JP5283320B2 - Pack cosmetic - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pack cosmetic having a high water absorption and humectant function, dissolving collagen quickly and imparting it into a skin. <P>SOLUTION: This pack cosmetic consists of a substrate fiber without being dissolved in water and having water absorbency, and a fibrous sheet containing dissolvable collagen fibers having &le;0.5 pH isoionic point, and by using the substrate fiber and dissolvable collagen fiber, a fibrous sheet such as a woven fabric, a nonwoven fabric, a hair-planted cloth, etc., can be prepared. The fibrous sheet may contain a non-water soluble binder resin, and it is blended as particle or fiber forms and point-bonds the substrate fibers to each other. The quickly dissolvable collagen fiber is obtained by ejecting/spinning the dissolvable aqueous collagen solution (A) into an organic solvent (S1) in a filament like state, stretching the obtained dissolvable collagen fiber (F) and immersing in a hydrophilic organic solvent (S2). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a pack cosmetic that is composed of collagen, is easy to apply to and remove from the skin, and can be removed cleanly without changing the application time of the pack as needed.

  Pack cosmetics are cosmetics in which various active ingredients are blended into a pack base, and the active ingredients are supplied to the skin by applying to the skin and holding for a predetermined time. Conventional pack cosmetics are roughly classified into a washing type that is washed off after use, and a peeling type that forms and peels off a film. In the case of a washing-type pack cosmetic, the pack base is creamy, viscous liquid, foamy, etc., and is applied to the skin and left standing, and then washed off with water or lukewarm water or wiped with a wet towel. In the case of the peeling type, the pack base is in the form of a jelly, paste or viscous liquid, and after being applied to the skin, a film is formed by drying or the reaction of the base. Cosmetics can be peeled off by hand. From the viewpoint of labor after use, the peel type tends to be preferred by general users over the cleaning type.

  In the peel-type pack cosmetic, the following matters relating to the feeling of use and film formation are problematic.

    1) If the strength of the film is weak, peeling off occurs, and if the strength of the film is increased to prevent peeling off, the skin may be uncomfortable and the skin may be damaged when peeling off.

    2) A container designed to prevent film formation during storage before use is necessary.

  Various improvements have been attempted to improve these, and for example, pack cosmetics such as the following Patent Documents 1 and 2 have been proposed. In Patent Document 1, a pack cosmetic composed of a gel-like part containing a water-soluble alginic acid salt and a powder part containing a metal salt and a reaction retarding agent is used to improve the temporal stability of the pack cosmetic. In Patent Document 2, a first agent containing a water-reactive metal oxide, a carbonate and a starch / acrylic acid graft polymer, an acid, A pack cosmetic composed of a second agent containing an aqueous solution is proposed.

On the other hand, as a new type, facial mask type pack cosmetics in which a cosmetic ingredient is included in a substrate such as a non-woven fabric has been provided in recent years. If necessary, the pack cosmetic can be peeled off at any time. For example, the following Patent Document 3 proposes a cosmetic material containing a dry cosmetic ingredient in a nonwoven fabric, and the following Patent Document 4 proposes a cosmetic tool in which a dry water-soluble moisturizing ingredient is attached to the surface of the cotton body. Has been.
JP-A-6-179614 JP 2003-89615 A JP 2004-51521 A JP 2002-255726 A

  In a facial mask type pack cosmetic, collagen is introduced into a substrate in a dry state in order to prevent deterioration of collagen having low thermal stability. However, when a non-woven fabric or cotton is used as a base material and an aqueous collagen solution is impregnated or applied to the base material and dried, the dried collagen coats the fibers constituting the base material in a thick film shape, and thus impedes water absorption of the base fiber. As a result, the water retention amount of the mask as a whole is significantly reduced. Therefore, even if water is added to the mask, it dries in a short time due to insufficient water retention when it is applied to the skin, and does not exhibit a satisfactory moisturizing function. In addition, the surface area of the collagen thick film in contact with water is insufficient, and the dissolution rate of collagen becomes extremely slow. Since the amount of collagen dissolved also decreases due to insufficient water absorption of the base fiber, a sufficient amount of collagen cannot be applied to the skin. When a large amount of collagen is placed on the substrate, the solubilized collagen solidified while adhering to the substrate fiber impairs the flexibility of the substrate fiber, so that the touch is very bad and the mask is hard and difficult to handle.

  The present invention solves the above-mentioned points, and provides a pack cosmetic that does not inhibit the water absorption of the base fiber, collagen is quickly dissolved and appropriately applied to the skin, and sufficiently exhibits the moisturizing function. Is an issue.

  It is another object of the present invention to provide a pack cosmetic that is comfortable to touch and easy to handle.

  In order to solve the above-mentioned problems, the present inventors have made extensive studies, and as a result, can create a sheet having a good touch using solubilized collagen fibers, and apply this to use as a pack cosmetic. Thus, the present inventors have found that it is possible to provide a pack cosmetic that has a high moisturizing function, has a good touch and is easy to handle when applied to the skin, and has completed the present invention.

  According to one aspect of the present invention, the pack cosmetic has a fiber sheet containing base fiber that is insoluble in water and absorbs water, and solubilized collagen fiber having an isoionic point of pH 5.0 or less. Is the gist.

  According to the present invention, a soft and comfortable sheet can be prepared using solubilized collagen fibers, and using this, it is easy to handle, has a sufficient moisture retention function due to its high water absorption capacity, and has an appropriate amount of collagen. A pack cosmetic that can be applied to the skin can be provided. In addition, collagen can be quickly dissolved using commercially available lotion, etc., and collagen can be efficiently supplied to the skin in an optimal state that meets the needs of each user, and the product specifications are subdivided. It can be widely provided to various users without doing so.

  Collagen is a major protein that forms animal skins, tendons, bones, etc., and is a substance in which three polypeptide chains are formed in a helix, usually against water, dilute acid, dilute alkali, organic solvents, etc. Although it is insoluble, a solubilized aqueous collagen solution can be obtained by solubilization treatment. For the solubilization treatment, a method using a proteolytic enzyme (see, for example, Japanese Patent Publication No. 44-1175, hereinafter referred to as an enzyme treatment method), a small amount of amines in an aqueous solution in which caustic alkali and sodium sulfate coexist or It can be roughly classified into a method of treating with a substance added with an analog (for example, refer to Japanese Examined Patent Publication No. 46-15033, hereinafter referred to as an alkali treatment method). It is considered that the binding between peptide chains is released by cross-linking or cleavage of the telopeptide itself and solubilized.

