WO2008035728A1

WO2008035728A1 - Sheet for pack

Info

Publication number: WO2008035728A1
Application number: PCT/JP2007/068243
Authority: WO
Inventors: Junko Suda; Changming Zhao
Original assignee: Advanced Softmaterials Inc.
Priority date: 2006-09-21
Filing date: 2007-09-20
Publication date: 2008-03-27
Also published as: JP2009292727A

Abstract

A sheet for packs which has excellent water-supplying performance and has such strength and flexibility that it can be provided as a large sheet for the whole face, etc. without any support. The sheet for packs comprises i) a first polyrotaxane and ii) a substance which is the following a) and/or b): a) a first polymer which is not a polyrotaxane; and b) a second polyrotaxane, the first polyrotaxane i) and the substance ii) being bonded to each other chemically and/or physically. The first and/or second polyrotaxane comprises first and/or second cyclic molecules, a first and/or second linear molecule with which the first and/or second cyclic molecules are pierced and clathrated, and a first and/or second blocking group disposed at each end of the first and/or second linear molecule so as not to release the first and/or second cyclic molecules from the first and/or second linear molecule. The sheet for packs has a maximum elongation of 200% or higher, breaking strength of 30 kPa or higher, and initial modulus of 5-100 kPa.

Description

Specification

Pack sheet

Technical field

TECHNICAL FIELD [0001] The present invention relates to a pack sheet having a polytaxane, particularly a pack gel sheet, and more particularly to a pack sheet excellent in flexibility and strength and suitable for supplying moisture to the skin, and particularly to a pack gel sheet. .

Background art

[0002] V, a conventional peel-off type packing material having the ability to form a film such as polybutyl alcohol, and the like. S, impregnation of sheet-like base material such as nonwoven fabric impregnated with a pack agent Nylon pack materials and gel sheet-type knock materials (see Patent Document 1), in which a gel layer containing a pack agent is provided on the sheet base material, have been developed and are gaining popularity due to their ease of use. . In addition to moisturizing, many products for special care such as whitening and anti-aging are available on the market.

Patent Document 1: JP-A-58-180408.

Patent Document 2: Japanese Patent Laid-Open No. 2005-008613.

Disclosure of the invention

Problems to be solved by the invention

[0003] However, the impregnated type pack material does not have a sufficient amount of impregnated retention of cosmetic liquid or the like, and the moisture of the cosmetic liquid tends to evaporate during use! Therefore, there is a limit to the supply of moisture to the skin. Gel sheet type products, on the other hand, prefer softness with a high moisture content, a cool and cool feeling, but lack hydration to the skin and release of cosmetic ingredients, and have a weak pack effect. There is a problem. In addition, since these conventional types of sheet packs include an opaque base material such as a nonwoven fabric, there is a problem in that it may seem uncomfortable when applied to the face.

To solve this problem, a gel sheet type packing material composed only of transparent or translucent gel has been developed (see Patent Document 2), but it is used for partial packs such as the eyes and mouth. Limited and full face composed of no support or composed of gel only Large packs for body use are still commercialized.

[0004] Therefore, an object of the present invention is to solve the above-described problems.

Specifically, the object of the present invention is to provide a pack sheet, particularly a pack gel sheet, which has excellent moisture supply performance and has strength and flexibility so that it can be made into a large sheet for the entire face without a support. Is to provide.

Means for solving the problem

[0005] The present inventors have found that the above object can be achieved by using a poly (oral taxane). Specifically, the present inventors have found the following invention.

<1> i) the first poly-ortaxane; and ii) the following substances a) and / or b): a) the first polymer other than the poly-ortaxane;

b) a second polymouth taxane,

And i) a first poly-oral taxane and ii) a chemical and / or physically bonded pack sheet, particularly a pack gel sheet,

The i) first poly (taxane) taxane includes a first cyclic molecule, a first linear molecule that includes the first cyclic molecule in a skewered manner, and the first linear molecule from the first linear molecule. Having a first blocking group disposed at both ends of the first linear molecule so that the cyclic molecule of

The b) second poly-taxane is a second cyclic molecule that may be the same as or different from the first cyclic molecule, and a second linear chain that includes the second cyclic molecule in a skewered manner. A second linear molecule which may be the same as or different from the first linear molecule, and the second cyclic molecule is detached from the second linear molecule. A second blocking group disposed at both ends of the second linear molecule so that the second blocking group may be the same as or different from the first blocking group,

The pack sheet as described above, wherein the maximum elongation of the pack sheet is 200% or more, the breaking strength is 30 kPa or more, and the initial elastic modulus is 5 to OOkPa.

<2> In the above item <1>, the first and / or second linear molecular force S, polybulal alcohol, polybulurpyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxymethylenosenore Loin, hydroxyethinoresolerose, hydroxypropinoresenorelose, etc.), polyacrylamide, polyethylene oxide, polyethylene glycol, polypropylene glyco Copolymers with polyethylene, polybutylacetal resins, polymethyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or their copolymers, polyethylene, polypropylene, and other olefinic monomers. Polyolefin resins such as polymerized resins, polyester resins, polychlorinated bur resins, polystyrene resins such as polystyrene and talylonitrile-toluene styrene copolymer resins, polymethyl methacrylate and (meth) acrylic acid ester copolymers, acrylonitrile methyl Acrylate resins such as acrylate resins, polycarbonate resins, polyurethane resins, butyl chloride butyl acetate copolymer resins, polybutyl propylal resins, etc .; and derivatives or modified products thereof, polyisobutylene, polytetrahydrofura , Polyaniline, acrylonitrile butadiene styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polygens such as polyisoprene and polybutadiene, polysiloxanes such as polydimethylolsiloxane, polysulfone , Polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and their derivatives. For example, polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene are preferably selected. , Polypropylene glycol, poly tetrahydrophthalic run, polydimethylsiloxane, polyethylene, and be selected from the group consisting of polypropylene Yogu is good is in particular polyethylene glycol.

