WO2015162676A1 - Porous material and porous sheet - Google Patents

Porous material and porous sheet Download PDF

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Publication number
WO2015162676A1
WO2015162676A1 PCT/JP2014/061206 JP2014061206W WO2015162676A1 WO 2015162676 A1 WO2015162676 A1 WO 2015162676A1 JP 2014061206 W JP2014061206 W JP 2014061206W WO 2015162676 A1 WO2015162676 A1 WO 2015162676A1
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Prior art keywords
porous material
silk fibroin
porous
containing compound
hydroxyl group
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PCT/JP2014/061206
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French (fr)
Japanese (ja)
Inventor
直祐 角
亜季子 川口
一稔 小林
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Resonac Corp
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Hitachi Chemical Co Ltd
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Priority to PCT/JP2014/061206 priority Critical patent/WO2015162676A1/en
Priority to PCT/JP2015/062023 priority patent/WO2015163294A1/en
Priority to JP2016514930A priority patent/JP6638647B2/en
Publication of WO2015162676A1 publication Critical patent/WO2015162676A1/en
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07KPEPTIDES
    • C07K14/00Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof
    • C07K14/435Peptides having more than 20 amino acids; Gastrins; Somatostatins; Melanotropins; Derivatives thereof from animals; from humans
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum

Definitions

  • the present invention relates to a porous material and a porous sheet obtained using a fibroin porous material.
  • Porous materials that can be produced using biological substances such as proteins and sugars are used in cosmetics and esthetics for the purpose of moisturizing and other purposes for esthetic salons and individuals, wound dressings, sustained release carriers for drugs, etc.
  • Medical field daily necessities such as disposable diapers, sanitary products, water purification field that can be used as a support for living organisms such as microorganisms and bacteria, tissue culture that can be used as a cell culture support (scaffold material), tissue regeneration support, etc. ⁇ Used in a wide range of industrial fields such as regenerative medical engineering.
  • saccharides such as cellulose and chitin
  • protein groups such as collagen, keratin, and fibroin are known.
  • fibroin especially silk fibroin
  • silk fibroin is industrially used from the viewpoint of stable supply of raw materials and price stability. Furthermore, it has a track record of being used as a surgical suture for a long time other than clothing, and has recently been used as an additive for foods and cosmetics. Since silk fibroin has no problem with respect to safety to the human body, its use for porous materials has been studied. There are several reports on the technique for producing silk fibroin porous materials. For example, a method in which a silk fibroin aqueous solution is rapidly frozen and then immersed in a crystallization solvent and melted and crystallized at the same time (Patent Document 1).
  • Patent Document 2 a method of producing a porous material by adding a small amount of a water-soluble organic solvent to a silk fibroin aqueous solution, and then freezing and melting for a certain time to obtain a silk fibroin porous material.
  • Patent Document 3 a method of producing a porous material by adding a small amount of a water-soluble organic solvent to a silk fibroin aqueous solution, and then freezing and melting for a certain time to obtain a silk fibroin porous material.
  • JP-A-8-41097 JP 2006-249115 A Japanese Patent No. 3412014
  • the porous body produced by the above method is soft in a wet state containing water, but is brittle in a dry state where water is removed by drying such as freeze-drying, and is inferior in workability and appearance due to generation of cracks, etc. was there.
  • An object of the present invention is to provide a porous material and a porous sheet using a fibroin porous body that is soft even in a dry state and excellent in appearance after drying and slice processability.
  • a porous material wherein the fibroin porous material contains 20 to 75% by mass of a hydroxyl group-containing compound having a molecular weight of 1,000 or less.
  • the hydroxyl group-containing compound is selected from glycerin, polyglycerin, polyethylene glycol, triethyl citrate, lactic acid, polyvinyl alcohol, propylene glycol, butylene glycol, alcohol, glycerin fatty acid ester, polyglycerin fatty acid ester, and sorbitan fatty acid ester.
  • the porous material according to [1].
  • the porous material and the porous sheet according to the present invention are soft even in a dry state, and are excellent in appearance after drying and slicing workability.
  • FIG. 2 is a photograph showing the appearance after drying of the porous material produced in Example 1.
  • FIG. 2 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Example 1.
  • FIG. 2 is a photograph showing the appearance of a porous material produced in Comparative Example 1 after drying.
  • 4 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Comparative Example 1.
  • FIG. 5 is a photograph showing the appearance after drying of the porous material produced in Comparative Example 2.
  • 5 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Comparative Example 2.
  • the porous material according to the present invention is characterized in that the fibroin porous body contains 20 to 75% by mass of a hydroxyl group-containing compound having a molecular weight of 1,000 or less. That is, in the porous material of the present invention, the fibroin porous body holds the hydroxyl group-containing compound.
  • the hydroxyl group-containing compound may be one having one or more hydroxyl groups per molecule, preferably one having 1 to 10 hydroxyl groups per molecule, more preferably one having 1 to 4 hydroxyl groups per molecule. preferable. Further, the molecular weight of the hydroxyl group-containing compound is 1,000 or less, preferably 800 or less, and more preferably 500 or less. The lower limit of the molecular weight of the hydroxyl group-containing compound is not particularly limited, but is preferably 50 or more, and more preferably 80 or more.
  • the hydroxyl group-containing compound examples include glycerin, polyglycerin, polyethylene glycol, triethyl citrate, lactic acid, polyvinyl alcohol, propylene glycol, butylene glycol, alcohol, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and the like. Of these, one or more of them can be used.
  • Glycerin, polyethylene glycol, triethyl citrate, polyglycerin, lactic acid, propylene glycol, and butylene glycol are preferred from the viewpoints of handling properties, slice processability, and safety.
  • glycerin since glycerin has an effect of moisturizing the skin, it is particularly preferable in applications where the glycerin is used by being attached to the skin such as skin care materials and wound dressings.
  • the content of the hydroxyl group-containing compound in the porous material according to the present invention needs to be 20 to 75% by mass.
  • the content of the hydroxyl group-containing compound is more preferably 25 to 60% by mass, and further preferably 25 to 45% by mass.
  • a porous material excellent in flexibility, workability, and handling properties can be obtained. More specifically, if it is 20% by mass or more, it is excellent in flexibility, hardly cracked during drying, does not become brittle, is not easily cracked during slicing, and provides excellent handling properties.
  • the hardness of the porous material of the present invention can be adjusted by changing the content within the above range. As the content of the hydroxyl group-containing compound is increased, the porous material becomes more flexible.
  • fibroin used as a raw material for the fibroin porous material examples include silkworms, silk fibroin produced from natural silkworms such as rabbits, wild silkworms and tempura, and transgenic silkworms.
  • silk fibroin is preferably used as a raw material from the viewpoint of obtaining a porous material and a porous sheet that are soft even in a dry state and excellent in appearance after drying and slice processability.
  • the silk fibroin porous material can be obtained from a silk fibroin solution, but when dissolved in water, silk fibroin has poor solubility in water and is difficult to dissolve directly in water.
  • a method for obtaining a silk fibroin aqueous solution any known method may be used, but a method in which silk fibroin is dissolved in a high concentration lithium bromide aqueous solution and desalted by dialysis to obtain a silk fibroin aqueous solution is preferable. It is done.
  • a method for adjusting the concentration of silk fibroin in an aqueous solution a method through concentration by air drying is simple and preferable.
  • the method for producing the silk fibroin porous material is not limited, but, for example, a method of obtaining a silk fibroin aqueous solution by rapidly freezing a silk fibroin aqueous solution and then immersing it in a crystallization solvent and simultaneously proceeding with melting and crystallization (Patent Document 1), A method for producing a porous material by freezing a silk fibroin aqueous solution for a long time (Patent Document 2), and adding a small amount of a water-soluble liquid organic substance to a silk fibroin aqueous solution, and then freezing for a certain time. And a technique for obtaining a porous body by melting the composition (Patent Document 3).
  • the silk fibroin porous material is preferably produced by adding a specific additive to a silk fibroin aqueous solution, freezing the aqueous solution, and then thawing it.
  • the concentration of silk fibroin is preferably 10 to 400 g / L, more preferably 15 to 200 g / L, and more preferably 20 to 120 g / L in the silk fibroin solution. More preferably. By setting within this range, a silk fibroin porous body having sufficient strength can be efficiently produced.
  • Preferred examples of the additive include carboxylic acids, amino acids, and water-soluble liquid organic substances.
  • the carboxylic acids used in the production of the silk fibroin porous material preferably have a pKa of 5.0 or less, more preferably 3.0 to 5.0, and more preferably 3.5 to 5.0. More preferred.
  • the carboxylic acids are not particularly limited as long as they are organic acids having at least one carboxy group in the molecule, and examples thereof include monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids.
  • carboxylic acids are preferable, aliphatic carboxylic acids having 1 to 6 carbon atoms are more preferable, and aliphatic carboxylic acids having 2 to 5 carbon atoms are more preferable. These aliphatic carboxylic acids may be saturated or unsaturated.
  • carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, acrylic acid, and 2-butenoic acid; oxalic acid, malonic acid, succinic acid, maleic acid, and the like. Of these, dicarboxylic acids are preferred. These can be used alone or in combination of two or more. In view of safety to the human body, acetic acid, lactic acid, and succinic acid are more preferable.
  • the amino acid is not particularly limited, and examples thereof include monoaminocarboxylic acids such as valine, leucine, isoleucine, glycine, alanine, serine, threonine, and methionine, and monoaminodicarboxylic acids (acidic amino acids) such as aspartic acid and glutamic acid.
  • monoaminocarboxylic acids such as valine, leucine, isoleucine, glycine, alanine, serine, threonine, and methionine
  • monoaminodicarboxylic acids acidic amino acids
  • Preferred examples include aliphatic amino acids, aromatic amino acids such as phenylalanine, and amino acids having a heterocyclic ring such as hydroxyproline, among which acidic amino acids and oxyamino acids such as hydroxyproline, serine, and threonine are preferred from the viewpoint of easy shape adjustment. preferable.
  • monoaminocarboxylic acid is more preferable among acidic amino acids, aspartic acid and glutamic acid are particularly preferable, and hydroxyproline is more preferable among oxyamino acids.