  In recent years, makeup products, skin care products, and the like in which collagen is blended as a component for enhancing the moisture retention property of skin using the moisture retention property of collagen have been provided. Collagen used in such an application is solubilized collagen, and the aqueous solution of solubilized collagen becomes a solid dried product when water is removed. The denaturation start temperature of solubilized collagen in an aqueous solution is very low, about 30 ° C. for cows and pigs, and about 20 ° C. for puffer fish, tie, etc. In this case, the temperature is around 100 ° C., and there is no fear of denaturation during normal handling. Moreover, unlike the aqueous solution, the collagen in a dry state has no fear of spoilage.

  When a porous body having water absorption ability, water retention ability such as non-woven fabric or cotton is used as a base, and this is impregnated or coated with a solubilized collagen aqueous solution and dried, the base fiber whose surface is covered with solidified collagen is: Since water absorption is inhibited and the amount of water retention is remarkably reduced, the function of moisturizing the skin is lowered, and the amount and rate of dissolution of collagen are small. In addition, the fibers of the substrate are covered with the solidified solubilized collagen, the flexibility is impaired, and the touch is extremely lowered.

  Compared to this, when a fiber sheet is prepared using solubilized collagen fibers as part of the raw material fibers constituting the substrate, and this is used as a pack cosmetic, the collagen is prevented from falling off due to the entanglement of the fibers. Therefore, it is not necessary to fix the collagen to the base fiber, and the water absorption inhibition and the decrease in flexibility of the base fiber are avoided. Since the fibers are fibers, the amount of collagen used can be arbitrarily and easily adjusted. Moreover, the solubilized collagen fiber has flexibility, and the fiber sheet prepared using this has good tactile sensation.

  Below, the fiber sheet using the solubilized collagen fiber which comprises the pack cosmetics of this invention is demonstrated.

  The fiber sheet contains base fiber that is insoluble in water and absorbs water, and solubilized collagen fiber. A base fiber is a fiber used for manufacture of a general woven fabric and a nonwoven fabric, and what has water absorption is used. The solubilized collagen fiber is a collagen fiber that can be dissolved in water by a solubilization treatment, and can be prepared by discharging a solubilized collagen aqueous solution into salt water or an organic solvent and coagulating and spinning in accordance with a known method. For example, it can be obtained by referring to the method for producing a dried solubilized collagen disclosed in JP-A-6-228505. Below, the form of the fiber used for manufacture of a fiber sheet and a fiber sheet is demonstrated.

  The base fiber may be either a hydrophilic fiber or a hydrophobic fiber as long as it has water absorption properties. However, considering the water retention ability of the entire fiber sheet, the hydrophilic fiber is preferable. Examples of hydrophilic fibers include plant fibers, animal fibers, regenerated fibers, and semi-synthetic fibers. Specifically, plant fibers such as cotton fibers, hemp fibers, and Japanese paper fibers; animal fibers represented by silk fibers and wool Examples thereof include animal fibers such as fibers; regenerated fibers such as rayon and cupra; semisynthetic fibers such as acetate, cellulose, and regenerated protein. Further, insoluble collagen fibers obtained by subjecting solubilized collagen fibers to crosslinking / insolubilization treatment according to a known method (for example, JP-A No. 50-141190) can also be suitably used. In the case of a hydrophobic fiber, it is necessary to make the fiber surface porous to impart water absorption due to capillary action, or to impart hydrophilicity by chemical treatment. In pack cosmetics containing collagen, the water absorption of the base fiber is important, and the base fiber alone has a water content of 500% or more throughout the pack time of about 10 minutes [100 × (mass after water absorption−before water absorption). (Mass) / mass before water absorption] is preferable if water retention can be stably maintained.

  As the solubilized collagen fiber, one having an isoionic point of pH 5.0 or less is used so as to dissolve in water at a pH of general cosmetics from weak acidity to neutrality. When spinning with a solubilized collagen aqueous solution having a pH higher than the isoionic point of the solubilized collagen fiber, the resulting solubilized collagen fiber has a fast dissolution rate in weakly acidic to neutral water, and particularly has a fineness of about 10 dtx or less. It dissolves in water within 30 seconds. In addition, solubilized collagen fibers having a fineness of about 10 dtx or less are suitable for processing because they have a low frictional resistance in the sliver or web state, are very comfortable to touch, and have high flexibility. When the solubilized collagen fiber after spinning is dried in a state without a tensile load, it is properly crimped by shrinkage and is particularly suitable for producing a nonwoven fabric.

The fiber sheet may be a woven fabric or a non-woven fabric, and may be a flocked woven fabric or a flocked non-woven fabric in which flocked fibers are planted, solubilizing a part of fibers constituting a general woven fabric or non-woven fabric. It can be considered that it was replaced with collagen fibers. As a pack cosmetic such as a facial mask, the solubilized collagen fibers per unit area of the sheet is preferably about 0.2 to 30 g / m ^2, and in terms of fit to a curved surface, etc. Is preferably about 20 to 100 g / m ² and a thickness of about 0.2 to 5 mm. In the case of a woven fabric, a blended yarn obtained by blending short fibers of a base fiber and a solubilized collagen short fiber, and a twisted yarn obtained by twisting these long fibers can also be used. When a blended yarn or a twisted yarn containing fibers is used, the form of the fiber sheet is not limited.