<3> In <1> or <2> above, the first and / or second linear molecules have a molecular weight of 10,000 or more, preferably 20,000 or more, more preferably 3 . It should be more than 50,000

<4> According to any one of the above <1> to <3>, the first and / or second blocking group is a dinitrophenyl group, a cyclodextrin, an adamantane group, a trityl group, or a fluorescein. , Pyrenes, substituted benzenes (substituents include, but are not limited to, alkyl, alkyloxy, hydroxy, halogen, cyano, snorefoninore, force novoxinore, amino, phenol). One or more may be present), may be substituted! / ヽ may be! / ヽ polynuclear aromatics (same as the above as substituents) However, it is not limited to these. One or more substituents may be present. ) And steroids. It is preferable to select from the group consisting of dinitrophenyl groups, cyclodextrines, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably adamantane groups or trityl groups. It is good.

[0008] <5> In any one of the above items <1> to <4>, the first and / or second cyclic molecule may be substituted! /, Or may! / ヽ. Les.

<6> In any one of the above items <1> to <5>, the first and / or second cyclic molecule may be a substituted cyclodextrin molecule, and the cyclodextrin molecule is α- It is selected from the group consisting of cyclodextrin, 13-cyclodextrin, γ-cyclodextrin, and derivatives thereof.

<7> In any one of the above items <1> to <6>, the first and / or second cyclic molecule may be substituted α-cyclodextrin, and the first and / or second The linear molecule is preferably polyethylene glycol.

<8> In any one of the above items <1> to <7>, when the first cyclic molecule is skewered by the first linear molecule, the first cyclic molecule is included to the maximum extent. The amount of the first cyclic molecule is 0.001 to 0.6, preferably 0.01 to 0.5, more preferably 0.05 to 0.4. It is preferable that the chain molecules are included in a skewered manner.

<9> According to any of <1> to <8> above, the second cyclic molecule is the largest when the second cyclic molecule is skewered by the second linear molecule. When the amount included in the limit is 1, the second cyclic molecular force is 0.001 to 0.6, preferably (or 0.01 to 0.5, more preferably (or 0.05 to 0.4). It should be included in a skewered manner in the first linear molecule in quantity.

The invention's effect

[0010] According to the present invention, it is possible to provide a pack sheet, particularly a gel sheet for packs, which has excellent moisture supply performance and has strength and flexibility so that it can be made into a large sheet for the entire face without a support. .

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The present invention comprises: i) a first polyortaxane; and ii) the following substances a) and / or b): a) a first polymer other than a polyortaxane;

b) a second polymouth taxane,

And a sheet for a pack comprising i) the first poly (oral taxane) and ii) the substance chemically and / or physically bonded. The pack sheet has a maximum elongation of 200% or higher, a breaking strength of 30 kPa or higher, and an initial elastic modulus of 5 to OOkPa.

[0012] In the sheet of the present invention, i) a first polyoral taxane, and ii) a substance, that is, a) a first polymer other than a polyoral taxane; and / or b) a second polyoral taxane; It is preferable that at least a part of is crosslinked. The cross-linking is preferably the following cross-linking (i) to (no). That is, a) Cross-linking of poly-oral taxanes (first poly-orth-taxane and second poly-oral-taxane), cross-linking of polymers other than poly-oral taxanes (ie, “first polymer”) and poly-oral taxanes. , ノ,) Cross-linking in which the above ii) and mouth) are present together.

Further, the cross-linking may be chemical cross-linking or physical cross-linking, preferably chemical cross-linking, more preferably chemical cross-linking via a cyclic molecule. Is good.

[0013] The sheet of the present invention itself preferably has the following maximum elongation, breaking strength, and initial elastic modulus.

That is, the sheet of the present invention has a maximum elongation of 200% or more, preferably 300% or more, more preferably 400% or more, and a breaking strength of 30 kPa or more, preferably 50 kPa or more, more preferably lOOkPa or more. And an initial elastic modulus of 5 to 100 kPa, preferably 10 to 80 kPa, more preferably (15 to 60 kPa).

By having these characteristics, the sheet of the present invention has sufficient strength and fits to the undulations of the face even though it is thin, even though it has an area that can cover the entire face. Providing a flat or three-dimensional sheet that also has the flexibility to be able to handle.

In particular, the flexibility that can fit the undulations of the face is defined by the initial modulus and maximum elongation. If the initial elastic modulus exceeds the upper limit, the fitting property tends to deteriorate. Below the lower limit of the maximum elongation, the sheet can be bent and stretched freely. Tendency to affect the fit.

Moreover, sufficient strength is defined by the breaking strength and the initial elastic modulus. If the breaking strength is below the lower limit, the sheet tends to be unable to withstand its own weight and the sheet tends to be broken. Further, when the initial elastic modulus is below the lower limit, the elongation due to its own weight tends to be too large and the shape cannot be maintained. As a result, the sheet tends to be extremely difficult. Therefore, according to the present invention, a sheet having moderate elasticity and flexibility can be provided.

