shape. Furthermore, when the shape of the water-permeable sheet 3 is a belt-like shape, the water-permeable sheet 3 is preferably provided with an adhesive layer 4 at the front end portion 3A in the length direction in plan view. Furthermore, the pressure-sensitive adhesive layer 4 is preferably provided over the entire width direction of the water-permeable sheet 3. The water-permeable sheet 3 and the pressure-sensitive adhesive layer 4 constitute the pressure-sensitive adhesive sheet 20 of this embodiment.
The pressure-sensitive adhesive sheet 20 may have a release sheet on the surface of the pressure-sensitive adhesive layer 4. This release sheet may be peeled before the water permeable sheet 3 is laminated on the film-like laminate 10.

The material substance of the water permeable sheet 3 is at least one selected from the group consisting of nonwoven fabric and paper.
Examples of the material of the nonwoven fabric include aramid fiber, glass fiber, cellulose fiber, nylon fiber, vinylon fiber, polyester fiber, polyethylene fiber, polypropylene fiber, polyolefin fiber, and rayon fiber.
Examples of the paper include glassine paper, high-quality paper, and coated paper.
The air permeability of the water permeable sheet 3 is preferably 100,000 seconds or less, and more preferably 50,000 seconds or less, from the viewpoint of ease of permeation of water or the like in the water permeable sheet 3. . Specifically, the air permeability can be measured by the method described in Examples in accordance with JIS-P8117.
The thickness of the water permeable sheet 3 is preferably 25 μm or more, and more preferably 30 μm or more and 1000 μm or less. If the thickness of the water permeable sheet 3 is 25 μm or more, when a wound body is produced and the wound body is immersed in the liquid medium, the liquid medium is immersed in the wound body through the water permeable sheet. Can be included.
Moreover, when the shape of the water-permeable sheet 3 is a belt-like shape, the width dimension in plan view of the water-permeable sheet 3 is preferably 1200 mm or less, more preferably 400 mm or less, and 150 mm or less. Is particularly preferred. If the width dimension of the water permeable sheet 3 is 1200 mm or less, the work of peeling the polymer thin film and the water permeable sheet together from the process film becomes easy. Moreover, the length dimension in planar view of the water-permeable sheet 3 is although it does not specifically limit, Usually, they are 1 m or more and 1000 m or less.

(Adhesive layer)
The pressure-sensitive adhesive layer 4 can be formed using a known pressure-sensitive adhesive. Such an adhesive is not particularly limited, and examples thereof include an acrylic adhesive, a rubber adhesive, a silicone adhesive, a polyurethane adhesive, and a polyester adhesive.

  From the viewpoint of workability, the thickness of the pressure-sensitive adhesive layer 4 is preferably 1 μm or more and 300 μm or less, more preferably 5 μm or more and 200 μm or less, and further preferably 10 μm or more and 100 μm or less.

[Method for producing polymer thin film dispersion]
Next, the manufacturing method of the polymer thin film dispersion of this embodiment is demonstrated.
Moreover, the manufacturing method of the polymer thin film dispersion 200 according to the present embodiment is as follows:
(A) A polymer thin film 1 including a polymer thin film 1 and a process film 2 provided on one surface of the polymer thin film 1, and a water permeable sheet 3 as shown in FIG. 1 and the water permeable sheet 3 are laminated so that they face each other (see FIG. 3);
(B) a process of peeling the process film 2 from the polymer thin film 1 (see FIG. 4);
(C) The process (refer FIG. 5) which obtains the wound body 100 wound by roll shape, and the polymer thin film 1 and the water-permeable sheet 3 were wound by roll shape together,
(D) a step of immersing the wound body 100 in a liquid medium (see FIGS. 6 and 7);
(E) removing the water-permeable sheet 3 peeled off from the polymer thin film 1 from the liquid medium 5 (see FIG. 8);
(F) A manufacturing method including the step of chopping and dispersing the polymer thin film 1 in the liquid medium 5 to obtain a polymer thin film dispersion 200 (see FIG. 9).
According to the method for producing a polymer thin film dispersion of this embodiment, a polymer thin film dispersion 200 as shown in FIG. 9 can be produced.