  • amino acids can be used alone or in combination of two or more.
  • Amino acids include L-type and D-type optical isomers, but when L-type and D-type are used, there is no difference in the resulting porous material. good.
  • the water-soluble liquid organic substance is liquid at room temperature (20 ° C.) and dissolves or mixes without separation when mixed with water at room temperature (20 ° C.).
  • water-soluble liquid organic substances include alcohols such as methanol, ethanol, isopropanol, and butanol; polyhydric alcohols such as glycerin and propylene glycol; dimethyl sulfoxide (DMSO), dimethylformamide (DMF), pyridine, acetone, acetonitrile, and the like. Is preferred. These can be used alone or in combination of two or more. In consideration of safety to the human body, ethanol, dimethyl sulfoxide, glycerin, and acetone are preferable, and ethanol and glycerin are more preferable.
  • the content of the additive is preferably 0.1 to 18% by volume, more preferably 0.1 to 5.0% by volume, More preferably, it is 4.0 volume%. By setting within this range, a porous body having sufficient strength can be produced.
  • the content of amino acid is preferably 1 to 500% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 30% by mass with respect to silk fibroin.
  • the freezing of the silk fibroin aqueous solution is preferably performed by pouring a solution obtained by adding an additive to the silk fibroin aqueous solution into a container and placing the container in a liquid-cooled low-temperature thermostat.
  • the freezing temperature is not particularly limited as long as the silk fibroin aqueous solution added with the additive is frozen, but is preferably about ⁇ 5 to ⁇ 40 ° C., more preferably about ⁇ 10 to ⁇ 30 ° C., and ⁇ 15 to More preferably, -25 ° C.
  • the freezing time is preferably 2 hours or longer, and more preferably 4 hours or longer so that the silk fibroin aqueous solution to which the additive is added can be sufficiently frozen and kept frozen. In particular, it is preferable to freeze by holding for 1 to 100 hours under a temperature condition of ⁇ 15 to ⁇ 25 ° C.
  • the silk fibroin aqueous solution to which the additive has been added may be frozen at once to the freezing temperature.
  • a silk fibroin porous body having a uniform structure can be obtained by temporarily holding an aqueous silk fibroin solution to which an additive has been added at about ⁇ 5 ° C. for about 2 hours, and then freezing it to a freezing temperature. it can.
  • the structure and strength of the porous body can be controlled to some extent by adjusting the time taken from ⁇ 5 ° C. to the freezing temperature.
  • the silk fibroin porous material is obtained by freezing the silk fibroin aqueous solution by the above method and then melting the frozen water.
  • the melting method is not particularly limited, and preferred methods include natural melting and storage in a thermostatic bath.
  • the silk fibroin porous material thus obtained contains an additive, and when it is necessary to remove the additive depending on the application, the additive is removed from the silk fibroin porous material by an appropriate method.
  • an appropriate method Can be used.
  • the simplest method is to remove the additive by immersing the silk fibroin porous material in pure water.
  • the silk fibroin porous body has a sponge-like porous structure. Normally, this silk fibroin porous body contains water unless it is removed by freeze-drying or the like. is there.
  • a dried silk fibroin porous material can be obtained by freeze-drying the silk fibroin porous material. In freeze-drying, when the drying is completed without completely sublimating the water, the pores are crushed due to the effect of the surface tension of the remaining water. Therefore, it is preferable to dry until the water is completely sublimated.
  • the temperature condition is preferably about ⁇ 5 to ⁇ 80 ° C.
  • the silk fibroin porous material can be formed into a shape suitable for the purpose, such as a film shape, a sheet shape, a block shape, a tubular shape, a spherical shape, etc., by appropriately selecting a container for producing the silk fibroin porous material.
  • the container is not limited as long as the silk fibroin solution has a shape and shape that does not flow out, and as the material, a material having high thermal conductivity such as iron, stainless steel, aluminum, gold, silver, copper, or the like is used. From the viewpoint of reducing the process time required for freezing. Further, the thickness of the mold and the wall of the container is preferably 0.5 mm or more from the viewpoint of its function and deformation due to expansion during freezing, etc., and is easy to handle and efficient in cooling Therefore, the thickness is more preferably 1 to 3 mm.
  • the mold and container used here can be provided with a release layer on the inner wall surface in contact with the silk fibroin solution inside for the purpose of preventing the silk fibroin porous body from sticking.
  • a sheet made of a fluororesin such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA),
  • PTFE polytetrafluoroethylene
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • PFA tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer
  • a release-treated sheet made of polyethylene terephthalate (PET), polypropylene (PP), or the like, or a coating layer made of the above fluororesin is preferable.
  • the thickness of the release layer is preferably 1000 ⁇ m or less, more preferably 500 ⁇ m or less, and further preferably 200 ⁇ m or less.
  • the thickness of the release layer is within the above range, it is difficult to inhibit heat conduction, and therefore the process time required for freezing can be shortened.
  • This silk fibroin porous material may be subjected to a cutting process or a cutting process after the melting step described above.
  • the surface structure is selected by cutting the film layer be able to.
  • a block-shaped mold or container in which a release layer such as a Teflon (registered trademark) sheet is provided on the inner wall surface is taken out from the mold or container, and then the four side film layers are formed.
  • the porous body which consists only of a porous layer can be obtained by removing and cutting or excising the part of a porous layer.
  • porous body having a film layer only on one side using a mold or a container provided with a release layer such as a Teflon (registered trademark) sheet on the inner wall only on one side and a filter paper on the inner wall on the other side You can also get
  • the method of incorporating the hydroxyl group-containing compound into the silk fibroin porous material is not particularly limited.
  • the method of blending it into the silk fibroin solution or the production of the silk fibroin porous material It may be a method of immersing in a solution containing a hydroxyl group-containing compound to such an extent as to immerse.
  • the content of the hydroxyl group-containing compound in the solution containing the hydroxyl group-containing compound is not particularly limited and is, for example, preferably 0.5 to 20% by volume, more preferably 1 to 10% by volume. When the content is within the above range, the hydroxyl group-containing compound is sufficiently introduced into the silk fibroin porous body, and a fibroin porous body containing a hydroxyl group-containing compound suitable for drying is obtained.
  • the immersion time is not particularly limited, but may be any time as long as the concentration of the hydroxyl group-containing compound in the silk fibroin fibroin porous body becomes uniform. For example, it is preferably 1 to 48 hours, and preferably 12 to 36 hours. Is more preferable.
  • the immersion time is within the above range, the hydroxyl-containing compound is sufficiently introduced into the silk fibroin porous material, and there is no variation in concentration in the silk fibroin porous material, and the hydroxyl-containing compound is uniformly contained. In addition, a homogeneous porous material can be obtained.
  • the hydroxyl group-containing compound is contained in the pores of the silk fibroin porous body constituting the porous material and the porous body so as to constitute the porous body itself.
  • a plasticizing effect, a moisturizing effect, and a water absorbing property are exhibited. Since it is such a structure, it is thought that the porous material of the present invention is soft even in a dry state and has excellent appearance after drying and slicing workability.
  • the porous sheet according to the present invention is made of the above porous material, and the film thickness thereof is 0.1 to 50 mm, preferably 0.2 to 10 mm, more preferably 0.5 to 5 mm. preferable.
  • the porous sheet can be easily produced by slicing the porous material.
  • Example 1 (Preparation of silk fibroin solution) Silk fibroin aqueous solution is prepared by dissolving silk fibroin powder (“Silk Powder IM (trade name)”, KB Selen Co., Ltd.) in 9M lithium bromide aqueous solution, removing insoluble matter by centrifugation, and then adding ultrapure water. It was obtained by repeating dialysis against. The obtained silk fibroin aqueous solution was air-dried in a dialysis tube and concentrated. Acetic acid was added as an additive to the concentrated solution to prepare a silk fibroin solution having a silk fibroin concentration of 30 g / L and an acetic acid concentration of 2% by volume.
  • the silk fibroin solution was poured into a mold (inside size: 400 mm ⁇ 300 mm ⁇ 20 mm, 60 mm ⁇ 30 mm ⁇ 10 mm, 100 mm ⁇ 10 mm ⁇ 10 mm) made of an aluminum plate, and cooled at ⁇ 5 ° C. in advance. It was placed in a thermostatic bath (manufactured by Maekawa Seisakusho) and allowed to stand at -5 ° C. for 2 hours. As the refrigerant, “Nibline Z1 (trade name)” (manufactured by Maruzen Petrochemical Co., Ltd.) was used. Thereafter, it was cooled to ⁇ 20 ° C.
  • Example 2 the porous material was the same as in Example 1 except that the type of the hydroxyl group-containing compound and the content of the hydroxyl group-containing compound in the porous material were changed to those shown in Tables 1 to 4. Obtained material. Tables 1 to 4 also show the evaluation results of appearance after drying, slicing workability, and winding property.
  • the porous material of the present invention in which the silk fibroin porous material contains a hydroxyl group-containing compound having a molecular weight of 1,000 or less is excellent in appearance after drying and slice processability.
  • a compound containing no hydroxyl group, or a material containing a compound containing a hydroxyl group but having a molecular weight higher than 1,000 has cracks after drying, abnormal appearance, It was confirmed that cracking occurred during slicing.
  • Example 28-35 and Comparative Examples 7 and 8 In Example 1, the raw material of the silk fibroin aqueous solution was made from silk fibroin powder scoured slag (manufactured by Nagasuna Coffee Co., Ltd.), the silk fibroin aqueous solution had a silk fibroin concentration of 40 g / L, and the hydroxyl group-containing compound solution
  • the porous material was prepared in the same manner as in Example 1 except that the concentration of the compound in the inside was changed to that shown in Table 5, and the size of the mold made of an aluminum plate was changed to that having an inner diameter of 400 mm ⁇ 300 mm ⁇ 20 mm. Obtained. Table 5 also shows the evaluation results of appearance after drying, slicing workability, and winding property.
  • the porous material of the present invention can be widely applied to the cosmetics and esthetic fields, and is extremely useful as a face mask or eye mask adapted to the shape of the face.
  • medical fields such as wound dressings, sustained drug carriers, hemostatic sponges, daily necessities such as disposable diapers and sanitary products, cell culture supports and tissue regeneration supports in tissue engineering and regenerative medical engineering, water purification applications and environmental fields It can be applied to various industries, such as a support that becomes a place of residence for microorganisms and bacteria.