In the present application, the term “sheet” is intended to include a three-dimensional shape, for example, a shape that conforms to the undulations of the face when the entire force is locally flat. For example, as shown in FIG. 1, even a three-dimensional shape along the undulation of the face is included in the “sheet” in the present application because it is locally flat. In addition, the whole or flat plate described later in FIG. 2 is also included in the “sheet” in the present application. Note that the sheet having the shape shown in FIG. 1 is formed in a three-dimensional manner, and has a relatively narrow opening at the positions of the eyes, nose and mouth of the human face. The sheet shown in Fig. 1 is useful as a sheet that can cover the entire face, and is effective in that it can uniformly pack the entire face at once and enhances the moisturizing action.

[0014] As described above, the sheet of the present invention includes the first poly-oral taxane, and includes the second poly-oral taxane and / or the first polymer. Hereinafter, these constituent substances contained in the sheet of the present invention will be described in detail.

[0015] <Polymouth taxane>

Each of the first and / or second poly (taxane) taxanes in the present invention seems to be a cyclic molecule, a linear molecule that includes the cyclic molecule in a skewered manner, and a cyclic molecule that does not desorb from the linear molecule. Have blocking groups located at both ends of the linear molecule.

The second polymouth taxane may be the same as or different from the first polymouth taxane. More specifically, the second cyclic molecule may be the same as or different from the first cyclic molecule, and the second linear molecule may be the same as or different from the first linear molecule. The second blocking group may be the same as or different from the first blocking group. Further, the blocking group disposed at one end of the linear molecule may be the same as or different from the blocking group disposed at the other end. [0016] <Linear molecule of poly (oral taxane)>

In the polymouth taxane of the material of the present invention, the linear molecule is not particularly limited as long as it is a molecule extending in the longitudinal direction, that is, a linear molecule. As this linear molecule, polybulal alcohol, polypyrrole pyrrolidone, poly (meth) acrylic acid, cellulose resin (carboxy methinoresenorelose, hydroxyethinoresenorelose, hydroxypropinoresenorelose, etc.), polyacrylamide, Polyethylene oxide, polyethylene glycol, polypropylene glycol, polybulacetal resin, polybulumethyl ether, polyamine, polyethyleneimine, casein, gelatin, starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and others Polyolefin resins such as copolymer resins with polyolefin monomers, polyester resins, polychlorinated bur resins, polystyrene resins such as polystyrene and talylonitrile tristyrene copolymer resins Acrylic resins such as polymethyl methacrylate and (meth) acrylic acid ester copolymer, acrylonitrile methyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, butyl chloride acetate copolymer copolymer, polybutyl pentyl resin, etc .; And derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyaniline, acrylonitrile butadiene styrene copolymer (ABS resin), polyamides such as nylon, polygens such as polyimides, polyisoprene, and polybutadiene. Polysiloxanes such as polydimethylenosiloxane, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins And good be selected from the group consisting of induction conductors les, but particularly limited, such les.

For example, it is more preferably selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene, and preferably polyethylene glycol, polypropylene glycol, polytetrahydrofuran, It is particularly preferable to select polyethylene glycol from the group consisting of polydimethylsiloxane, polyethylene, and polypropylene.

[0017] The linear molecule may have a molecular weight of 10,000 or more, preferably 20,000 or more, more preferably 30,000 or more. <0018 Blocking Group of Poly Mouth Taxane>

In the polymouth taxane of the material of the present invention, the blocking groups are arranged at both ends of the linear molecule as described above. In addition, the blocking group has an effect that the cyclic molecule is not detached from the linear molecule. There is no particular limitation as long as it is a blocking group having these functions. The blocking groups arranged at both ends of the linear molecule may be the same or different at one end and the other end. As blocking groups, dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes (substituents include alkyl, alkyloxy, hydroxy, halogen, cyan, snorfoninore, carboxyl, amino But not limited thereto, one or more substituents may be present), polynuclear aromatics that may be substituted (substituents are the same as those described above) One or more substituents may be present, but not limited thereto.

. ) And steroids. The dinitrophenyl group is preferably selected from the group consisting of cyclodextrins, adamantane groups, trityl groups, fluoresceins, and pyrenes, more preferably adamantane groups or trityl groups. There should be.

[0019] <Polycyclic taxane cyclic molecule>

The cyclic molecule is not particularly limited as long as it is cyclic and takes the above-described state. The cyclic molecule may be an optionally substituted cyclodextrin molecule. The cyclodextrin molecule may be selected from the group consisting of α-cyclodextrin, 13-cyclodextrin and γ-cyclodextrin, and derivatives thereof.

[0020] In the polymouth taxane of the material of the present invention, the cyclic molecule may be an α-cyclodextrin which may be substituted, and the linear molecule may be polyethylene glycol.

In addition, in the polymouth taxane of the material of the present invention, when the amount of cyclic molecules to be maximally included when the cyclic molecules are skewered by linear molecules is 1, the cyclic molecular force It is preferable to be included in the form of skewers in a linear molecule in an amount of 0.001—0.6, preferably (0,01—0.5, more preferably (0,05—0.4).