<Process (a)>
Step (a) is a step of laminating the film-like laminate 10 and the water permeable sheet 3 so that the polymer thin film 1 and the water permeable sheet 3 face each other, as shown in FIG. . In the present embodiment, a mode in which the belt-like film-like laminate 10 and the belt-like water-permeable sheet 3 are laminated will be described as an example. Here, it is preferable to use a pressure-sensitive adhesive sheet 20 including a water-permeable sheet 3 and a pressure-sensitive adhesive layer 4 partially provided on one surface of the water-permeable sheet 3 as shown in FIG.
In the step (a), the film-like laminate 10 and the pressure-sensitive adhesive sheet 20 are laminated by bonding the polymer thin film 1 and the pressure-sensitive adhesive layer 4. From the viewpoint of workability, the width dimension of the water permeable sheet 3 is preferably smaller than the width dimension of the polymer thin film 1.

<Step (b)>
Step (b) is a step of peeling the step film 2 from the polymer thin film 1 as shown in FIG.
In the step (b), the polymer thin film 1 and the water permeable sheet 3 are combined, and the process film 2 is peeled from the polymer thin film 1. In this embodiment, the process film 2 is peeled from the polymer thin film 1 with the tip 3A side (side on which the adhesive layer 4 is formed) of the water permeable sheet 3 as a starting point.

The peeling force from the polymer thin film 1 of the step film 2 in the step (b) is preferably 10 mN / 100 mm or more and 1000 mN / 100 mm or less, more preferably 20 mN / 100 mm or more and 500 mN / 100 mm or less, It is particularly preferably 30 mN / 100 mm or more and 350 mN / 100 mm or less.
If said peeling force is 10 mN / 100 mm or more, the malfunction that a process film and a polymer thin film will peel easily in a process (a) can be suppressed. Moreover, if said peeling force is 1000 mN / 100 mm or less, the process film will become difficult to peel from a polymer thin film in a process (b), and the malfunction that a polymer thin film will fracture | rupture can be suppressed.
Said peeling force can be adjusted by changing the kind of peeling agent used for the process film 2, for example.

<Step (c)>
Step (c) is a step of obtaining a wound body 100 in which the polymer thin film 1 and the water-permeable sheet 3 are wound together in a roll shape, as shown in FIG.
In the step (c), the polymer thin film 1 and the water permeable sheet 3 separated together in the step (b) are wound together in a roll shape to obtain a wound body 100. Here, after removing the adhesive layer 4 in advance, the polymer thin film 1 and the water permeable sheet 3 may be wound. By doing so, since the pressure-sensitive adhesive layer 4 does not exist in the wound body 100, impurities in the obtained polymer thin film dispersion can be reduced.
From the viewpoint of workability, the outermost layer of the wound body 100 is preferably the polymer thin film 1. Moreover, in this embodiment, you may preserve | save once in the state of the wound body 100, and may perform the following process (d) after that. Thus, when preserve | saving in the state of the wound body 100, it is preferable to cover the wound body 100 temporarily with a wrapping paper.

<Step (d)>
Step (d) is a step of immersing the wound body 100 in the liquid medium 5 as shown in FIG.
The liquid medium 5 permeates the water permeable sheet 3 of the wound body 100 by the step (d). Then, as shown in FIG. 7, the polymer thin film 1 peeled off from the water permeable sheet 3 floats in the liquid medium 5.

  The liquid medium 5 is not particularly limited as long as it does not dissolve the polymer thin film 1. Examples of the liquid medium 5 include water, water in which a salt is dissolved, water in which a surfactant is dissolved, and a buffer solution.

<Process (e)>
In the step (e), the water permeable sheet 3 peeled off from the polymer thin film 1 in the liquid medium 5 is removed from the liquid medium 5, and the liquid medium 5 in which the polymer thin film 1 is suspended as shown in FIG. It is the process of obtaining.
The method for removing the water permeable sheet 3 from the liquid medium is not particularly limited as long as the water permeable sheet 3 can be removed from the liquid medium. For example, the water permeable sheet 3 is grasped by using a gripping means such as tweezers. You can adopt the method of removing by.

<Step (f)>
In the step (f), the polymer thin film 1 in the liquid medium 5 is chopped and dispersed to obtain the polymer thin film dispersion 200 including the polymer thin film pieces 1a in the liquid medium 5 as shown in FIG. It is a process.
As a method of chopping and dispersing the polymer thin film 1, a method using a known disperser or a stirrer can be employed. As a disperser or a stirrer, it is preferable to use a homogenizer, a microfluidizer, a sonicator, or the like. Here, the chopping does not necessarily need to be cut into small pieces, and can be cut into a predetermined size or a fixed shape.