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Abstract

Provided are a porous material and porous sheet which use a fibroin porous body that exhibits excellent handling properties and slicing properties, and is flexible even in a dry state. The porous material is characterized in that the fibroin porous body contains 20-75 mass% of a hydroxyl-group-containing compound having a molecular weight of 1,000 or less.

Description

多孔質材料及び多孔質シートPorous material and porous sheet

 本発明は、フィブロイン多孔質体を用いて得られる多孔質材料及び多孔質シートに関するものである。 The present invention relates to a porous material and a porous sheet obtained using a fibroin porous material.

 タンパク質や糖類等の生物由来物質を利用して作製可能である多孔質体は、エステティックサロンや個人での使用による保湿等を目的とした化粧品・エステ分野、創傷被覆材、薬剤徐放担体等の医療分野、紙おむつ、生理用品等の生活日用品分野、微生物や細菌等の住処になる支持体として活用しうる浄水分野、細胞培養支持体(足場材料)、組織再生支持体等として活用しうる組織工学・再生医工学分野等、産業上幅広い分野で利用される。
 これら多孔質体を構成する生体由来物質として、セルロースやキチン等の糖類、コラーゲン、ケラチン、フィブロイン等のタンパク質群等が知られている。
Porous materials that can be produced using biological substances such as proteins and sugars are used in cosmetics and esthetics for the purpose of moisturizing and other purposes for esthetic salons and individuals, wound dressings, sustained release carriers for drugs, etc. Medical field, daily necessities such as disposable diapers, sanitary products, water purification field that can be used as a support for living organisms such as microorganisms and bacteria, tissue culture that can be used as a cell culture support (scaffold material), tissue regeneration support, etc.・ Used in a wide range of industrial fields such as regenerative medical engineering.
As biologically-derived substances constituting these porous bodies, saccharides such as cellulose and chitin, protein groups such as collagen, keratin, and fibroin are known.

 これらの生体由来物質のうち、フィブロイン、とりわけシルクフィブロインは、原料の安定供給や価格の安定性から工業的に利用される。さらに、衣類用途以外に、手術用縫合糸として長く使用されてきた実績があり、近年、食品や化粧品の添加物としても利用されている。シルクフィブロインは人体に対する安全性にも問題がないことから多孔質体への使用が検討されている。
 シルクフィブロイン多孔質体を作製する手法に関しては、いくつか報告がある。例えば、シルクフィブロイン水溶液を急速冷凍したのち結晶化溶媒に浸漬し、融解と結晶化を同時進行することによって得る方法(特許文献1)、シルクフィブロイン水溶液を冷凍した後に長時間凍結状態を維持することで多孔質体を作製する手法(特許文献2)、シルクフィブロイン水溶液に対して少量の水溶性有機溶媒を添加した後に、一定時間冷凍して融解することによってシルクフィブロイン多孔質体が得られる手法である(特許文献3)。
Of these bio-derived substances, fibroin, especially silk fibroin, is industrially used from the viewpoint of stable supply of raw materials and price stability. Furthermore, it has a track record of being used as a surgical suture for a long time other than clothing, and has recently been used as an additive for foods and cosmetics. Since silk fibroin has no problem with respect to safety to the human body, its use for porous materials has been studied.
There are several reports on the technique for producing silk fibroin porous materials. For example, a method in which a silk fibroin aqueous solution is rapidly frozen and then immersed in a crystallization solvent and melted and crystallized at the same time (Patent Document 1). (Patent Document 2), a method of producing a porous material by adding a small amount of a water-soluble organic solvent to a silk fibroin aqueous solution, and then freezing and melting for a certain time to obtain a silk fibroin porous material. Yes (Patent Document 3).

特開平8-41097号公報JP-A-8-41097 特開2006-249115号公報JP 2006-249115 A 特許第3412014号公報Japanese Patent No. 3412014

 上記の手法によって作製した多孔質体は水を含んだ湿潤状態では柔らかいものの、凍結乾燥等の乾燥により水を除去した乾燥状態では脆く、クラックが発生する等して加工性や外観に劣るという課題があった。
 本発明は、乾燥状態でも柔らかく、乾燥後の外観及びスライス加工性に優れるフィブロイン多孔質体を用いた多孔質材料及び多孔質シートを提供することを課題とする。
The porous body produced by the above method is soft in a wet state containing water, but is brittle in a dry state where water is removed by drying such as freeze-drying, and is inferior in workability and appearance due to generation of cracks, etc. was there.
An object of the present invention is to provide a porous material and a porous sheet using a fibroin porous body that is soft even in a dry state and excellent in appearance after drying and slice processability.

 本発明者は、前記課題を達成するために鋭意研究を重ねた結果、下記の発明により当該課題を解決できることを見出した。
[1]フィブロイン多孔質体が、分子量が1,000以下の水酸基含有化合物を20~75質量%含むことを特徴とする多孔質材料。
[2]前記水酸基含有化合物が、グリセリン、ポリグリセリン、ポリエチレングリコール、クエン酸トリエチル、乳酸、ポリビニルアルコール、プロピレングリコール、ブチレングリコール、アルコール、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、及びソルビタン脂肪酸エステルから選択される1種以上である[1]に記載の多孔質材料。
[3]前記水酸基含有化合物がグリセリンである[1]に記載の多孔質材料。
[4][1]~[3]のいずれかに記載の多孔質材料からなり、膜厚が0.1~50mmである多孔質シート。
As a result of intensive studies to achieve the above problems, the present inventor has found that the problems can be solved by the following invention.
[1] A porous material, wherein the fibroin porous material contains 20 to 75% by mass of a hydroxyl group-containing compound having a molecular weight of 1,000 or less.
[2] The hydroxyl group-containing compound is selected from glycerin, polyglycerin, polyethylene glycol, triethyl citrate, lactic acid, polyvinyl alcohol, propylene glycol, butylene glycol, alcohol, glycerin fatty acid ester, polyglycerin fatty acid ester, and sorbitan fatty acid ester. [1] The porous material according to [1].
[3] The porous material according to [1], wherein the hydroxyl group-containing compound is glycerin.
[4] A porous sheet made of the porous material according to any one of [1] to [3] and having a thickness of 0.1 to 50 mm.

 本発明に係る多孔質材料及び多孔質シートは、乾燥状態でも柔らかく、乾燥後の外観やスライス加工性に優れる。 The porous material and the porous sheet according to the present invention are soft even in a dry state, and are excellent in appearance after drying and slicing workability.

実施例1で製造された多孔質材料の乾燥後の外観を示す写真である。2 is a photograph showing the appearance after drying of the porous material produced in Example 1. FIG. 実施例1で製造された多孔質材料をスライス加工して得られた多孔質シートの外観を示す写真である。2 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Example 1. FIG. 比較例1で製造された多孔質材料の乾燥後の外観を示す写真である。2 is a photograph showing the appearance of a porous material produced in Comparative Example 1 after drying. 比較例1で製造された多孔質材料をスライス加工して得られた多孔質シートの外観を示す写真である。4 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Comparative Example 1. FIG. 比較例2で製造された多孔質材料の乾燥後の外観を示す写真である。5 is a photograph showing the appearance after drying of the porous material produced in Comparative Example 2. 比較例2で製造された多孔質材料をスライス加工して得られた多孔質シートの外観を示す写真である。5 is a photograph showing the appearance of a porous sheet obtained by slicing the porous material produced in Comparative Example 2. FIG.