[0021] <ii) Substance>

The sheet of the present invention has ii) a substance in addition to i) the first polyoral taxane. This ii) substance is Either a) below, b) or a mixture of a) and b). a) is the first polymer that is other than a polyoral taxane. In addition, b) is a second polytaxane that may be the same as or different from the first polyrotaxane.

[0022] <ii) Substance a) First polymer>

The first polymer is a polymer other than the polyoral taxane, and is not particularly limited.

The first polymer is not particularly limited, but the main chain or side chain is OH group, NH group,

2 It should have at least one selected from the group consisting of COOH group, epoxy group, bur group, thiol group, and photocrosslinking group. Examples of the photocrosslinking group include, but are not limited to, cinnamate, coumarin, chalcone, anthracene, styrylpyridine, styrylpyridinium salt, and styrylquinolium salt.

[0023] The first polymer may be a homopolymer or a copolymer. It may have two or more polymers. When it has two or more polymers, it is preferable that at least one polymer is bonded to the polyoral taxane via a cyclic molecule. If the first polymer is a copolymer, it may consist of two, three or more monomer forces. When it is a copolymer, the force S can include, but is not limited to, block copolymers, alternating copolymers, random copolymers, graft copolymers, and the like.

[0024] Examples of the first polymer include polybulal alcohol, polybulurpyrrolidone, poly (meth) acrylic acid, cellulose resins (carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, etc.), polyacrylamide, polyethylene Oxide, Polyethylene glycol, Polypropylene glycol, Polybuacetal resin, Polyvinylmethyl ether, Polyamine, Polyethyleneimine, Casein, Gelatin, Starch, etc. and / or copolymers thereof, polyethylene, polypropylene, and other resins Polyolefin resins such as copolymer resins with polyester monomers, polyester resins, polychlorinated bur resins, polystyrene resins such as polystyrene and acrylonitrile styrene copolymer resins, Acrylic resins such as methyl metatalylate, (meth) acrylic acid ester copolymer, and attarylonitrile trimethyl acrylate copolymer resin, polycarbonate resin, polyurethane resin, butyl chloride, butyl acetate copolymer resin, polybutyral resin, etc. And derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, polyauri , Acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polyisoprene, polybutadiene such as polybutadiene, polysiloxanes such as polydimethylsiloxane, polysulfones, polyimines, poly Forces S that may include acetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof are not limited to these. In addition, as the derivative, the above-described groups, that is, —OH group, —NH group, —COOH group,

2

It is preferable to have at least one selected from the group consisting of an epoxy group, a bur group, a thiol group, and a photocrosslinking group.

[0025] <ii) Substance a) Second poly-oral taxane>

The material of the present invention may have a second polymouth taxane. In this case, the second polymouth taxane may be the same as or different from the first polymouth taxane as described above. The substances constituting the second poly-oral taxane are as described above.

[0026] The sheet of the present invention may have various components as a pack sheet in addition to the constituent materials described above. As various components, for example, humectants such as dipropylene glycol, 1,3-butylene cornore, 1,2-pentanediol, glycerin, propylene glycolanol, collagen, hyanorenoic acid; lecithin, polyglycerin fatty acid ester Emulsifiers such as; oily substances such as squalane, jojoba oil, olive oil; and power S that can include preservatives such as parabens, phenoxyethanol, ethanol, etc., but is not limited thereto.

EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to a present Example.

Example 1

[0027] <Preparation of poly (oral) taxane (main chain molecular weight: 100,000)>

<<Preparation of PEG-carboxylic acid by TEMPO oxidation of polyethylene glycol>> Polyethylene glycol (PEG) (molecular weight 100,000) 10g, TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical) 50mg And 0.25 g of sodium bromide was dissolved in 110 ml of water. To the obtained solution, 2.5 ml of a commercially available sodium hypochlorite aqueous solution (effective chlorine concentration: about 5%) was added and reacted at room temperature with stirring. Immediately after the addition of the reaction, the pH of the system suddenly decreases. IN NaOH is added to maintain the pH as high as 10 to 11; Prepared. The drop in pH almost disappeared within 3 minutes, but the mixture was further stirred for 10 minutes. Excess ethanol was added to terminate the reaction. Extraction with 50 ml of methylene chloride was repeated three times to extract components other than inorganic salts, and then the methylene chloride was removed with an evaporator. After dissolving in 250 ml of warm ethanol, it was placed in a freezer at 4 ° C. to precipitate PEG-carboxylic acid, that is, PEG having both ends replaced with carboxylic acid (one COOH). The precipitated PEG strong rubonic acid was recovered by centrifugation. This hot ethanol dissolution precipitation centrifugation cycle was repeated several times, and finally dried by vacuum drying to obtain PEG-carboxylic acid. Yield over 95%. Carboxylation rate is 95% or more.

[0028] <<Preparation of inclusion complex using PEG-carboxylic acid and α-cyclodextrin >>

Dissolve 6 g of PEG carboxylic acid prepared above and 24 g of α-cyclodextrin (a-CD) separately in 100 ml of 70 ° C hot water, mix them, and then mix them in the refrigerator (4 ° C). It was left still for 3 days. The clathrate complex deposited in cream was lyophilized and collected.