  The polymer thin film dispersion 200 according to the present embodiment includes a polymer thin film piece 1 a in the liquid medium 5. And this polymer thin film piece 1a is applicable to biological tissues, such as a healthy skin, a skin wound surface, an organ wound surface, and a cornea.

(Operational effect of this embodiment)
According to this embodiment, the following operational effects can be achieved.
(1) A method for producing the polymer thin film dispersion 200 having high production efficiency and suitable for mass production can be provided.
(2) In the method for producing the polymer thin film dispersion 200, the polymer thin film 1 is formed on the process film 2, and then the polymer thin film 1 is peeled off from the process film 2. Smoothness can be improved.
(3) In the method of manufacturing the polymer thin film dispersion 200, the polymer thin film 1 that is fragile and difficult to handle is easily peeled off from the process film 2 starting from the pressure-sensitive adhesive layer 4 provided on the water permeable sheet 3. Is possible.
(4) In the manufacturing method of the polymer thin film dispersion 200, the wound body 100 in which the polymer thin film 1 and the water permeable sheet 3 are wound together in a roll shape is used. Then, the water permeable sheet 3 can be easily removed from the polymer thin film 1 by immersing the wound body 100 in the liquid medium 5.

[Modification of Embodiment]
The present embodiment is not limited to the above-described embodiment, and modifications, improvements, and the like within the scope that can achieve the object of the present embodiment are included in the present embodiment.
For example, in the above-described embodiment, the pressure-sensitive adhesive sheet 20 in which the pressure-sensitive adhesive layer 4 is provided in advance on one surface of the water-permeable sheet 3 is used, but the present invention is not limited thereto. For example, the adhesive layer 4 may be provided on the water-permeable sheet 3 when the film-like laminate 10 and the water-permeable sheet 3 are laminated. Moreover, when laminating the film-like laminate 10 and the water-permeable sheet 3, the film-like laminate 10 and the water-permeable sheet 3 are attached with an adhesive tape from above the water-permeable sheet 3. Also good.

In the water permeable sheet 3 in the above-described embodiment, the front end portion 3A in the length direction in plan view is a region in the vicinity of one end portion in the length direction of the band-shaped water permeable sheet 3, and one end This is a region having a predetermined area from the portion toward the other end. By providing a pressure-sensitive adhesive layer at the tip 3A, the polymer thin film 1 is moved from the process film 2 side to the water-permeable sheet 3 side after the water-permeable sheet 3 and the film-like laminate 10 are bonded together. Easy to do. Therefore, the shape and material of the pressure-sensitive adhesive layer 4 are not particularly limited as long as the pressure-sensitive adhesive layer 4 is formed on the tip portion 3A so that the polymer thin film 1 can be transferred.
In the said embodiment, although the shape of the water-permeable sheet 3 and the film-like laminated body 10 was made into strip | belt shape, it is not limited to this. As long as the water-permeable sheet 3 and the polymer thin film 1 have such a length that they can be rolled up together, the shape of the water-permeable sheet 3 and the film-like laminate 10 may not be a belt shape.

[Example 1]
1. Manufacturing method of wound body (1) Manufacturing of sheet-shaped laminate (1) -1 Manufacturing of process film The process film of Example 1 has a base material and a release layer laminated on the surface of the base material.
100 parts by mass of a poly (4-methyl-1-pentene) -based resin having a carboxyl group (manufactured by Mitsui Chemicals, Inc., melting point 180 ° C.) is mixed with 900 mass% of a mixed solvent of methylcyclohexane / ethyl acetate = 80 mass% / 20 mass%. Isocyanurate compound (produced by Mitsui Chemicals, Inc.), which is a compound in which 1,5-pentamethylene diisocyanate as an aliphatic polyisocyanate compound forms an isocyanurate ring with respect to a solution (solid content 10% by mass) dissolved in a part. After adding 10 parts by mass of Stabio D-370N, solid content 100% by mass, the mixture was diluted with a toluene / n-heptane mixed solvent to a solid content concentration of 5% by mass to prepare a release agent composition.
Subsequently, after applying the obtained release agent composition to the surface of a band-shaped polyethylene terephthalate film (Mitsubishi Resin Co., Ltd., Diafoil T100) having a thickness of 38 μm as a base material using a Mayer bar, By heating and drying at 100 ° C. for 60 seconds to cure, a release layer having a thickness of 500 nm was obtained, and a strip-shaped process film was obtained.