 本発明に係る多孔質材料は、フィブロイン多孔質体が、分子量が1,000以下の水酸基含有化合物を20~75質量%含むことを特徴とするものである。すなわち、本発明の多孔質材料においては、フィブロイン多孔質体が上記水酸基含有化合物を保持している。 The porous material according to the present invention is characterized in that the fibroin porous body contains 20 to 75% by mass of a hydroxyl group-containing compound having a molecular weight of 1,000 or less. That is, in the porous material of the present invention, the fibroin porous body holds the hydroxyl group-containing compound.

 上記水酸基含有化合物としては、1分子当り1つ以上の水酸基を有するものであればよく、1分子当り1~10の水酸基を有するものが好ましく、1分子当り1~4の水酸基を有するものがより好ましい。
 また、水酸基含有化合物の分子量は、1,000以下であり、800以下あることが好ましく、500以下であることがより好ましい。水酸基含有化合物の分子量の下限は特に制限はないが、50以上であることが好ましく、80以上であることがより好ましい。
The hydroxyl group-containing compound may be one having one or more hydroxyl groups per molecule, preferably one having 1 to 10 hydroxyl groups per molecule, more preferably one having 1 to 4 hydroxyl groups per molecule. preferable.
Further, the molecular weight of the hydroxyl group-containing compound is 1,000 or less, preferably 800 or less, and more preferably 500 or less. The lower limit of the molecular weight of the hydroxyl group-containing compound is not particularly limited, but is preferably 50 or more, and more preferably 80 or more.

 水酸基含有化合物の具体例としては、例えば、グリセリン、ポリグリセリン、ポリエチレングリコール、クエン酸トリエチル、乳酸、ポリビニルアルコール、プロピレングリコール、ブチレングリコール、アルコール、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル等が挙げられ、このうち1種又は2種以上を用いることができる。ハンドリング性、スライス加工性、安全性の観点から、グリセリン、ポリエチレングリコール、クエン酸トリエチル、ポリグリセリン、乳酸、プロピレングリコール、ブチレングリコールが好ましい。これらの中でも、グリセリンは、肌を保湿する効果があるので、スキンケア材料、創傷被覆材等の肌に貼り付けて使用する用途において特に好ましい。 Specific examples of the hydroxyl group-containing compound include glycerin, polyglycerin, polyethylene glycol, triethyl citrate, lactic acid, polyvinyl alcohol, propylene glycol, butylene glycol, alcohol, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, and the like. Of these, one or more of them can be used. Glycerin, polyethylene glycol, triethyl citrate, polyglycerin, lactic acid, propylene glycol, and butylene glycol are preferred from the viewpoints of handling properties, slice processability, and safety. Among these, since glycerin has an effect of moisturizing the skin, it is particularly preferable in applications where the glycerin is used by being attached to the skin such as skin care materials and wound dressings.

 本発明に係る多孔質材料、すなわち水酸基含有化合物を含むフィブロイン多孔質体中の水酸基含有化合物の含有量は、20~75質量%であることを要する。また、水酸基含有化合物の含有量は、25~60質量%であることがより好ましく、25~45質量%であることがさらに好ましい。水酸基含有化合物の含有量が上記範囲内であると、柔軟性、加工性、ハンドリング性に優れる多孔質材料を得ることができる。より具体的には、20質量%以上であると柔軟性に優れ、乾燥時に割れにくく、脆くなることがなく、スライス加工時に割れにくく、また優れたハンドリング性が得られる。一方、75質量%以下であると柔軟性に優れ、凍結乾燥前後での収縮が小さく、多孔質材料の表面のタックが良好であり、スライス加工時にロールに巻きつきにくく、優れたハンドリング性が得られる。
 また、本発明の多孔質材料は、上記範囲内において含有量を変化させることで、その硬さを調整することができる。水酸基含有化合物の含有量を多くするほど、多孔質材料は柔軟になる。
The content of the hydroxyl group-containing compound in the porous material according to the present invention, that is, the fibroin porous material containing the hydroxyl group-containing compound, needs to be 20 to 75% by mass. The content of the hydroxyl group-containing compound is more preferably 25 to 60% by mass, and further preferably 25 to 45% by mass. When the content of the hydroxyl group-containing compound is within the above range, a porous material excellent in flexibility, workability, and handling properties can be obtained. More specifically, if it is 20% by mass or more, it is excellent in flexibility, hardly cracked during drying, does not become brittle, is not easily cracked during slicing, and provides excellent handling properties. On the other hand, when it is 75% by mass or less, it has excellent flexibility, small shrinkage before and after lyophilization, good surface tack of the porous material, hardly wraps around the roll during slicing, and has excellent handling properties. It is done.
Moreover, the hardness of the porous material of the present invention can be adjusted by changing the content within the above range. As the content of the hydroxyl group-containing compound is increased, the porous material becomes more flexible.

 フィブロイン多孔質体の原料として用いられるフィブロインとしては、例えば家蚕、野蚕、天蚕等の天然蚕、トランスジェニック蚕等から産生されるシルクフィブロイン等が挙げられる。本発明においては、乾燥状態でも柔らかく、乾燥後の外観やスライス加工性に優れる多孔質材料及び多孔質シートを得る観点から、シルクフィブロインを原料とすることが好ましい。 Examples of the fibroin used as a raw material for the fibroin porous material include silkworms, silk fibroin produced from natural silkworms such as rabbits, wild silkworms and tempura, and transgenic silkworms. In the present invention, silk fibroin is preferably used as a raw material from the viewpoint of obtaining a porous material and a porous sheet that are soft even in a dry state and excellent in appearance after drying and slice processability.

 以下、フィブロインとして好ましいシルクフィブロインを例にとって説明する。シルクフィブロイン多孔質体は、シルクフィブロイン溶液から得られるが、水に溶解させる場合、シルクフィブロインは水に対する溶解性が悪く、直接水に溶解することは困難である。シルクフィブロイン水溶液を得る方法としては、公知のいかなる手法を用いてもよいが、高濃度の臭化リチウム水溶液にシルクフィブロインを溶解後、透析により脱塩し、シルクフィブロイン水溶液を得る方法が好適に挙げられる。また、水溶液中のシルクフィブロインの濃度調整の方法としては、風乾による濃縮を経る手法が簡便で好ましい。
 シルクフィブロイン多孔質体は、その製造方法は問わないが、例えば、シルクフィブロイン水溶液を急速冷凍したのち結晶化溶媒に浸漬し、融解と結晶化を同時進行することによって得る方法(特許文献1)、シルクフィブロイン水溶液を冷凍した後に長時間凍結状態を維持することで多孔質体を作製する手法(特許文献2)、シルクフィブロイン水溶液に対して少量の水溶性液状有機物質を添加した後に、一定時間冷凍して融解することによって多孔質体を得る手法(特許文献3)が挙げられる。
Hereinafter, a silk fibroin preferable as a fibroin will be described as an example. The silk fibroin porous material can be obtained from a silk fibroin solution, but when dissolved in water, silk fibroin has poor solubility in water and is difficult to dissolve directly in water. As a method for obtaining a silk fibroin aqueous solution, any known method may be used, but a method in which silk fibroin is dissolved in a high concentration lithium bromide aqueous solution and desalted by dialysis to obtain a silk fibroin aqueous solution is preferable. It is done. Further, as a method for adjusting the concentration of silk fibroin in an aqueous solution, a method through concentration by air drying is simple and preferable.
The method for producing the silk fibroin porous material is not limited, but, for example, a method of obtaining a silk fibroin aqueous solution by rapidly freezing a silk fibroin aqueous solution and then immersing it in a crystallization solvent and simultaneously proceeding with melting and crystallization (Patent Document 1), A method for producing a porous material by freezing a silk fibroin aqueous solution for a long time (Patent Document 2), and adding a small amount of a water-soluble liquid organic substance to a silk fibroin aqueous solution, and then freezing for a certain time. And a technique for obtaining a porous body by melting the composition (Patent Document 3).

 また、シルクフィブロイン多孔質体は、シルクフィブロイン水溶液に特定の添加剤を加えて、該水溶液を凍結させ、次いで融解させることにより製造することが好ましい。
 シルクフィブロイン多孔質体の製造において、シルクフィブロインの濃度は、シルクフィブロイン溶液中で10~400g/Lであることが好ましく、15~200g/Lであることがより好ましく、20~120g/Lであることがさらに好ましい。この範囲内に設定することで、十分な強度を持ったシルクフィブロイン多孔質体を効率的に製造することができる。
The silk fibroin porous material is preferably produced by adding a specific additive to a silk fibroin aqueous solution, freezing the aqueous solution, and then thawing it.
In the production of a silk fibroin porous body, the concentration of silk fibroin is preferably 10 to 400 g / L, more preferably 15 to 200 g / L, and more preferably 20 to 120 g / L in the silk fibroin solution. More preferably. By setting within this range, a silk fibroin porous body having sufficient strength can be efficiently produced.