[0029] <<Sealing of inclusion complex using adamantanamin and BOP reagent reaction system>

Adamantaneamine 0 · 26g, BOP reagent (benzotriazole-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) 0.60g, diisopropylethylamine 0 · 28ml Was added to a solution of 120 ml of dehydrated dimethylformamide (DMF), shaken well, and allowed to stand in a refrigerator. Thereafter, 120 ml of methanol was added, and stirring, centrifugation, and removal of the supernatant were performed. Next, 200 ml of a DMF / methanol = 1: 1 mixed solution was added, and the same operation was performed twice. Further, the same operation was performed twice using 200 ml of methanol, and the resulting precipitate was vacuum-dried and then dissolved in 140 ml of dimethylsulfoxide (DMSO). This solution was dropped into 1400 ml of pure water to precipitate poly-tacky taxane. Precipitated polymouth taxane was collected by centrifugation and dried in vacuum. Further, the same reprecipitation operation was performed to obtain 16 g of a polymouth taxane. As a result of N MR measurement of the obtained poly (oral taxane), the ratio (molar ratio) of CD to PEG monomer was CD: PEG monomer = 13.5: 100 (inclusion rate: 27%)

15 ml of IN NaOH aqueous solution, poly oral taxane (main chain molecular weight 100,000) (inclusion rate 27%) 3. Dissolve Og completely, add 0.6 ml of 1,4-butanediol diglycidyl ether (BDG E) to this solution, mix, remove bubbles with ultrasound, and make a mask with a thickness of 0.8 mm And poured into a sample mold for measurement (a strip type with a thickness of 0.5 mm and a width of 4 mm) and left to stand at 25 ° C for 24 hours. The obtained gel-like sheet is taken out from each mold, washed with ion-exchanged water until the alkali is removed from the sheet and becomes neutral, and pack gel sheet A-1 (See Fig. 2 for the front view of the sheet. And the sample A2 for measurement were obtained.

Example 2

[0031] <Preparation of poly (oral) taxane (main chain molecular weight 350,000)>

<<Preparation of PEG-carboxylic acid by TEMPO oxidation of PEG>>

10 g of PEG (molecular weight 350,000), 100 mg of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy radical), and lg of sodium bromide were dissolved in 100 ml of water. 5 ml of a commercially available sodium hypochlorite aqueous solution (effective chlorine concentration: about 5%) was added to the resulting solution, and the mixture was allowed to react at room temperature with stirring. As the reaction progressed, the pH of the system rapidly decreased immediately after the addition, but was prepared by adding IN NaOH so as to maintain the pH: 10 to 11 as much as possible. The pH drop generally disappeared within 3 minutes, but was stirred for another 10 minutes. Ethanol was added in a range up to about 5 m to terminate the reaction. Extraction with 50 ml of methylene chloride was repeated 3 times to extract components other than inorganic salts, and then methylene chloride was distilled off with an evaporator. After dissolving in 250 ml of hot ethanol, it was placed in a freezer at −4 ° C. to precipitate PEG-powered rubonic acid, that is, one in which both ends of PEG were substituted with carboxylic acid (one COOH). The precipitated PEG strong rubonic acid was recovered by centrifugation. This cycle of hot ethanol dissolution, precipitation, and centrifugal separation was repeated several times, and finally dried by vacuum drying to obtain PEG strong rubonic acid. Yield over 95%. Carboxylation rate is 95% or more.

[0032] <<Using PEG-carboxylic acid and α-CD! /, Preparation of inclusion complex >>

3 g of PEG carboxylic acid prepared above and a-CD9 g were dissolved in 50 ml of warm water of 70 ° C separately prepared, then mixed together, and then left overnight in a refrigerator (4 ° C). . The inclusion complex precipitated in the form of cream was lyophilized and recovered.

[0033] <<Sealing of inclusion complex using adamantanamin and BOP reagent reaction system> Adamantaneamine 0 · 13g, BOP reagent (benzotriazole-1-yl-oxy-tris (dimethylamino) phosphonium hexafluorophosphate) 0.38g, diisopropylethylamine 0 · 14ml A solution dissolved in 50 ml of dehydrated dimethylformamide (DMF) was added, shaken well, and allowed to stand in a refrigerator. Thereafter, 50 ml of methanol was added, followed by stirring, centrifugation, and removal of the supernatant. Subsequently, 100 ml of a DMF / methanol = 1: 1 mixed solution was added, and the same operation was performed twice. Further, the same operation was performed twice using 100 ml of methanol, and the resulting precipitate was vacuum-dried and then dissolved in 50 ml of dimethyl sulfoxide (DMSO). This solution was added dropwise to 700 ml of pure water to precipitate a polymouth taxane. Precipitated polymouth taxane was collected by centrifugation and dried in vacuum. Further, the same reprecipitation operation was carried out to obtain 9 g of a polymouth taxane (main chain molecular weight: 350,000). As a result of NMR measurement of the polypolytaxane obtained, the ratio (molar ratio) of CD to PEG monomer was CD: PEG monomer = 12.5 · 100 (inclusion rate: 25%)

1. To 15 ml of 5N NaOH aqueous solution, dissolve 3.0 g of poly (or polytaxane) (main chain molecular weight 350,000), add 6 ml of BDGEO. To this solution, mix, and remove bubbles with ultrasound. Then, it was poured into a mask mold having a thickness of 0.8 mm and a sample mold for measurement (a strip mold having a thickness of 0.5 mm and a width of 4 mm) and allowed to stand at 25 ° C. for 15 hours. The obtained gel-like sheets were taken out from the respective molds and washed with ion-exchanged water until the alkali was removed from the sheets and became neutral, and pack gel sheet B-1 and measurement sample B-2 were obtained.