  When the fiber sheet is a nonwoven fabric, the fiber sheet is obtained by molding and processing a fiber mixture obtained by mixing base fibers and solubilized collagen fibers in accordance with a general nonwoven fabric manufacturing method. In general, short fibers are preferably used as the fibers for forming the nonwoven fabric, and the fiber length is preferably about 2.5 to 10 cm in terms of workability in processing, but the fibers have crimps. Should have a length of about 10 mm or more. The fineness of the base fiber is preferably about 10 dtx or less. From the viewpoint of the flexibility of the nonwoven fabric, a fiber of about 0.5 to 5 dtx is preferable, but this point also depends on the fiber material. To do. The solubilized collagen short fiber for producing the nonwoven fabric can be suitably produced according to the previous application (Japanese Patent Application No. 2004-121513) by the present applicant, and the average fineness is 20 dtx (dtx: grams per 10000 m of fiber). To about 100 dtx. In this case, the average fiber length can be appropriately changed by adjusting the solvent flow during spinning, and is preferably adjusted to about 2.5 to 10 cm. When thin short fibers of 10 dtx or less are used, they may be cut after the long fibers are produced according to the method for producing solubilized collagen fibers described later. When it is naturally crimped during drying, it may be cut to a length of about 10 mm or more. The amount of the solubilized collagen fiber is 30% by mass or less of the total of the base fiber and the solubilized collagen fiber, preferably so that the shape of the fiber sheet is maintained after the solubilized collagen fiber of the fiber sheet is dissolved in water. Is preferably about 3 to 15% by mass. The base fiber and solubilized collagen fiber in such a ratio are defibrated and mixed using, for example, a carding machine to obtain a uniform sliver, and the fibers are fastened and densified using a needle punch or the like. As a result, a non-woven fiber sheet is formed. Or after adding the short fiber of the base fiber to the dispersion of the solubilized collagen short fiber as obtained in Japanese Patent Application No. 2004-121513 and uniformly dispersing it, the solvent is removed according to the wet papermaking method to obtain a nonwoven fabric. good. You may shape | mold into the nonwoven fabric of the structure which laminated | stacked the several layer in which the fiber was located in parallel. The thickness of the nonwoven fabric can be determined in consideration of the amount of solubilized collagen fibers per unit area, the flexibility of the fiber sheet, and the like according to the necessity in the usage form. In the production of a general nonwoven fabric, a binder that bonds fibers may be used. However, in the present invention, when using a binder, the amount used should be considered so as not to prevent water absorption of the base fiber. desirable.

When the fiber sheet is a woven fabric (the woven fabric in the present application includes not only a narrowly-defined woven fabric using warp and weft but also a knitted fabric), the woven fabric includes a base fiber and a solubilized collagen fiber. It can be formed by using the blended yarn or the twisted yarn that is contained, or can be a woven or knitted fabric using the yarn containing the base fiber and the yarn containing the solubilized collagen fiber. In any case, since the shape of the sheet after the solubilized collagen fiber is dissolved can be maintained by the base fiber, the proportion of the solubilized collagen fiber in the fiber sheet can be freely set, but the solubilized collagen as a pack cosmetic It is preferable to be about 0.2 to 30 g / m ² per unit area, which is an appropriate amount of fiber.

When the fiber sheet is a flocked fabric, that is, a flocked woven fabric or a flocked non-woven fabric, the basic flocked fabric is composed of a base fabric that forms the sheet shape and flocked fibers that are implanted in the base fabric. In order to maintain the sheet shape after the solubilized collagen fibers are dissolved, the base fabric is formed using the base fiber, but may contain solubilized collagen fibers. The flocked fiber may be either a base fiber or a solubilized collagen fiber, but as a pack cosmetic, the flocked fiber is a solubilized collagen fiber from the viewpoint of collagen solubility and application to the skin. preferable. The flocking of the flocked fiber to the base fabric can be performed using a needle punch or the like. When the base fabric is a woven fabric, the shape of the sheet after the solubilized collagen fibers are dissolved is maintained by the base fiber, so the proportion of the solubilized collagen fibers in the fiber sheet can be freely set. In the case of a non-woven fabric, the proportion of the solubilized collagen fiber of the base fabric is preferably 30% by mass or less in order to maintain the shape of the base fabric as described above. If a woven or non-woven fabric made of a base fiber is used as a base fabric and a solubilized collagen fiber is planted as a flocked fiber, manufacturing and design changes are easy. A preferable form includes, for example, a gauze-like cotton base fabric in which solubilized collagen fibers are implanted. As pack cosmetics, it is preferable that the solubilized collagen fiber per unit area of the fiber sheet is about 0.2 to 30 g / m ² . It should be noted that when a solubilized collagen short fiber is entangled with a base fiber and a yarn raised in a mohair shape is spun and a woven fabric is produced using this, a fiber sheet similar to a flocked woven fabric is obtained.

  The fiber sheet can be constituted as a non-woven fabric or a flocked fabric of solubilized collagen fibers alone without using base fibers, but in this case, the amount of solubilized collagen fibers per unit area becomes high, so that pack cosmetics As an inefficiency. In this regard, if a fiber sheet is knitted into a lace shape using thin solubilized collagen long fibers, the amount of collagen per unit area can be appropriately reduced, and when used as a pack cosmetic, no residue remains after use. .

  A method for producing a solubilized collagen fiber capable of obtaining a fine collagen fiber having a fineness of 10 dtx or less is described below.

  Insoluble collagen can be suitably prepared by conventional methods using the skin of animals such as cows, pigs and birds, and other tissues containing collagen, and the raw material is not particularly limited. Insoluble collagen may be obtained from aqueous biological raw materials such as fish skin and fish scales. Although there is a difference in the denaturation temperature of collagen depending on the raw material from which collagen is obtained, there is no problem in ordinary handling in the dry state even if solubilized collagen derived from any raw material. In demand, it is preferable to use collagen derived from pigs or aquatic organisms as a raw material in relation to BSE countermeasures.

  Collagen raw materials such as cow skin and pork skin are prepared into raw material pieces of appropriate dimensions by performing treatment such as hair removal by lime pickling, water washing, shredding using a chopper, etc. Subject to solubilization treatment.