 前記添加剤としては、カルボン酸類、アミノ酸、及び水溶性液状有機物質等が好ましく挙げられる。また、シルクフィブロイン多孔質体の製造において用いられるカルボン酸類としては、pKaが、5.0以下のものが好ましく、3.0~5.0のものがより好ましく、3.5~5.0のものがさらに好ましい。 Preferred examples of the additive include carboxylic acids, amino acids, and water-soluble liquid organic substances. The carboxylic acids used in the production of the silk fibroin porous material preferably have a pKa of 5.0 or less, more preferably 3.0 to 5.0, and more preferably 3.5 to 5.0. More preferred.

 カルボン酸類としては、少なくとも分子中に一つのカルボキシ基を有する有機酸であれば特に制限はないが、例えばモノカルボン酸、ジカルボン酸、トリカルボン酸等が挙げられる。カルボン酸類としては、カルボン酸類が好ましく、炭素数1~6の脂肪族カルボン酸がより好ましく、炭素数2~5の脂肪族カルボン酸がさらに好ましい。これらの脂肪族カルボン酸は飽和であってもよく、不飽和であってもよい。このようなカルボン酸として、具体的には、例えば、蟻酸、酢酸、プロピオン酸、酪酸、乳酸、アクリル酸、2-ブテン酸等のモノカルボン酸;シュウ酸、マロン酸、コハク酸、マレイン酸等のジカルボン酸等が好ましく挙げられる。これらは単独で、又は複数種を組み合わせて用いることができる。人体への安全性を考慮すると、酢酸、乳酸、コハク酸がより好ましい。 The carboxylic acids are not particularly limited as long as they are organic acids having at least one carboxy group in the molecule, and examples thereof include monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids. As the carboxylic acids, carboxylic acids are preferable, aliphatic carboxylic acids having 1 to 6 carbon atoms are more preferable, and aliphatic carboxylic acids having 2 to 5 carbon atoms are more preferable. These aliphatic carboxylic acids may be saturated or unsaturated. Specific examples of such carboxylic acids include monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, lactic acid, acrylic acid, and 2-butenoic acid; oxalic acid, malonic acid, succinic acid, maleic acid, and the like. Of these, dicarboxylic acids are preferred. These can be used alone or in combination of two or more. In view of safety to the human body, acetic acid, lactic acid, and succinic acid are more preferable.

 前記アミノ酸としては、特に制限はなく、例えば、バリン、ロイシン、イソロイシン、グリシン、アラニン、セリン、スレオニン、メチオニン等のモノアミノカルボン酸、アスパラギン酸、グルタミン酸等のモノアミノジカルボン酸(酸性アミノ酸)等の脂肪族アミノ酸、フェニルアラニン等の芳香族アミノ酸、ヒドロキシプロリン等の複素環を有するアミノ酸等が好ましく挙げられ、中でも形状の調整が容易な観点から酸性アミノ酸や、ヒドロキシプロリン、セリン、スレオニン等のオキシアミノ酸が好ましい。同様な観点で、酸性アミノ酸の中でもモノアミノカルボン酸がより好ましく、アスパラギン酸やグルタミン酸が特に好ましく、オキシアミノ酸の中でもヒドロキシプロリンがより好ましい。これらのアミノ酸は、いずれか1種を単独で、あるいは2種以上組み合わせて使用することができる。
 なお、アミノ酸には、L型とD型の光学異性体があるが、L型とD型を用いた場合に、得られる多孔質体に違いが見られないため、どちらのアミノ酸を用いても良い。
The amino acid is not particularly limited, and examples thereof include monoaminocarboxylic acids such as valine, leucine, isoleucine, glycine, alanine, serine, threonine, and methionine, and monoaminodicarboxylic acids (acidic amino acids) such as aspartic acid and glutamic acid. Preferred examples include aliphatic amino acids, aromatic amino acids such as phenylalanine, and amino acids having a heterocyclic ring such as hydroxyproline, among which acidic amino acids and oxyamino acids such as hydroxyproline, serine, and threonine are preferred from the viewpoint of easy shape adjustment. preferable. From the same viewpoint, monoaminocarboxylic acid is more preferable among acidic amino acids, aspartic acid and glutamic acid are particularly preferable, and hydroxyproline is more preferable among oxyamino acids. These amino acids can be used alone or in combination of two or more.
Amino acids include L-type and D-type optical isomers, but when L-type and D-type are used, there is no difference in the resulting porous material. good.

 前記水溶性液状有機物質は、常温(20℃)で液状であり、常温(20℃)で水と混合した際に、分離せずに溶解、又は混和するものをいう。水溶性液状有機物質としては、例えばメタノール、エタノール、イソプロパノール、ブタノール等のアルコール類;グリセリン、プロピレングリコール等の多価アルコール類;ジメチルスルホキシド(DMSO)、ジメチルホルムアミド(DMF)、ピリジン、アセトン、アセトニトリル等が好ましく挙げられる。これらは単独で、又は複数種を組み合わせて用いることができる。人体への安全性を考慮すると、エタノール、ジメチルスルホキシド、グリセリン、アセトンが好ましく、エタノール、グリセリンがより好ましい。 The water-soluble liquid organic substance is liquid at room temperature (20 ° C.) and dissolves or mixes without separation when mixed with water at room temperature (20 ° C.). Examples of water-soluble liquid organic substances include alcohols such as methanol, ethanol, isopropanol, and butanol; polyhydric alcohols such as glycerin and propylene glycol; dimethyl sulfoxide (DMSO), dimethylformamide (DMF), pyridine, acetone, acetonitrile, and the like. Is preferred. These can be used alone or in combination of two or more. In consideration of safety to the human body, ethanol, dimethyl sulfoxide, glycerin, and acetone are preferable, and ethanol and glycerin are more preferable.

 シルクフィブロイン水溶液に添加剤を用いる場合の添加剤の含有量は、0.1~18体積%であることが好ましく、0.1~5.0体積%であることがより好ましく、0.5~4.0体積%であることがさらに好ましい。この範囲内に設定することで、十分な強度を持った多孔質体を製造することができる。
 また、アミノ酸の含有量は、シルクフィブロインに対して、1~500質量%であることが好ましく、5~50質量%であることがより好ましく、10~30質量%であることがさらに好ましい。
When the additive is used in the silk fibroin aqueous solution, the content of the additive is preferably 0.1 to 18% by volume, more preferably 0.1 to 5.0% by volume, More preferably, it is 4.0 volume%. By setting within this range, a porous body having sufficient strength can be produced.
The content of amino acid is preferably 1 to 500% by mass, more preferably 5 to 50% by mass, and still more preferably 10 to 30% by mass with respect to silk fibroin.

 シルクフィブロイン水溶液の凍結は、シルクフィブロイン水溶液に添加剤を加えた溶液を容器に流し込み、該容器を液冷式の低温恒温槽中に入れることで行うことが好ましい。
 凍結温度としては、添加剤を加えたシルクフィブロイン水溶液が凍結する温度であれば特に制限はないが、-5~-40℃程度が好ましく、-10~-30℃程度がより好ましく、-15~-25℃がさらに好ましい。凍結時間としては、添加剤を加えたシルクフィブロイン水溶液が十分に凍結し、かつ凍結状態を一定時間保持できるよう、2時間以上であることが好ましく、4時間以上であることがさらに好ましい。また、特に-15~-25℃の温度条件下、1時間から100時間保持して凍結することが好ましい。
The freezing of the silk fibroin aqueous solution is preferably performed by pouring a solution obtained by adding an additive to the silk fibroin aqueous solution into a container and placing the container in a liquid-cooled low-temperature thermostat.
The freezing temperature is not particularly limited as long as the silk fibroin aqueous solution added with the additive is frozen, but is preferably about −5 to −40 ° C., more preferably about −10 to −30 ° C., and −15 to More preferably, -25 ° C. The freezing time is preferably 2 hours or longer, and more preferably 4 hours or longer so that the silk fibroin aqueous solution to which the additive is added can be sufficiently frozen and kept frozen. In particular, it is preferable to freeze by holding for 1 to 100 hours under a temperature condition of −15 to −25 ° C.

 ここで、添加剤を加えたシルクフィブロイン水溶液を一気に凍結温度まで下げて凍結してもよいが、凍結の前に過冷却状態を経ることが、均一な構造のシルクフィブロイン多孔質体を得る上で好ましい。例えば、添加剤を加えたシルクフィブロイン水溶液を一旦、-5℃程度で2時間程度保持して、その後、凍結温度まで下げて凍結することで、均一な構造のシルクフィブロイン多孔質体を得ることができる。-5℃から凍結温度までにかける時間を調整することで、多孔質体の構造や強度をある程度制御することが可能である。 Here, the silk fibroin aqueous solution to which the additive has been added may be frozen at once to the freezing temperature. However, it is necessary to pass a supercooled state before freezing to obtain a silk fibroin porous body having a uniform structure. preferable. For example, a silk fibroin porous body having a uniform structure can be obtained by temporarily holding an aqueous silk fibroin solution to which an additive has been added at about −5 ° C. for about 2 hours, and then freezing it to a freezing temperature. it can. The structure and strength of the porous body can be controlled to some extent by adjusting the time taken from −5 ° C. to the freezing temperature.

 上記の手法でシルクフィブロイン水溶液を凍結させた後、次いで凍結した水分を融解することによって、シルクフィブロイン多孔質体が得られる。融解の方法としては、特に制限はなく、自然融解や恒温槽での保管等の方法が好ましく挙げられる。 The silk fibroin porous material is obtained by freezing the silk fibroin aqueous solution by the above method and then melting the frozen water. The melting method is not particularly limited, and preferred methods include natural melting and storage in a thermostatic bath.