Example 3

[0035] 2. 12 g of the poly oral taxane prepared in Example 1 (main chain molecular weight 10 million, inclusion rate 26%) was completely dissolved in 12 ml of IN NaOH aqueous solution to obtain a poly oral taxane solution. Separately, polyhydroxyethyl methacrylate (abbreviated as “p-HEMA”. Molecular weight 300,000, manufactured by Aldrich) 1.0 g was dissolved in 5 ml of IN NaOH aqueous solution to obtain a p-HEMA solution. 11.3 ml of poly-taxane solution and 3.8 ml of p-HEMA solution are mixed in an ice bath, 0.45 ml of BDGE is added, air bubbles are removed with a centrifuge, and a mask type with a thickness of 0.8 mm is obtained. The sample was poured into a measurement sample mold (strip shape with a thickness of 0.5 mm and a width of 4 mm) and allowed to stand at 2 ° C. for 48 hours. The obtained gel-like sheet is taken out from each mold and ion exchange is performed until the alkali is removed from the sheet and becomes neutral. The gel sheet C1 for packs and the sample C2 for measurement were obtained by washing with water.

[0036] (Comparative Example 1)

Polypolytaxane prepared in Example 1 (main chain molecular weight 10 million, inclusion rate 26%) to 15 ml of IN NaOH aqueous solution 2. Ig is completely dissolved, and 6 ml of BDGEO. Is added to this solution and mixed. Then, bubbles were removed with ultrasonic waves and poured into a mask mold having a thickness of 0.8 mm and a sample mold for measurement (a strip mold having a thickness of 0.5 mm and a width of 4 mm) and left to stand at 25 ° C. for 24 hours. The obtained gel sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral, to obtain a gel sheet for packing A′-1 and a measurement sample A′-2.

[0037] (Comparative Example 2)

In 10 ml of IN NaOH aqueous solution, 1.5 g of the poly oral taxane prepared in Example 1 (main chain molecular weight 10 million, inclusion rate 26%) was completely dissolved to obtain a poly oral taxane solution. Separately, hydroxyethyl cellulose (abbreviated as “HEC”; Aldrich) 0 · 75 g was dissolved in 5 ml of IN NaOH aqueous solution to obtain an HEC solution. Mix 10 ml of polymouth taxane solution and 5 ml of HEC solution, add 45 ml of BDGEO., Remove air bubbles with a centrifuge, and then remove the air bubble with a 0.8 mm thick mask mold and a measurement sample mold (thickness 0.5 mm, width). 4mm strip type) and left at 25 ° C for 24 hours. The obtained gel-like sheets were taken out from the respective molds and washed with ion-exchanged water until the neutral force was removed from the sheets until they became neutral, and pack gel sheet D-1 and measurement sample D-2 were obtained. .

[0038] (Comparative Example 3)

In 10 ml of IN NaOH aqueous solution, 1.5 g of the poly oral taxane prepared in Example 1 (main chain molecular weight 10 million, inclusion rate 26%) was completely dissolved to obtain a poly oral taxane solution. Separately from this, polybulualcohol (abbreviated as “PVA”, Mw: 31,000 to 50,000, manufactured by Aldrich) 0.7 5 g was dissolved in 5 ml of IN NaOH aqueous solution to obtain a PVA solution. Mix 10 ml of polymouth taxane solution and 5 ml of PVA solution, add 45 ml of BDGEO. Remove the bubbles with a centrifuge and remove 0-8 mm thick mask mold and measurement sample mold (thickness 0.5 mm, width 4 mm) And was allowed to stand at 25 ° C for 24 hours. The obtained gel-like sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral, to obtain a gel sheet E1 for packs and a sampnore E-2 for measurement. [0039] Examples:! To 3 and Comparative Example 1 The initial elastic modulus, the maximum elongation, and the breaking strength of the measurement samples prepared in 3 were measured with RSA-III of Rheometric 'Scientific' F 'company. It was measured. The measurement was performed at 25 ° C and an elongation speed of 0.3 mm / s. The initial elastic modulus was obtained from the slope of the approximate straight line of the Stress-Strain curve up to an elongation of 50% (Fig. 3 shows the initial elastic modulus of the measurement sample A-2 in Example 1. — Indicates an approximate straight line of the strain curve). The maximum extension rate is L for the length of the sample before extension, and the length of the sample at the maximum extension.

0

When L is L, the following equation is obtained. The results are shown in Table 1.

max

[0040] 圖

Maximum elongation = " ^Q x l00 (%)

[0041] [Table 1] Table 1

[0042] The gel sheet for packs obtained in Example 1 3 is a sheet that covers the upper half of the face. It has sufficient strength and flexibility, and the sheet does not become brittle due to its own weight. Could be used.

On the other hand, the pack gel sheet of Comparative Example 1 was broken when the gel was removed from the mold, or when it was picked up with a finger, it could not withstand its own weight and was torn.

Further, the pack gel sheet of Comparative Example 2 was difficult to follow the unevenness of the face, which was poorly stretched. On the other hand, it was torn when it was stretched forcibly along the unevenness of the face.

Further, the pack gel sheet of Comparative Example 3 was torn during the operation until the shells were held on the face, such as pinching the sheet with fingers and spreading it. From these, it was found that the sheet having the characteristics of the present invention, that is, the maximum elongation, breaking strength, and initial elastic modulus, has the desired performance for the face pack sheet.