  Insoluble collagen is solubilized by a method using a proteolytic enzyme (see, for example, Japanese Patent Publication No. 44-1175, hereinafter referred to as an enzyme treatment method), and a small amount of amine in an aqueous solution in which caustic alkali and sodium sulfate coexist. It can be roughly classified into a method of treating with an additive or a similar one (see, for example, Japanese Examined Patent Publication No. 46-15033, hereinafter referred to as an alkali treatment method). In the present invention, any solubilization treatment method may be used, but the solubilized collagen obtained has an isoionic point (pH range in which the solubility in water is the smallest) depending on the solubilization treatment method, and the alkali treatment method. The isoionic point of the solubilized collagen obtained in (1) is generally about 4.8 to 5.0 by changing the asparagine residue and glutamine residue to aspartic acid residue and glutamic acid residue, respectively, by deamination reaction. In general, the enzyme treatment method has a pH of around 7. The cosmetic is preferably weakly acidic to neutral, and it is necessary for the collagen to rapidly dissolve in this pH range. Therefore, when solubilized by an enzyme treatment method, the isoionic point of the resulting collagen is determined. It is necessary to shift from near neutral to pH 5 or lower. In solubilized collagen products by general enzyme treatment methods, succinylation is applied to lower the isoionic point to increase neutral solubility, so the solubilized collagen obtained by such methods is preferably used can do. The lower the solubilized collagen isoionic point, the higher the solubility in weakly acidic to neutral aqueous solvents. In order to increase the dissolution rate of collagen fibers used as cosmetics, the solubilized collagen isoionic point Is preferably about pH 4.8 or less.

  The solubilized collagen is obtained in the form of a viscous aqueous solution through neutralization of alkali used for solubilization and succinylation and desalting (for example, centrifugation, dialysis, washing with water, etc.). If water is removed from this, a solubilized collagen dried product can be obtained. As a method for removing water from an aqueous collagen solution, there are a freeze-drying method using liquid nitrogen or the like, a spray-drying method, and a method of coagulating in an organic solvent. The freeze-drying method requires a manufacturing cost, and the spray-drying method can obtain a suitable solubilized collagen powder at a low cost, but the manufacturing efficiency is low. The method of coagulating a solubilized collagen aqueous solution in an organic solvent utilizes the fact that the collagen in the aqueous solution coagulates when it comes into contact with the organic solvent. The solvent can be easily and efficiently removed from the coagulated collagen, and the production cost is low. Inexpensive. In the previous application (Japanese Patent Application No. 2004-121513), the applicant of the present application refers to the method for producing a dried solubilized collagen disclosed in JP-A-6-228505, and uses a nozzle or the like to form a solubilized collagen aqueous solution into a thread shape. Although it has been proposed to prepare collagen fibers by discharging and coagulating, this method has limitations in forming finer collagen fibers, and it is difficult to produce fibers of 10 dtx or less, and the fineness is around 10 dtx. When producing a thin collagen fiber, the fibers adhere to each other and are fused to form a lump when the fiber is dried. Fine collagen fibers with a fineness of 10 dtx or less are obtained by stretching the solubilized collagen fibers to be spun during coagulation, and by immersing the spun collagen fibers in a hydrophilic organic solvent before drying, The adhesion of collagen fibers can be prevented.

  The solubilized collagen can be coagulated with either a hydrophilic organic solvent or a hydrophobic organic solvent, but a hydrophilic organic solvent is preferred in that it effectively dissipates the water contained in the coagulated collagen to the outside. In order to efficiently dry the fibers, a volatile solvent is preferable as an organic solvent for coagulating solubilized collagen. Examples thereof include alcohols such as methanol, ethanol and isopropanol, acetone, and the like, and may be a mixed solvent in which a plurality of such solvents are combined. Practically, an organic solvent containing a small amount of water can also be used. In that case, the moisture content is about 15% by mass or less, preferably 10% by mass or less. If the moisture content is high, collagen does not coagulate properly.

  The solubilized collagen aqueous solution is discharged into an organic solvent in the form of a thread using a nozzle or the like, and the collagen is coagulated (ie, spun) into a fiber. As the spinning means, a nozzle having a discharge hole capable of discharging a fluid such as a nozzle or a shower head can be selected and used as necessary. In general, a solubilized collagen aqueous solution having a collagen concentration of 2 to 10% by mass, preferably 3 to 7% by mass, at a discharge speed of 20 to 500 g / min, preferably 30 to 150 g / min, and a pore size of 0.02 to 1 mm. Solubilized with an average fineness of about 10 to 100 dtx (value measured at 20 ° C. and 65% RH using a fineness meter). Collagen fibers are formed. In spinning in a free state, the fineness becomes higher than that during discharge due to shrinkage during coagulation. Therefore, in order to enable the preparation of fine fibers of 10 dtx or less, the spun collagen fibers are spun at a speed higher than the discharge speed. Then, the fiber is drawn by a tensile force applied to the collagen fiber being spun. However, if the winding speed is too high, the fiber is cut, so that the ratio of the winding speed to the discharge speed is adjusted to 1.5 or less and stretched. The thickness of the solubilized collagen fiber can be reduced by lowering the concentration of the solubilized collagen aqueous solution to be discharged or by reducing the pore diameter of the nozzle to be discharged, but if the concentration of the solubilized collagen aqueous solution is too low The fiber to be spun is easily cut or a powdery coagulum is easily formed. On the other hand, if the nozzle hole diameter is too small, the liquid flow resistance increases and an excessive discharge pressure is applied to the nozzle. Taking these into consideration, preferred conditions for spinning collagen fibers having an average fineness of 10 dtx or less are 3 to 7% by mass, preferably 3.5 to 5% by mass, and the nozzle hole diameter is 0.02%. It is about 0.18 mm, preferably about 0.05 to 0.11 mm, and the ratio of the winding speed to the discharge speed can be 1 or more and 1.5 or less, preferably 1.0 to 1.2. From the point of implementation, it is practical to set the discharge speed in the range of about 2 to 7 m / min and the winding speed in the range of about 2 to 10 m / min.

  The wound solubilized collagen fibers are dried by air drying using aseptic air or vacuum distillation to obtain solubilized collagen fibers that can be used for cosmetics. In the case of thin fibers, the fibers are in contact with each other. When they are dried, they adhere and bond to each other. This is because the residual water in the collagen fiber redissolves the coagulated collagen due to the organic solvent first evaporating during the drying, and becomes more prominent as the fiber is thinner. In order to prevent this, the solubilized collagen fibers before drying are immersed in a hydrophilic organic solvent. As a result, the moisture in the collagen fibers is dissipated in the organic solvent and is replaced with the organic solvent, so that the water content is reduced, the amount of the organic solvent is increased, and the adhesion of the fibers during drying is reduced. However, it is necessary that the hydrophilic organic solvent to be immersed has a low moisture content, and specifically, an organic solvent having a moisture content of 5% by mass or less is used. Examples of the organic solvent to be used include alcohols such as methanol, ethanol and isopropanol, and hydrophilic organic solvents such as acetone. A mixed solvent in which a plurality of such solvents are combined may be used. In order to avoid only water remaining when the collagen fibers are dried, it is effective to use a solvent having a boiling point close to that of water or a solvent azeotropic with water, and ethanol and isopropanol are preferable in this respect. Etc. The hydrophilic organic solvent may be gently flowed, or the solubilized collagen fibers soaked may be swung to promote the diffusion of moisture.