 このようにして得られたシルクフィブロイン多孔質体には添加剤が含まれており、用途に応じて添加剤を除去する必要がある場合には、適当な方法でシルクフィブロイン多孔質体から添加剤を除去して用いることができる。例えば、シルクフィブロイン多孔質体を、純水中に浸漬して、添加剤を除去することが最も簡便な方法として挙げられる。 The silk fibroin porous material thus obtained contains an additive, and when it is necessary to remove the additive depending on the application, the additive is removed from the silk fibroin porous material by an appropriate method. Can be used. For example, the simplest method is to remove the additive by immersing the silk fibroin porous material in pure water.

 シルクフィブロイン多孔質体は、スポンジ状の多孔質構造を有しており、通常このシルクフィブロイン多孔質体には凍結乾燥等により水除去を行わなければ水が含まれ、含水状態で柔らかい構造物である。また、シルクフィブロイン多孔質体を凍結乾燥することにより、シルクフィブロイン多孔質体の乾燥品を得ることができる。凍結乾燥は、水分を完全に昇華させずに乾燥を終えると、残った水分の表面張力の影響で空孔が潰れてしまうため、水分が完全に昇華するまで乾燥することが好ましい。例えば、温度条件として-5~-80℃程度であることが好ましい。 The silk fibroin porous body has a sponge-like porous structure. Normally, this silk fibroin porous body contains water unless it is removed by freeze-drying or the like. is there. In addition, a dried silk fibroin porous material can be obtained by freeze-drying the silk fibroin porous material. In freeze-drying, when the drying is completed without completely sublimating the water, the pores are crushed due to the effect of the surface tension of the remaining water. Therefore, it is preferable to dry until the water is completely sublimated. For example, the temperature condition is preferably about −5 to −80 ° C.

 このシルクフィブロイン多孔質体は、シルクフィブロイン多孔質体作製時の容器を適宜選択することにより、フィルム状、シート状、ブロック状、管状、球状等、目的に応じた形状とすることができる。
 容器としては、シルクフィブロイン溶液が流出しない形状及び形態のものであれば制限はなく、その素材としては、鉄、ステンレス、アルミニウム、金、銀、銅等の熱伝導率が高い素材を用いることが、凍結に要する工程時間を短縮できる観点から好ましい。また、型や容器の壁の厚さは、その機能と凍結の際の膨張等による変形等を防止する観点から、0.5mm以上であることが好ましく、取り扱いが容易で、冷却効率的な観点から、より好ましくは1~3mmである。
The silk fibroin porous material can be formed into a shape suitable for the purpose, such as a film shape, a sheet shape, a block shape, a tubular shape, a spherical shape, etc., by appropriately selecting a container for producing the silk fibroin porous material.
The container is not limited as long as the silk fibroin solution has a shape and shape that does not flow out, and as the material, a material having high thermal conductivity such as iron, stainless steel, aluminum, gold, silver, copper, or the like is used. From the viewpoint of reducing the process time required for freezing. Further, the thickness of the mold and the wall of the container is preferably 0.5 mm or more from the viewpoint of its function and deformation due to expansion during freezing, etc., and is easy to handle and efficient in cooling Therefore, the thickness is more preferably 1 to 3 mm.

 ここで用いられる型や容器は、シルクフィブロイン多孔質体の固着の予防を目的として、その内側のシルクフィブロイン溶液と接する内壁面に、離型層を設けることができる。
 離型層としては、ポリテトラフルオロエチレン(PTFE)、テトラフルオロエチレン-ヘキサフルオロプロピレン共重合体(FEP)やテトラフルオロエチレン-パーフルオロアルキルビニルエーテル共重合体(PFA)等のフッ素樹脂からなるシート、あるいはポリエチレンテレフタレート(PET)やポリプロピレン(PP)等からなる離型処理されたシート、また上記フッ素樹脂からなるコーティング層等が好ましく挙げられる。これらの離型層を用いた場合、シルクフィブロイン多孔質体の表面には細孔が少なく平滑なフィルム層が形成される。また、フィルム層を設けたくない場合は、ろ紙等といった表面が粗いシートを用いることで、フィルム層の大部分を剥離させることができる。離型層の採用については、例えば化粧品及びエステ分野の用途において、揮発しやすい化粧成分を含有させて用いる場合で、該化粧成分の揮発を抑えてより長時間の化粧成分の効果を得ようとする場合は、フィルム層を有することが好ましいので、採用することが好ましい。このように、離型層は、フィルム層の要否に応じて、適宜選択すればよい。
 また、離型層の厚さは、1000μm以下であることが好ましく、500μm以下であることがより好ましく、200μm以下であることがさらに好ましい。離型層の厚さが上記範囲内であると、熱伝導を阻害しにくいため、凍結に要する工程時間を短縮することができる。
The mold and container used here can be provided with a release layer on the inner wall surface in contact with the silk fibroin solution inside for the purpose of preventing the silk fibroin porous body from sticking.
As the release layer, a sheet made of a fluororesin such as polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP) or tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), Alternatively, a release-treated sheet made of polyethylene terephthalate (PET), polypropylene (PP), or the like, or a coating layer made of the above fluororesin is preferable. When these release layers are used, a smooth film layer with few pores is formed on the surface of the silk fibroin porous body. When it is not desired to provide a film layer, most of the film layer can be peeled off by using a sheet having a rough surface such as filter paper. Regarding the use of the release layer, for example, in the cosmetics and esthetics applications, in the case of using a cosmetic component that easily volatilizes, an attempt is made to obtain a longer-lasting cosmetic component effect by suppressing the volatilization of the cosmetic component. When it does, since it is preferable to have a film layer, it is preferable to employ | adopt. Thus, what is necessary is just to select a mold release layer suitably according to the necessity of a film layer.
Further, the thickness of the release layer is preferably 1000 μm or less, more preferably 500 μm or less, and further preferably 200 μm or less. When the thickness of the release layer is within the above range, it is difficult to inhibit heat conduction, and therefore the process time required for freezing can be shortened.

 このシルクフィブロイン多孔質体は、上記した融解する工程に次いで、切削加工や切断加工を施してもよい。シルクフィブロイン多孔質体をシート形状とする場合において、多孔質層のみからなる多孔質体とする場合には、容器の材質を選択するほかに、フィルム層を切除することで、表面構造を選択することができる。具体的には、例えば、テフロン(登録商標)シート等の離型層をその内壁面に設けたブロック状の型あるいは容器を用い、該型あるいは容器から取り出してから、側面の四面のフィルム層を取り除き、多孔質層の部分を切削あるいは切除する等して、多孔質層のみからなる多孔質体を得ることができる。また、一面のみにテフロン(登録商標)シート等の離型層をその内壁面に設け、その他の面の内壁面にろ紙を設けた型あるいは容器を用い、一面のみにフィルム層を有する多孔質体を得ることもできる。 This silk fibroin porous material may be subjected to a cutting process or a cutting process after the melting step described above. When making a silk fibroin porous body into a sheet shape, when making a porous body consisting only of a porous layer, in addition to selecting the material of the container, the surface structure is selected by cutting the film layer be able to. Specifically, for example, a block-shaped mold or container in which a release layer such as a Teflon (registered trademark) sheet is provided on the inner wall surface is taken out from the mold or container, and then the four side film layers are formed. The porous body which consists only of a porous layer can be obtained by removing and cutting or excising the part of a porous layer. Also, a porous body having a film layer only on one side using a mold or a container provided with a release layer such as a Teflon (registered trademark) sheet on the inner wall only on one side and a filter paper on the inner wall on the other side You can also get

 シルクフィブロイン多孔質体に水酸基含有化合物を含有させる方法は特に限定されず、シルクフィブロイン多孔質体を製造する際に、シルクフィブロイン溶液に配合する方法や、シルクフィブロイン多孔質体の作製後に、その全体が浸る程度の水酸基含有化合物を含む溶液に浸漬させる方法であってもよい。 The method of incorporating the hydroxyl group-containing compound into the silk fibroin porous material is not particularly limited. When producing the silk fibroin porous material, the method of blending it into the silk fibroin solution or the production of the silk fibroin porous material, It may be a method of immersing in a solution containing a hydroxyl group-containing compound to such an extent as to immerse.

 水酸基含有化合物を含む溶液中の、水酸基含有化合物の含有量は特に制限はなく、例えば0.5~20体積%であることが好ましく、1~10体積%であることがより好ましい。含有量が上記範囲内であると、シルクフィブロイン多孔質体中に水酸基含有化合物が十分に導入され、乾燥に適した水酸基含有化合物を含んだフィブロイン多孔質体が得られる。 The content of the hydroxyl group-containing compound in the solution containing the hydroxyl group-containing compound is not particularly limited and is, for example, preferably 0.5 to 20% by volume, more preferably 1 to 10% by volume. When the content is within the above range, the hydroxyl group-containing compound is sufficiently introduced into the silk fibroin porous body, and a fibroin porous body containing a hydroxyl group-containing compound suitable for drying is obtained.