Example 4

[0043] In 15 ml of DMSO, 1.5 g of PVA (Mw: 85,000 to 124,000 · Aldrich) was dissolved to obtain a PVA solution. In this PVA solution, 1.5 g of the polymouth taxane prepared in Example 2 (main chain molecular weight: 35,000, inclusion rate: 25%) was completely dissolved, and 1,2,3,4-butanetetracarboxylic acid dihydrate was dissolved. Add 300 mg of non-hydrate (hereinafter abbreviated as “BTA”) and triethylamine 15 1, remove air bubbles with a centrifuge, and remove 0.8 mm thick mask mold and measurement sample mold (thickness 0). 5 mm and 4 mm wide strips) and left at 25 ° C for 7 hours. The obtained gel-like sheet is taken out from each mold, washed with ion-exchanged water until DMSO is removed from the sheet and the solvent is completely exchanged with water, and the gel sheet F-1 for measurement and the sample for measurement are used. F-2 was obtained. Example 5

[0044] PVA (Mw: 85,000 to 124,000. Aldrich) 1 · 5 g was dissolved in 15 ml of DMSO to obtain a PVA solution. In this PVA solution, 1 · 5g of the polymouth taxane prepared in Example 1 (main chain molecular weight 100,000, inclusion rate 27%) was completely melted, and BTA 150mg and triethinoleamine 15〃1 were calorie-free. Then, bubbles were removed with a centrifuge and poured into a mask mold having a thickness of 0.8 mm and a sample mold for measurement (a strip mold having a thickness of 0.5 mm and a width of 4 mm) and allowed to stand at 25 ° C. for 6 hours. The obtained gel-like sheets are taken out from the respective molds, washed with ion-exchanged water until DMSO is removed from the sheets and the solvent is completely replaced with water, and the gel sheet G-1 for packs and the sampnore G-2 for measurement are used. Got.

Example 6

[0045] In 10 ml of 2N NaOH aqueous solution, the poly oral taxane prepared in Example 1 (main chain molecular weight 100,000, inclusion rate 27%) 3. Og was completely dissolved to obtain a poly oral taxane solution. Separately, 1.5 g of methylcellulose (hereinafter simply abbreviated as “MC”) (“Metroses (registered trademark) SM-15” manufactured by Shin-Etsu Chemical Co., Ltd.)) is dissolved in 10 ml of water to obtain an MC solution. It was. Mix 10.4 g of poly-taxane taxane solution and 8.6 g of MC solution, add BDGE600 1 and remove bubbles with a centrifuge to remove the 0 · 8 mm thickness mask sample and the measurement sample die (thickness 0 · 5 mm and 4 mm wide strips) and left at 25 ° C for 19 hours. Take out the obtained gel sheet from each mold Then, the sheet was washed with ion-exchanged water until alkali was removed from the sheet and became neutral, to obtain a gel sheet H-1 for pack and a sampnore H-2 for measurement.

Example 7

[0046] <Preparation of poly (oral) taxane (main chain molecular weight: 500,000)>

Except that the molecular weight of PEG was 500,000 and the inclusion rate was 19%, a polyortaxane (main chain molecular weight 500,000, inclusion rate 19%) was obtained in the same manner as in Example 1.

In 15 ml of IN NaOH aqueous solution, 1.5 g polypolytaxane (main chain molecular weight: 500,000, inclusion rate: 19%) is completely dissolved. Add BDGESOO ^ l to this solution, mix, and remove bubbles with ultrasound. Then, it was poured into a mask mold with a thickness of 0.8 mm and a sample mold for measurement (a strip with a thickness of 0.5 mm and a width of 4 mm) and left at 25 ° C. for 24 hours. The obtained gel-like sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral, thereby obtaining a pack gel sheet I1 and a measurement sample I2.

Example 8

[0048] In 25 ml of IN NaOH aqueous solution, 25 g of polymouth taxane prepared in the same manner as in Example 7 (main chain molecular weight 500,000, inclusion rate 19%) 2. 25 g was completely dissolved, and BDGE450 1 Add and mix, remove bubbles with ultrasonic waves, pour into a mask mold with a thickness of 0.8 mm and a sample mold for measurement (a strip with a thickness of 0.5 mm and a width of 4 mm), and let stand at 25 ° C for 24 hours. I put it. The obtained gel sheets were taken out from the respective molds and washed with ion exchanged water until the alkali was removed from the sheets and became neutral, to obtain pack gel sheet I 3 and measurement sample I 4. Example 9

[0049] In 15 ml of DMS, a polymouth taxane prepared in the same manner as in Example 7 (main chain molecular weight 500,000, inclusion rate 19%) 2. 25 g was completely dissolved. Add and mix xamethylene diisocyanate 150 1 and remove bubbles with ultrasonic waves, then pour into a mask mold with a thickness of 0.8 mm and a sample mold for measurement (a strip with a thickness of 0.5 mm and a width of 4 mm). And left at 60 ° C for 15 hours. The obtained gel-like sheets are taken out from the respective molds, washed with ion-exchanged water until DMSO is removed from the sheets and the solvent is completely exchanged with water, and the gel sheet J1 for measurement and the measurement sample J2 are removed. Obtained. [0050] (Comparative Example 4)

HEC (manufactured by Aldrich) in 15 ml of IN NaOH aqueous solution 3. Og is completely dissolved, BDGE600 1 is added to this solution and mixed, and bubbles are removed by ultrasonic to measure a mask type with a thickness of 0.8 mm. The sample was poured into a sample mold (strip type with a thickness of 0.5 mm and a width of 4 mm) and allowed to stand at 25 ° C for 20 hours. The obtained gel-like sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral, to obtain a pack gel sheet M-1 and a measurement sample M-2.