  When the spun solubilized collagen fiber is immersed in a hydrophilic organic solvent, the water content of the hydrophilic organic solvent increases. Therefore, it is necessary to replace the organic solvent whose water content has become excessive by repeating the dipping process. In this regard, reducing the amount of liquid contained in the fiber by lightly squeezing or centrifugally dehydrating the solubilized collagen fiber immediately before dipping in the organic solvent is effective in reducing the exchange frequency of the dipped organic solvent.

  The solubilized collagen fiber obtained by dipping in an organic solvent and then drying contains about 10 to 20% by mass of water even in the standard state (20 ± 2 ° C., humidity 65 ± 2% RH), but the denaturation temperature is high, It becomes around 100 ° C. for collagen derived from cattle and pigs.

  The closer the pH of the solubilized collagen fiber is to the pH of the aqueous liquid for preparing the cosmetic, the easier it is to dissolve in the aqueous liquid. Therefore, the pH of the solubilized collagen aqueous solution used for spinning is preferably close to the pH of the aqueous cosmetic solution. Considering that general cosmetics are weakly acidic to neutral, the pH of the solubilized collagen aqueous solution is Is adjusted to pH 5.5 to 10.0, especially pH 6.5 to 8.0, the spun collagen fiber dissolves quickly in commercially available skin lotion and serum, and the solubilized collagen having a fineness of 10 dtx or less. Fibers can be dissolved in water within 30 seconds. Therefore, collagen can be easily blended in cosmetics that are arbitrarily used by the user. If the alkali used to adjust the pH of the spinning collagen aqueous solution is only NaOH, the viscosity of the solubilized collagen aqueous solution is likely to increase, and the solution from the tank containing the collagen aqueous solution to the nozzle or the small diameter as described above. It becomes difficult to pass through the nozzle when discharging the collagen aqueous solution from the hole. Such viscosity increase is suppressed by adding an inorganic salt such as sodium sulfate or an organic acid salt such as sodium lactate in pH adjustment. There are organic acid salts that are soluble in organic solvents and those that are hardly soluble or insoluble, and when a salt that is hardly soluble or insoluble is used, it precipitates when the solubilized collagen aqueous solution is discharged into the organic solvent, Although it remains inside the fiber or adheres in the form of powder when the collagen fiber is dried, this point can be solved by using a salt that is soluble in an organic solvent. Specifically, when alcohol is used as the organic solvent for spinning and a salt that dissolves in alcohol such as sodium lactate is used during pH adjustment, the salt can be removed from the collagen fiber together with the solvent. Further, when the collagen fibers before drying are immersed in a hydrophilic organic solvent, the organic acid salt for pH adjustment can be removed by using alcohol. The organic solvent at the time of spinning and dipping is useful because it also has a function of removing organic impurities derived from the raw collagen.

  Solubilized collagen fibers spun from an aqueous solution of solubilized collagen having a pH of 5.5 or higher have a pH of 5.5 or higher when the collagen fibers are dissolved in deionized water at a rate of 0.5 mass% (in terms of anhydrous amount), Since it is different from the case of spinning from a collagen aqueous solution having a pH lower than the isoionic point of the solubilized collagen (becomes about pH 4.0 to 4.5), not only the dissolution rate in neutral water but also when dissolved It can also be easily distinguished by pH.

  In the above description, the shape of the discharge hole and the cross section of the collagen fiber are described as circular. However, the solubility in an aqueous solvent is improved by increasing the surface area of the fiber. The shape of the shape is not limited to a circle, and the discharge hole may be deformed so that a solubilized collagen fiber having a complicated cross-sectional shape such as an ellipse, a polygon, or a star is formed. It is also possible to provide a groove or the like. However, it is necessary to consider that it becomes easy to cut | disconnect in extending | stretching.

  In general, the crimping of the fiber is possible by applying a mechanical load such as applying a tensile load or twisting, or folding the fiber or passing between the gears. In the case of solubilized collagen fibers, when the spun solubilized collagen fibers are dried without applying a load, they are suitably crimped by natural shrinkage.

  In the above spinning, a large number of solubilized collagen stretched to 10 dtx or less by winding at a winding speed higher than the discharge speed while discharging into an organic solvent using a showerhead-like nozzle having a large number of discharge holes. A bundle of fibers is formed. This is immersed in a hydrophilic organic solvent to reduce the moisture content of the fiber, and then dried without applying a tensile load to the fiber bundle, whereby a bundle of crimped solubilized collagen fibers is obtained. When the fiber bundle is defibrated while being cut to a length of about 10 mm or more, solubilized collagen cotton is obtained and can be used as a raw material fiber or a raw material material for spinning. When dried by applying a tensile load, a bundle of straight fibers is obtained. In this case, when the fiber bundle is chopped while being cut so that the fiber length is about 2.5 cm or more, it becomes entangled in a cotton shape, as a nonwoven material fiber It can be suitably used.

  FIG. 1 shows an example of a production apparatus for producing solubilized collagen fibers as described above. The manufacturing apparatus 1 includes a first solvent tank 3 that contains isopropanol as an organic solvent S1, a piston tank 5 that contains a solubilized collagen aqueous solution A, and a plurality of solutions for discharging the solubilized collagen aqueous solution into the organic solvent S1. A nozzle 7 having discharge holes, a gear pump 9 for supplying the solubilized collagen aqueous solution A from the piston tank 5 to the nozzle 7, and a winding roll 11 for winding the spun solubilized collagen fiber at a predetermined winding speed. And a second solvent tank 13 containing isopropanol as the hydrophilic organic solvent S2. The piston tank 5 and the nozzle 7 are connected by a plastic conduit via a gear pump 9. In this embodiment, the first solvent tank 3 has an elongated shape having a predetermined length, and the nozzle 7 is installed on one end side in the first solvent tank 3 with the discharge hole directed in the horizontal direction. The collagen aqueous solution discharged from 7 moves horizontally in the organic solvent S1 to the other end side along the length direction of the first solvent tank 3 so that the collagen can contact the solvent for the time required for coagulation of the collagen. Is done.