 浸漬時間も特に制限はないが、シルクフィブロインフィブロイン多孔質体内の水酸基含有化合物の濃度が均一になる時間であればよく、例えば、1~48時間であることが好ましく、12~36時間であることがより好ましい。浸漬時間が上記範囲内であると、シルクフィブロイン多孔質体中に水酸基含有化合物が十分に導入され、またシルクフィブロイン多孔質体内における濃度のばらつきが生じることがなく、均一に水酸基含有化合物が含まれた、均質な多孔質材料が得られる。 The immersion time is not particularly limited, but may be any time as long as the concentration of the hydroxyl group-containing compound in the silk fibroin fibroin porous body becomes uniform. For example, it is preferably 1 to 48 hours, and preferably 12 to 36 hours. Is more preferable. When the immersion time is within the above range, the hydroxyl-containing compound is sufficiently introduced into the silk fibroin porous material, and there is no variation in concentration in the silk fibroin porous material, and the hydroxyl-containing compound is uniformly contained. In addition, a homogeneous porous material can be obtained.

 このようにして得られる本発明の多孔質材料において、水酸基含有化合物は、該多孔質材料を構成するシルクフィブロイン多孔質体の細孔内、及び該多孔質体自体を構成するように多孔質体の構造内に存在することで、可塑効果、保湿効果、吸水性が発現する。このような構成であることから、本発明の多孔質材料は、乾燥状態でも柔らかく、乾燥後の外観及びスライス加工性に優れるものになっていると考えられる。 In the porous material of the present invention thus obtained, the hydroxyl group-containing compound is contained in the pores of the silk fibroin porous body constituting the porous material and the porous body so as to constitute the porous body itself. By existing in the structure, a plasticizing effect, a moisturizing effect, and a water absorbing property are exhibited. Since it is such a structure, it is thought that the porous material of the present invention is soft even in a dry state and has excellent appearance after drying and slicing workability.

 本発明に係る多孔質シートは、上記多孔質材料からなり、その膜厚は、0.1~50mmであり、0.2~10mmであることが好ましく、0.5~5mmであることがより好ましい。
 多孔質シートは、上記多孔質材料をスライスすることで容易に製造することができる。
The porous sheet according to the present invention is made of the above porous material, and the film thickness thereof is 0.1 to 50 mm, preferably 0.2 to 10 mm, more preferably 0.5 to 5 mm. preferable.
The porous sheet can be easily produced by slicing the porous material.

 以下に、本発明を実施例によりさらに具体的に説明するが、本発明は、これらの実施例によってなんら限定されるものではない。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

実施例1
(シルクフィブロイン溶液の調製)
 シルクフィブロイン水溶液は、シルクフィブロイン粉末(「シルクパウダーIM(商品名)」、KBセーレン(株)製)を9M臭化リチウム水溶液に溶解し、遠心分離で不溶物を除去したのち、超純水に対して透析を繰り返すことによって得た。得られたシルクフィブロイン水溶液を透析チューブ中で風乾し濃縮した。この濃縮液に添加剤として酢酸を添加し、シルクフィブロイン濃度が30g/L、酢酸濃度が2体積%であるシルクフィブロイン溶液を調製した。
Example 1
(Preparation of silk fibroin solution)
Silk fibroin aqueous solution is prepared by dissolving silk fibroin powder (“Silk Powder IM (trade name)”, KB Selen Co., Ltd.) in 9M lithium bromide aqueous solution, removing insoluble matter by centrifugation, and then adding ultrapure water. It was obtained by repeating dialysis against. The obtained silk fibroin aqueous solution was air-dried in a dialysis tube and concentrated. Acetic acid was added as an additive to the concentrated solution to prepare a silk fibroin solution having a silk fibroin concentration of 30 g / L and an acetic acid concentration of 2% by volume.

(シルクフィブロイン多孔質体の製造)
 このシルクフィブロイン溶液をアルミ板で作製した型(内側サイズ;400mm×300mm×20mm、60mm×30mm×10mm、100mm×10mm×10mm)に流し込み、予め-5℃に冷却しておいた液冷式低温恒温槽((株)前川製作所製)に入れて-5℃で2時間静置した。冷媒としては、「ナイブラインZ1(商品名)」(丸善石油化学(株)製)を用いた。
 その後、-3℃/時間の速度で-20℃まで冷却し、そのままの温度で5時間保持して凍結した。凍結した試料を自然解凍で室温に戻してから、型から取り出し、超純水に浸漬し、超純水を1日2回、3日間交換することによって、使用した酢酸を除去した。その後、凍結乾燥機(「FD-550P(型番)」、東京理化機械(株)製)を用いて3日間凍結乾燥し、内径60mm×30mm×10mmの型で作製したシルクフィブロイン多孔質体の乾燥質量を測定した。
(Manufacture of silk fibroin porous material)
The silk fibroin solution was poured into a mold (inside size: 400 mm × 300 mm × 20 mm, 60 mm × 30 mm × 10 mm, 100 mm × 10 mm × 10 mm) made of an aluminum plate, and cooled at −5 ° C. in advance. It was placed in a thermostatic bath (manufactured by Maekawa Seisakusho) and allowed to stand at -5 ° C. for 2 hours. As the refrigerant, “Nibline Z1 (trade name)” (manufactured by Maruzen Petrochemical Co., Ltd.) was used.
Thereafter, it was cooled to −20 ° C. at a rate of −3 ° C./hour, and kept at that temperature for 5 hours to freeze. The frozen sample was returned to room temperature by natural thawing, then removed from the mold, immersed in ultrapure water, and the acetic acid used was removed by exchanging the ultrapure water twice a day for 3 days. Thereafter, the silk fibroin porous material prepared by freeze-drying for 3 days using a freeze dryer (“FD-550P (model number)”, manufactured by Tokyo Rika Machinery Co., Ltd.) and having a diameter of 60 mm × 30 mm × 10 mm was dried. The mass was measured.

(水酸基含有化合物の導入)
 上記のようにして作製したシルクフィブロイン多孔質体の全体が浸る程度の5体積%グリセリン水溶液を用意し、24時間静置した状態で浸漬させ、その後これを凍結乾燥して多孔質材料を得た。また、この凍結乾燥後の多孔質材料の乾燥質量を測定した。
 多孔質材料中の水酸基含有化合物の含有量(質量%)は、多孔質材料に導入された水酸基含有化合物の質量を、水酸基含有化合物が導入された後の多孔質材料の乾燥質量で割ったものとし、以下の式で算出した。
(多孔質材料中の水酸基含有化合物の含有量(質量%))=((水酸基化合物導入後の多孔質材料の乾燥質量)-(水酸基含有化合物の未導入のシルクフィブロイン多孔質体の乾燥質量))/(水酸基含有化合物の導入後のシルクフィブロイン多孔質体の乾燥質量)×100
(Introduction of hydroxyl-containing compound)
A 5% by volume glycerin aqueous solution was prepared so that the entire silk fibroin porous material produced as described above was immersed, and was immersed for 24 hours, and then lyophilized to obtain a porous material. . Further, the dry mass of the porous material after lyophilization was measured.
The content (% by mass) of the hydroxyl group-containing compound in the porous material is obtained by dividing the mass of the hydroxyl group-containing compound introduced into the porous material by the dry mass of the porous material after the hydroxyl group-containing compound is introduced. And calculated by the following formula.
(Content of hydroxyl group-containing compound in porous material (% by mass)) = ((Dry mass of porous material after introduction of hydroxyl group compound) − (Dry mass of silk fibroin porous material into which hydroxyl group-containing compound has not been introduced) ) / (Dry mass of silk fibroin porous material after introduction of hydroxyl group-containing compound) × 100

 上述のようにして得た多孔質材料について、以下に示すようにして乾燥後の外観とスライス加工性とを評価した。評価結果を第1表に示す。
 (乾燥後の外観)
 乾燥後の多孔質材料の外観を観察し、目視で認識できる程度(幅0.3mm以上、長さ2mm以上)のクラックの有無と外観の状態を評価した。クラックの数が1つでもあれば「×」とし、クラックはないが多孔質材料に析出物等の外観異常がある場合は「△」とし、クラックも外観異常もないものは「○」と判定した。
(スライス加工性)
 乾燥後の多孔質材料を、スライス装置((有)北島マシンナイフ製)を用いてスライス後の厚みが1mm程度になるようにスライスした。スライス時にシートや多孔質体が割れたものを「×」とし、割れがないものを「○」と判定した。
(巻きつき性)
 乾燥後の多孔質材料を、スライス装置((有)北島マシンナイフ製)を用いてスライス後の厚みが1mm程度になるようにスライスした。3回スライスを行いスライス時にシートがロールに3回とも巻きついたものを「×」とし、1回又は2回巻きついたものを「△」、1回も巻きつかなかったものを「○」と判定した。
About the porous material obtained by making it above, the external appearance after drying and slicing workability were evaluated as shown below. The evaluation results are shown in Table 1.
(Appearance after drying)
The appearance of the porous material after drying was observed, and the presence or absence of cracks and the state of the appearance to the extent that they could be visually recognized (width 0.3 mm or more, length 2 mm or more) were evaluated. If the number of cracks is even one, it will be judged as “X”. If there are no cracks but there are appearance abnormalities such as precipitates in the porous material, it will be judged as “△”. did.
(Slicing workability)
The porous material after drying was sliced using a slicing device (manufactured by Kitajima Machine Knife) so that the thickness after slicing was about 1 mm. The case where the sheet or the porous body was broken at the time of slicing was determined as “x”, and the case where there was no crack was determined as “◯”.
(Winding property)
The porous material after drying was sliced using a slicing device (manufactured by Kitajima Machine Knife) so that the thickness after slicing was about 1 mm. Slice 3 times, and when the sheet is wound around the roll 3 times during slicing, “X” means that the sheet is wound once or twice, “△” means that the sheet has not been wound once, “○” It was determined.