(1) -2 Preparation of Polymer Thin Film Forming Solution Poly DL lactic acid having a weight average molecular weight of 180,000 (PURAC, PURASORB20) is dissolved in ethyl acetate, and the solid content concentration is 3 mass% at 25 ° C. A solution for forming a polymer thin film having a viscosity of 7.1 mPa · s was prepared.

(1) -3 Formation of Polymer Thin Film Next, using a reverse gravure coater, after applying the obtained polymer thin film forming solution to the release layer surface of the prepared process film, it was dried at 100 ° C. for 60 seconds. A polymer thin film having a thickness of 200 nm was formed to obtain a belt-like sheet-like laminate.

(2) Manufacture of pressure-sensitive adhesive sheet After drying on the leading edge in the length direction of 100 mm wide release paper (manufactured by Lintec Corporation, 8K) (10 mm area (10 mm × 100 mm) from the leading edge in the length direction of the release paper) Adhesive solution (BPS-5127, manufactured by Toyo Ink Co., Ltd.) is applied and dried so that the thickness of the pressure-sensitive adhesive layer is 25 μm, and a belt-shaped glassine paper (basis weight 73 g / m ² ) that becomes a water-permeable sheet. , Air permeability 5,000 seconds, thickness 60 μm, manufactured by Lintec Co., Ltd.) was bonded to obtain a belt-like pressure-sensitive adhesive sheet.

(3) Production of wound body The release paper of the pressure-sensitive adhesive sheet was peeled off, and the pressure-sensitive adhesive layer of the pressure-sensitive adhesive sheet was bonded to the polymer thin film of the sheet-like laminate. Next, the polymer thin film and the water permeable sheet were combined, wound while being peeled from the process film so that the polymer thin film was on the outside, and rolled to obtain a wound body. In addition, the strip | belt-shaped laminated body which comprises the obtained winding body was 100 mm in width dimension, and 10 m in length dimension.

2. Production of Polymer Thin Film Dispersion The obtained wound body was immersed in a liquid medium (purified water) to remove the nonwoven fabric peeled off from the polymer thin film.
When the polymer thin film in the solution was chopped using a homogenizer (manufactured by IKA, ULTRA-TURRAX Disperser T25 basic), a polymer thin film dispersion which was a high-viscosity liquid in which polymer thin film pieces were dispersed was obtained. .

3. Measurement and Evaluation (1) Peeling Force of Process Film The peel force when peeling the process film from the polymer thin film in the obtained sheet-like laminate was measured.
That is, after bonding an adhesive tape (Nitto Denko Corporation, No. 31B) to the process film in the sheet-like laminate, the process film in a state where the adhesive tape is bonded is peeled 180 ° from the polymer thin film. The peeling force (mN / 100 mm) during the measurement was measured. The obtained results are shown in Table 1.
(2) Air permeability The air permeability of the water-permeable sheet in the obtained sheet-like laminate was measured by the method described in JIS-P8117, using an air permeability tester (Asahi Seiko Co., Ltd., water column type Oken). It measured using the type | formula air permeability and smoothness tester KY6).

(3) Evaluation of peelability of polymer thin film The obtained polymer thin film laminate was immersed in a liquid medium (purified water).
The polymer thin film laminate was visually observed and evaluated according to the following criteria to evaluate the peelability of the polymer thin film. The obtained results are shown in Table 1.
A: The water-permeable sheet peeled off from the surface of the polymer thin film within 3 minutes after being immersed in the liquid medium.
B: The water-permeable sheet was peeled off from the surface of the polymer thin film within 3 minutes and within 10 minutes after being immersed in the liquid medium.
F: The water-permeable sheet was not peeled off from the surface of the polymer thin film even after 10 minutes had passed since it was immersed in the liquid medium.