  In the manufacturing apparatus 1 of FIG. 1, when the piston of the piston tank 5 is pressed with compressed air to operate the gear pump 9, the solubilized collagen aqueous solution A is supplied from the piston tank 5 to the nozzle 7, and from the plurality of discharge holes of the nozzle 7. It is discharged into the organic solvent S1 in the first solvent tank 3. By contact with the organic solvent S1, coagulation proceeds from the outer periphery to the inside of the solubilized collagen to be discharged into fibers, and the collagen fibers are spun into a bundle from the nozzle 7 by extending in the horizontal direction. The The bundle of elongating solubilized collagen fibers F is pulled up from the organic solvent S1 by the take-up roll 11 through the pulley on the other end side of the first solvent tank 3 and taken up. At this time, by setting the take-up speed of the take-up roll 11 to be higher than the discharge speed of the nozzle 7, the solubilized collagen fiber F to be spun is drawn during coagulation and is a fine fiber having an average fineness of 10 dtx or less. It becomes. The stretched bundle of solubilized collagen fibers F is put into the second solvent tank 13 from the take-up roll 11 and immersed in the hydrophilic organic solvent S2, and most of the water remaining in the solubilized collagen fibers F is in the solvent. And the coagulation inside the fiber is completed.

  If the solubilized collagen fiber F having a reduced water content is taken out from the second solvent tank 13 and dried by air drying or vacuum distillation using aseptic air, the solubilized collagen fiber bundle does not adhere to each other. Is obtained. When the bundle of solubilized collagen fibers F is dried without applying a tensile load, crimped solubilized collagen fibers are obtained, and solubilized collagen cotton is obtained by appropriately defibrating after drying. Even when not crimped by applying a load, a solubilized collagen cotton can be obtained by defibrating a fiber bundle having a fiber length of 2.5 cm or more.

  A fiber sheet is produced using the solubilized collagen cotton obtained by the above-described method and the base fiber. When the fiber sheet is brought into contact with an aqueous liquid for cosmetics, the solubilized collagen fibers are quickly dissolved to form a fiber sheet containing the collagen cosmetic, which is used as a pack cosmetic. In the case of a facial mask, the fiber sheet may be provided by cutting appropriately according to the face shape. Since the pack cosmetic of the present invention uses solubilized collagen fibers in the fiber sheet, it has a high water retention ability and is supplied because there is nothing to cover the surface that impedes the water absorption of the base fiber. The aqueous liquid is rapidly absorbed and retained by the base fiber to dissolve the solubilized collagen fiber, and appropriately supplies moisture to the skin. Since a large amount of moisture is retained in the base fiber, even if moisture is vaporized from the fiber sheet on the skin due to body temperature, sufficient moisture retention is maintained.

  When the fiber sheet prepared as described above is used, the entanglement between fibers is weakened when the solubilized collagen fiber is dissolved, depending on the mixing ratio, basis weight, cutting method, etc. of the fiber, and when the used sheet is peeled off from the skin. When the base fiber remains or when the fiber sheet is cut into a face shape, the cut portion of the fiber may become fluffy. In order to improve these, there is a method of introducing a resin binder mainly composed of a low melting point resin insoluble in water into the fiber sheet. Specifically, a part of the base fiber to be used is replaced with a water-insoluble resin binder to produce a fiber sheet containing the resin binder, and this is heated to melt the resin binder. Is heat-sealed to the base fiber to strengthen the bonding. By using a fiber or granular resin binder, it is possible to effectively form a bond by point adhesion and suppress the coating with the resin, so that the base fiber and the solubilized collagen fiber are not substantially shielded by the resin binder. , Bonded by partial adhesion to only part of the substrate fiber. Fibrous resin binders (hereinafter referred to as heat-bonded fibers) are advantageous because they can prevent the fibers from dropping off not only by bonding by fusion but also by entanglement with the base fiber. When the thickness of the heat-fusible fiber is close to that of the base fiber, it is advantageous in terms of an entanglement effect with the base fiber, and is preferably about 0.2 to 3 times the diameter of the base fiber. In particular, when it is about 1.5 times or less the diameter of the base fiber, it is effective to prevent the water supply of the base fiber from being damaged by the coating even if the fusion fiber melts. Fabrication of the fiber sheet using the heat-sealing fiber is a method in which the mixed sheet of the solubilized collagen fiber and the heat-sealing fiber is superposed on the sheet made of the base fiber and bonded and integrated by hot press, A method of heat-sealing a mixed sheet with a heat-fusible fiber to a solubilized collagen fiber sheet, or a method of fusing a heat-fusible fiber between a base fiber sheet and a solubilized collagen fiber sheet, etc. In these cases, both sides of the resulting fiber sheet are produced. The particulate resin binder is directly mixed with the base fiber and the solubilized collagen fiber to form a sheet, sandwiched between the base fiber sheet and the solubilized collagen fiber sheet, or based on a resin binder dispersion or emulsion. The material fiber (cotton or sheet) can be sprayed and dried, and then mixed with the solubilized collagen fiber to form a sheet. When mixing into a fiber with a particulate resin binder, depending on the basis weight of the sheet, it is possible to prevent dropping from the fiber sheet before hot pressing using particles having a size larger than the inter-fiber distance. Consideration is desirable.

  As the low-melting-point resin constituting the resin binder, a thermoplastic resin having a melting characteristic that can be fused by heating to such an extent that collagen does not change is used. Suitable resins include, for example, polyethylene (PE) and polypropylene (PP). , Polyethylene terephthalate (PET), polylactic acid (PLA), PP / PE, PET / PE, PET / PP, acrylic polymer, styrene-butadiene copolymer, vinyl alcohol-acrylic copolymer, vinyl alcohol-ethylene copolymer Examples thereof include, but are not limited to, polyvinyl acetate and acrylonitrile polymer, and can be appropriately selected from various low melting point resins that melt at 150 ° C. or lower.