[0051] (Comparative Example 5)

Dissolve PVA (Mw: 31,000-50,000 Aldrich) 3 · Og completely in 15 ml IN NaOH aqueous solution, add BDGEeOO ^ l to this solution, mix, and remove bubbles with ultrasound Then, it was poured into a mask mold having a thickness of 0.8 mm and a sample mold for measurement (a strip mold having a thickness of 0.5 mm and a width of 4 mm) and allowed to stand at 25 ° C. for 15 hours. The obtained gel-like sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral to obtain a pack gel sheet N-1 and a measurement sample N-2. Measurement sample N-2 was measured for initial strength, maximum elongation, and breaking strength. As a result, it was found that initial elastic modulus: lkPa, maximum elongation: 151%, and breaking strength: 3kPa. It was.

[0052] (Comparative Example 6)

IN NaOH aqueous solution 15ml, PVA (Mw: 85,000-124,000 · Aldrich) 2 · 25g is completely dissolved, BDGE450 1 is added to this solution and mixed, and bubbles are removed by ultrasonic to remove the thickness. It was poured into a mask mold of 0.8 mm and a sample mold for measurement (a strip of 0.5 mm thickness and 4 mm width) and allowed to stand at 25 ° C. for 15 hours. The obtained gel-like sheet was taken out from each mold and washed with ion-exchanged water until the alkali was removed from the sheet and became neutral, to obtain a pack gel sheet P-1 and a measurement sample P-2. As a result of measuring the initial elastic modulus, the maximum elongation rate, and the breaking strength of the measurement sample P-2, it was found that the initial elastic modulus: 3 kPa, the maximum elongation rate: 170%, and the breaking strength: 7 kPa.

[0053] The pack gel sheets obtained in Examples 4 to 9 are sheets that cover the upper half of the face, have sufficient strength and flexibility, and do not become brittle due to their own weight. We were able to use without. On the other hand, the pack gel sheet of Comparative Example 4 did not feel stretched even when pulled, and was severed when pulled strongly. Also, when the sheet was bent, the gel was cut or cracked when it was bent.

In the gel sheets for packing of Comparative Examples 5 and 6, the gels were easy to stick to each other, and it was very difficult to perform such operations as spreading them softly and putting them on the skin. Also, when I picked it up with my finger, I couldn't stand its own weight and got struck.

From these facts, it was found that the sheet having the characteristics of the present invention, that is, the maximum elongation, breaking strength, and initial elastic modulus has the desired performance for the face pack sheet.

[Table 2]

Table 2. Measurement results of samples of Examples 4 to 9 and Comparative Examples 4 to 6

Brief Description of Drawings

FIG. 1 is a view showing an embodiment of the “sheet” of the present application that covers the entire face and has a shape along the face undulation.

FIG. 2 is a diagram showing the mask molds used in Examples;! To 9 and Comparative Examples; In the figure, the numbers indicate the unit: mm.

FIG. 3 is a stress-strain curve graph for obtaining the initial elastic modulus of Example 1 (A-2).

Claims

The scope of the claims

[1] i) a first poly-oral taxane; and ii) the following substances a) and / or b):

a) a first polymer that is other than a polymouth taxane;

b) a second polymouth taxane,

And i) the first poly (oral taxane) and the ii) substance chemically and / or physically bonded,

[2] The first and / or second linear molecule is selected from the group consisting of polyethylene glycol, polyisoprene, polyisobutylene, polybutadiene, polypropylene glycol, polytetrahydrofuran, polydimethylsiloxane, polyethylene, and polypropylene. The sheet according to claim 1.

[3] The sheet according to claim 1 or 2, wherein the first and / or second linear molecule has a molecular weight of 10,000 or more.

[4] The first and / or second blocking group is replaced with dinitrophenyl groups, cyclodextrins, adamantane groups, trityl groups, fluoresceins, pyrenes, substituted benzenes, The sheet according to any one of claims 1 to 3, which is selected from the group consisting of Moyo! /, Polynuclear aromatics, and steroids.

[5] A cyclodextrin molecule in which the first and / or second cyclic molecule may be substituted. The sheet according to any one of claims 4 to 4.

[6] The first and / or second cyclic molecule may be substituted and may be a cyclodextrin molecule, and the cyclodextrin molecule may be α-cyclodextrin, 0-cyclodextrin and γ- The sheet according to any one of claims 1 to 5, which is selected from the group consisting of cyclodextrin and derivatives thereof.

[7] The first and / or second cyclic molecule is α-cyclodextrin which may be substituted, and the linear molecule is polyethylene glycol. The described sheet.

[8] When the first cyclic molecule is clasped by the first linear molecule in a skewered manner, the maximum amount of inclusion of the first cyclic molecule is 1. The sheet according to any one of claims 1 to 7, wherein 1 cyclic molecule is included in a skewered manner with the first linear molecule in an amount of 0.00;

[9] When the amount by which the second cyclic molecule is maximally included when the second cyclic molecule is included in a skewered manner by the second linear molecule is 1, The sheet according to any one of claims 1 to 8, wherein the two cyclic molecules are included in a skewered manner with the second linear molecule in an amount of 0.00;