実施例2~27及び比較例1~6
 実施例1において、水酸基含有化合物の種類、多孔質材料中の水酸基含有化合物の含有量を、第1表~第4表に記載のものにかえた以外は、実施例1と同様にして多孔質材料を得た。また、乾燥後の外観、スライス加工性、及び巻きつき性の評価結果も第1表~第4表に示す。
Examples 2 to 27 and Comparative Examples 1 to 6
In Example 1, the porous material was the same as in Example 1 except that the type of the hydroxyl group-containing compound and the content of the hydroxyl group-containing compound in the porous material were changed to those shown in Tables 1 to 4. Obtained material. Tables 1 to 4 also show the evaluation results of appearance after drying, slicing workability, and winding property.

 実施例1~27の結果より、シルクフィブロイン多孔質体が分子量1,000以下の水酸基含有化合物を含んでなる本発明の多孔質材料は、乾燥後の外観や、スライス加工性に優れていることが確認された。一方、比較例1~7の結果より、水酸基を含まない化合物や、水酸基を含むものの分子量が1,000より高い化合物を含んでなる材料は、乾燥後にクラックが発生したり、外観の異常や、スライス加工時に割れが生じることが確認された。 From the results of Examples 1 to 27, the porous material of the present invention in which the silk fibroin porous material contains a hydroxyl group-containing compound having a molecular weight of 1,000 or less is excellent in appearance after drying and slice processability. Was confirmed. On the other hand, from the results of Comparative Examples 1 to 7, a compound containing no hydroxyl group, or a material containing a compound containing a hydroxyl group but having a molecular weight higher than 1,000 has cracks after drying, abnormal appearance, It was confirmed that cracking occurred during slicing.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

 実施例28~35、並びに比較例7及び8
 実施例1において、シルクフィブロイン水溶液の原料をシルクフィブロイン粉末から精練済み切繭(ながすな繭(株)製)とし、シルクフィブロイン水溶液をシルクフィブロインの濃度が40g/Lのものとし、水酸基含有化合物溶液中の該化合物の濃度を第5表に記載のものとし、アルミ板で作製した型のサイズを内径400mm×300mm×20mmのものにかえた以外は、実施例1と同様にして多孔質材料を得た。また、乾燥後の外観、スライス加工性、及び巻きつき性の評価結果も第5表に示す。
Examples 28-35 and Comparative Examples 7 and 8
In Example 1, the raw material of the silk fibroin aqueous solution was made from silk fibroin powder scoured slag (manufactured by Nagasuna Coffee Co., Ltd.), the silk fibroin aqueous solution had a silk fibroin concentration of 40 g / L, and the hydroxyl group-containing compound solution The porous material was prepared in the same manner as in Example 1 except that the concentration of the compound in the inside was changed to that shown in Table 5, and the size of the mold made of an aluminum plate was changed to that having an inner diameter of 400 mm × 300 mm × 20 mm. Obtained. Table 5 also shows the evaluation results of appearance after drying, slicing workability, and winding property.

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

*1,GLy:グリセリン
PEG:ポリエチレングリコール
PGL:ポリグリセリン
TEC:クエン酸トリエチル
DGL:デカグリセリンラウレート
SL:ソルビタンラウレート
DMSO:ジメチルスルホキシド
PVA:ポリビニルアルコール
DOP:フタル酸ジオクチル
OIL:エポキシ化大豆油
*2,v:体積%、w:質量%
* 1, GLy: glycerin PEG: polyethylene glycol PGL: polyglycerin TEC: triethyl citrate DGL: decaglycerin laurate SL: sorbitan laurate DMSO: dimethyl sulfoxide PVA: polyvinyl alcohol DOP: dioctyl phthalate OIL: epoxidized soybean oil * 2, v: volume%, w: mass%

 また、実施例28、30~32及び比較例1で得られた多孔質材料について、下記の方法に基づいて25%圧縮応力を測定した。実施例28の多孔質材料の圧縮応力は80.1kPaであり、実施例30の多孔質材料の圧縮応力は55.1kPaであり、実施例31の多孔質材料の圧縮応力は46.8kPaであり、実施例32の多孔質材料の圧縮応力は43.1kPaであった。一方、比較例1の多孔質材料の圧縮応力は437.6kPaであり、実施例の多孔質材料の圧縮応力よりも10倍近く大きく、著しく柔軟性に劣っていることが確認された。
 また、図1~図6の写真画像より、実施例のものはクラックが発生していないが、比較例のものはクラックが発生していることが確認された。
Further, for the porous materials obtained in Examples 28, 30 to 32 and Comparative Example 1, 25% compressive stress was measured based on the following method. The compressive stress of the porous material of Example 28 is 80.1 kPa, the compressive stress of the porous material of Example 30 is 55.1 kPa, and the compressive stress of the porous material of Example 31 is 46.8 kPa. The compressive stress of the porous material of Example 32 was 43.1 kPa. On the other hand, the compressive stress of the porous material of Comparative Example 1 was 437.6 kPa, which was almost 10 times larger than the compressive stress of the porous material of the example, and was confirmed to be significantly inferior in flexibility.
Further, from the photographic images of FIGS. 1 to 6, it was confirmed that cracks did not occur in the examples but cracks in the comparative examples.

(25%圧縮応力の測定)
 各実施例及び比較例で得られた材料について、万能試験機(「EZ-(N)S(型番)」,(株)島津製作所製)を用い、ロードセルは50N、治具として直径8mmの円形の圧縮板を用いて、圧縮速度1mm/分、室温22℃の条件下で、材料の厚さの25%を圧縮板で押し込んだときのロードを測定し、以下の式により算出した値を25%圧縮応力(kPa)とした。
25%圧縮応力(kPa)=材料の厚さの25%を圧縮板で押し込んだときのロード/圧縮板の面積(mm2)×1000
(Measurement of 25% compressive stress)
For the materials obtained in each of the examples and comparative examples, a universal testing machine (“EZ- (N) S (model number)”, manufactured by Shimadzu Corporation) was used, the load cell was 50 N, and the jig was a circle with a diameter of 8 mm. , The load when 25% of the thickness of the material was pushed by the compression plate under the conditions of a compression speed of 1 mm / min and a room temperature of 22 ° C. was measured, and a value calculated by the following equation was 25 % Compressive stress (kPa).
25% compressive stress (kPa) = Load / compression plate area (mm 2 ) × 1000 when 25% of the thickness of the material is pressed with the compression plate

 本発明の多孔質材料は、化粧品及びエステ分野等に広く適用することができ、顔の形状に合わせたフェイスマスクやアイマスクとしても極めて有用である。また、創傷被覆材や薬剤徐放担体、止血スポンジ等の医療分野、紙おむつや生理用品等の生活日用品分野、組織工学や再生医工学における細胞培養支持体や組織再生支持体、浄水用途及び環境分野における微生物や細菌等の住処になる支持体等、種々の産業に適用が可能である。 The porous material of the present invention can be widely applied to the cosmetics and esthetic fields, and is extremely useful as a face mask or eye mask adapted to the shape of the face. In addition, medical fields such as wound dressings, sustained drug carriers, hemostatic sponges, daily necessities such as disposable diapers and sanitary products, cell culture supports and tissue regeneration supports in tissue engineering and regenerative medical engineering, water purification applications and environmental fields It can be applied to various industries, such as a support that becomes a place of residence for microorganisms and bacteria.

Claims (4)

 フィブロイン多孔質体が、分子量が1,000以下の水酸基含有化合物を20~75質量%含むことを特徴とする多孔質材料。 A porous material, wherein the fibroin porous material contains 20 to 75% by mass of a hydroxyl group-containing compound having a molecular weight of 1,000 or less.  前記水酸基含有化合物が、グリセリン、ポリグリセリン、ポリエチレングリコール、クエン酸トリエチル、乳酸、ポリビニルアルコール、プロピレングリコール、ブチレングリコール、アルコール、グリセリン脂肪酸エステル、ポリグリセリン脂肪酸エステル、及びソルビタン脂肪酸エステルから選択される1種以上である請求項1に記載の多孔質材料。 The hydroxyl group-containing compound is selected from glycerin, polyglycerin, polyethylene glycol, triethyl citrate, lactic acid, polyvinyl alcohol, propylene glycol, butylene glycol, alcohol, glycerin fatty acid ester, polyglycerin fatty acid ester, and sorbitan fatty acid ester It is the above, The porous material of Claim 1.  前記水酸基含有化合物がグリセリンである請求項1に記載の多孔質材料。 The porous material according to claim 1, wherein the hydroxyl group-containing compound is glycerin.  請求項1~3のいずれかに記載の多孔質材料からなり、膜厚が0.1~50mmである多孔質シート。 A porous sheet made of the porous material according to any one of claims 1 to 3 and having a thickness of 0.1 to 50 mm.
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