In the case of a fiber sheet containing a resin binder, the solubilized collagen fiber can be blended up to about 40% by mass of the fiber sheet, and the proportion of the solubilized collagen fiber in the fiber sheet is about 5 to 40% by mass, preferably It sets to about 10-30 mass%. In order to ensure the water retention of the fiber sheet, the base fiber is about 10 to 85% by mass, preferably about 30 to 70% by mass of the fiber sheet. The ratio of the resin binder for preventing fiber fluffing and detachment is about 10 to 80% by mass, preferably about 20 to 50% by mass of the fiber sheet, and the excess resin binder is from the viewpoint of water retention of the fiber sheet. It is not preferable. In terms of retention to the skin surface in the water-holding state, the basis weight of the fiber sheet, 10 to 100 g / ^{m 2,} preferably about adjusted to about 30 to 60 g / ^{m 2.}

  As a method of fusing the resin binder of the fiber sheet, there are a heat press that uses a heating member such as a heat roll and a heating flat plate, a method of supplying hot air, etc. A press is more advantageous. In the case of hot air, since it is necessary to increase the blending ratio of the resin binder, it is necessary to consider the balance between the feel of the sheet and the water absorption.

  When fusing a fiber sheet by hot pressing, it is ideal that only the surface portion of the resin binder melts to form a point bond, and the fiber sheet weight, resin binder composition and blending are so close to this. It is preferable to appropriately adjust the temperature, pressing pressure and pressing time of the heating member according to the ratio. Suitable press conditions vary slightly depending on the type of press and resin, but generally, when pressing with a heated flat plate, the temperature is suitably adjusted within the range of 90 to 150 ° C. and the pressure of 5 to 50 kPa. It is preferable to press at about 130 ° C. and a pressure of about 10 to 30 kPa for about 5 to 10 seconds. When heating is only from one side, it is desirable to heat both sides evenly by repeating the above press. When the heating temperature exceeds 150 ° C., an odor due to collagen alteration occurs. Moreover, in order to prevent the fluff at the time of cutting of a fiber sheet, you may heat a cutting blade or its vicinity.

  When used as a pack cosmetic, the aqueous liquid that dissolves collagen may be a liquid mainly composed of water whose pH in the state in which collagen is dissolved deviates from the isoionic point of collagen. It may be only. However, the solubility in pure water is reduced by the buffering action of the collagen itself, but this point is eliminated by the presence of the electrolyte. By adding a small amount of electrolyte such as acid, base, neutralized salt, buffer salt, etc. Solubility is improved. Particularly, a buffer salt (that is, a salt of a weak acid and a strong base) that stabilizes the pH from weakly acidic to neutral, such as sodium citrate, sodium lactate, and sodium phosphate, is added to the aqueous solution to adjust the pH of the aqueous solution to about 5. When it is set to 5 to 9.0, the solubility of collagen fibers can be stabilized, and collagen fibers having an average fineness of about 10 dtx or less can be easily dissolved within 30 seconds. However, excess salt makes collagen difficult to dissolve in an aqueous solution due to salting-out action. The electrolyte may be contained in the collagen fiber. When a solubilized collagen aqueous solution containing an electrolyte is used in the preparation of the collagen fiber, a solubilized collagen fiber containing the electrolyte is obtained. In this regard, it is acceptable in the present invention to use solubilized collagen in which the salt remains because the desalting after the solubilization treatment is not complete as a raw material.

  In addition, various components that are generally added to cosmetics can be added to the aqueous liquid as needed, as long as they do not hinder the dissolution of collagen in the aqueous liquid. For example, butanediol, pentanediol, glycerol, hyaluron Moisturizers such as acids, preservatives (preservatives) such as methyl p-hydroxybenzoate and phenoxyethanol, plant extracts such as aloe extract, alcoholic solvents such as ethanol, ultraviolet absorbers, vitamins, anti-inflammatory agents, olive oil And various functional components having cosmetic effects. When the ratio of combining the collagen fibers and the aqueous liquid is set so that the collagen content of the resulting cosmetic is about 0.1 to 6% by mass, particularly about 0.1 to 3% by mass, the makeup is uniformly dissolved. It is preferable because the composition can be obtained quickly and acts suitably as a cosmetic.

  According to the requirements of the aqueous liquid described above, commercially available lotions and cosmetic liquids are also included in the aqueous liquid. Therefore, the user can easily prepare a pack cosmetic by selecting a lotion or a cosmetic liquid according to preference and combining it with the fiber sheet. That is, it is possible to provide the user with a collagen pack cosmetic material that satisfies the user's needs in a fresh state as needed, and it can be adjusted to a suitable cosmetic material according to the skin quality of the user. Cold storage like conventional collagen cosmetics is also unnecessary.

  Collagen cosmetics after dissolution are easily denatured in the same way as ordinary aqueous collagen cosmetics, but the spinning of solubilized collagen fibers using alcohol has a bactericidal effect on collagen and is obtained after drying in sterile air Solubilized collagen fibers are not contaminated with bacteria. Moreover, the solubilized collagen in the dry state significantly suppresses the growth of bacteria and fungi compared to the solution state, so that the preservative treatment during distribution can be reduced, and no preservatives, preservatives, etc. are required. Become. Therefore, it can also be used as a pack cosmetic containing almost no ingredients other than collagen.

  The fiber sheet of the present invention can be sold alone as a pack cosmetic, or provided in combination with an aqueous liquid for cosmetics. The amount of time for use can be saved by making the cosmetic aqueous liquid into individual packs at one time or for each usage amount per sheet. A container with a scale indicating the required amount of the aqueous liquid may also be provided.

  Hereinafter, the cosmetic of the present invention and its production will be described in more detail with reference to examples.

<Preparation of aqueous solution of solubilized collagen>
Lime pickles were made from pork salted hides. Specifically, one piece of pork salted hide (about 4 kg) was cut into 3 cm square pieces, and 300% water and 0.6% nonionic surfactant were added to the mass. The skin pieces were washed by stirring and collected. Next, 300% water, 0.6% nonionic surfactant and 0.75% sodium carbonate were added to the skin mass and stirred for 2 hours to recover the skin. Further, after washing the collected skin piece twice with 700% water with respect to the skin piece mass, 300% water, 0.15% nonionic with respect to the skin piece mass. Surfactant, 3.6% sodium hydrosulfide, 0.84% sodium sulfide and 2.4% calcium hydroxide were added and stirred for 16 hours. Washing with 700% water was performed three times.