[Examples 2 to 7]
Except having changed the water-permeable sheet of Example 1 as shown in Table 1, it manufactured and evaluated the sheet-like laminated body, the wound body, and the polymer thin film dispersion by the same method as Example 1. . The obtained results are shown in Table 1.

[Comparative Examples 1 and 2]
Except having changed the water-permeable sheet | seat of Example 1 as shown in Table 1, the sheet-like laminated body and the wound body were manufactured and evaluated by the method similar to Example 1. FIG. The obtained results are shown in Table 1. As shown in Table 1, the air permeability of the sheets of Comparative Examples 1 and 2 is ∞, and these sheets are completely impervious gas and are not permeable to gases and liquids. It shows that. When the wound bodies of Comparative Examples 1 and 2 were immersed in a liquid medium, the polymer film dispersion could not be produced by the same method as in Example 1 because the water-permeable sheet was not peeled off.

As shown in Table 1, when the sheet having water permeability was used (Examples 1 to 7), it was confirmed that the peelability of the polymer thin film was good. Therefore, when using the wound body obtained in Examples 1 to 7, the polymer thin film dispersion can be easily manufactured. Thereby, according to the manufacturing method of the polymer thin film dispersion of Examples 1-7, it was confirmed that production efficiency is high and it is suitable for mass production.
On the other hand, when a sheet having no water permeability was used as the sheet (Comparative Examples 1 and 2), it was found that the peelability of the polymer thin film was insufficient.

DESCRIPTION OF SYMBOLS 1 ... Polymer thin film, 2 ... Process film, 3 ... Water-permeable sheet, 4 ... Adhesive layer, 5 ... Liquid medium, 10 ... Film-like laminated body, 100 ... Rolled body, 200 ... Polymer thin film dispersion.

Claims (11)

(A) a step of laminating a film-like laminate comprising a process film and a polymer thin film, and a water permeable sheet so that the polymer thin film and the water permeable sheet face each other;
(B) peeling the process film from the polymer thin film;
(C) The process of winding in roll shape and obtaining the wound body by which the said polymer thin film and the said water-permeable sheet were wound together in roll shape,
(D) immersing the wound body in a liquid medium;
(E) removing the water-permeable sheet peeled from the polymer thin film from the liquid medium;
(F) chopping and dispersing the polymer thin film in the liquid medium to obtain a polymer thin film dispersion;
A method for producing a polymer thin film dispersion, comprising: In the manufacturing method of the polymer thin film dispersion according to claim 1,
The method for producing a polymer thin film dispersion, wherein the water permeable sheet is at least one selected from the group consisting of a nonwoven fabric and paper. In the manufacturing method of the polymer thin film dispersion according to claim 1 or 2,
The method for producing a polymer thin film dispersion, wherein the polymer thin film has a thickness of 5 nm or more and 1000 nm or less. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 3,
The polymer thin film dispersion is characterized in that the polymer constituting the polymer thin film is at least one selected from the group consisting of polylactic acid, lactic acid copolymer, polylactone, lactone copolymer and polypeptide. Production method. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 4,
The method for producing a polymer thin film dispersion, wherein the water-permeable sheet has an air permeability of 100,000 seconds or less. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 5,
The method for producing a polymer thin film dispersion, wherein the water permeable sheet has a thickness of 25 μm or more. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 6,
The method for producing a polymer thin film dispersion, wherein a peeling force of the process film from the polymer thin film in the step (b) is 10 mN / 100 mm or more and 1000 mN / 100 mm or less. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 7,
The method for producing a polymer thin film dispersion, wherein the film-like laminate and the water-permeable sheet have a band shape. In the manufacturing method of the polymer thin film dispersion according to claim 8,
The width dimension in the planar view of the said water-permeable sheet | seat is 1200 mm or less. The manufacturing method of the polymer thin film dispersion characterized by the above-mentioned. In the manufacturing method of the polymer thin film dispersion according to any one of claims 1 to 9,
The water permeable sheet is partially provided with an adhesive layer on one side,
In the step (a), the polymer thin film dispersion and the water-permeable sheet are laminated by laminating the polymer thin film and the pressure-sensitive adhesive layer. Production method. In the manufacturing method of the polymer thin film dispersion according to claim 10,
The said water-permeable sheet is provided with the said adhesive layer in the front-end | tip part of the length direction in planar view. The manufacturing method of the polymer thin film dispersion characterized by the above-mentioned.

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