  8000 g of an aqueous solution containing 6% by mass of sodium hydroxide, 15% by mass of sodium sulfate and 1.25% by mass of monomethylamine was prepared, and 2000 g of the above-mentioned skin pieces (about 500 g as dry mass) were added and mixed with stirring. This was kept at 25 ° C. in a sealed container and incubated for 5 days to solubilize collagen. While the aqueous solution was gently stirred, the alkali in the aqueous solution was neutralized by dropwise addition of an equal amount of sulfuric acid to adjust the pH to 4.8. After the neutralized skin piece was taken out and squeezed to remove the liquid, the mixture was stirred for 30 minutes using about 8000 g of a lactic acid aqueous solution having a pH of 5.0, and then the skin piece was squeezed and dehydrated. This operation was repeated four more times for sufficient desalting. Collagen is solubilized because the skin is adjusted to a pH near the isoionic point of the solubilized collagen at the neutralization stage, but the shape of the skin is hardly dissolved even after desalting. Was holding.

  The collagen content of the skin after desalting is calculated from the result of total nitrogen measurement by the Kieldahl method. Based on this collagen content, the amount corresponding to the collagen mass of 120 g is separated from the skin after desalting, and the collagen concentration Water and sodium lactate were added and kneaded well so that the sodium lactate concentration was 1.2% by mass to obtain 4000 g of a solubilized collagen aqueous solution. Subsequently, the pH was adjusted to 6.7 by adding a small amount of 20% aqueous sodium hydroxide solution and kneading.

<Preparation of solubilized collagen fiber>
In the tank 5 of the manufacturing apparatus 1 having the structure shown in FIG. 1, 4000 g of the solubilized collagen aqueous solution obtained above was stored, and 18 L of isopropanol as an organic solvent was stored in the first solvent tank 3 having a length of 3 m and a width of 10 cm. The gear pump 9 is operated to solubilize a solubilized collagen aqueous solution from the discharge hole (hole diameter: 0.10 mm, hole number: 1000) of the nozzle 7 oriented in the horizontal direction (discharge speed: 4.8 m / min). ) In an organic solvent. A bundle of solubilized collagen fibers spun in isopropanol was wound up at a winding speed of 5 m / min by a winding roll 11 and immersed in a second solvent tank 13 containing 5.0 L of isopropanol.

  The bundle of solubilized collagen fibers in the second solvent tank 13 is pulled up, cut to about 90 cm, blown with sterile air over a horizontal bar, and sufficiently dried under no load, so that the average fineness is 3.7 dtx ( However, 50 g of bundles of solubilized collagen fibers (isoionic point: pH 4.9) on which natural crimps (excluding 10 m at both ends of the fibers) were applied were obtained. In addition, the fineness measured 20 pieces per sample in the environment of 20 degreeC and 65% RH using the fineness meter (DENIEL COMPUTER DC-11A, SEARCH CO. LTD company make), and calculated the average value. The pH of a 0.5 mass% solution in which this solubilized collagen fiber was dissolved in deionized water was 6.8.

  The obtained bundle of solubilized collagen fibers was cut into a length of 35 mm and defibrated using a hand card machine to prepare a solubilized collagen cotton.

  The isoionic point of the solubilized collagen fiber was confirmed as follows.

(Measurement of iso-ion points)
The ratio of the cation exchange resin (Amberlite IPR-120B, manufactured by Organo Corp.) and the anion exchange resin (Amberlite IPA-400, manufactured by Organo Corp.), activated and washed in advance, in a ratio of 2: 5. To prepare a mixed bed ion exchanger. After equilibrating 100 ml of the mixed bed ion exchanger with deionized water, add 50 ml of the sample solution prepared so that the protein concentration becomes 5%, and keep gently in the water bath at 40 ° C. for 30 minutes. The supernatant was separated from the mixture and the pH of the supernatant was measured, and the value was taken as the isoionic point (refer to the method described in JW Janus, AW Kenchington and AGWard, Research, 4247 (1951)) .

<Manufacture of fiber sheet>
(Sample 1)
Using needle punch, solubilized collagen in 100% cotton non-woven fabric (KP cotton gauze, basis weight: 40 g / m ² , manufactured by Kawamoto Sangyo Co., Ltd.) so that the proportion of the solubilized collagen cotton is 10% by mass. Cotton was planted to obtain a fiber sheet with fluffy solubilized collagen fibers.

(Sample 2)
A fiber sheet of Sample 2 was obtained in the same manner as Sample 1, except that the proportion of solubilized collagen cotton was 20% by mass.

(Sample 3)
Using the desalted skin obtained in the preparation of the solubilized collagen aqueous solution, a soluble or less collagen aqueous solution (collagen: 1% by mass, glycerin: 10% by mass) containing glycerin was prepared. Using this aqueous solution, the fiber sheet of Sample 3 was obtained by impregnating and drying the 100% cotton non-woven fabric used in the preparation of Sample 1 so that the solubilized collagen content was 10% by mass.

(Sample 4)
The fiber sheet of Sample 4 was obtained by fuzzing the 100% cotton non-woven fabric by needle punching without using solubilized collagen cotton.

(Sample 5)
Solubilized collagen cotton was planted in the same manner as in Sample 1 except that a commercially available 100% cotton woven fabric (white gauze manufactured by White Cross Co., Ltd.) was used as the base fabric to obtain a fiber sheet.

(Sample 6)
The fiber sheet of Sample 6 was obtained by fuzzing the 100% cotton woven fabric used in Sample 5 with a needle punch without using solubilized collagen fibers.

<Measurement of moisture content>
The following operations were performed using the fiber sheets of Samples 1 to 6 described above and the above-described 100% cotton non-woven fabric (control 1) and 100% cotton woven fabric (control 2) as control fiber sheets.

  The fiber sheet was cut into a shape for an eye pack and stored for 24 hours in a constant temperature and humidity chamber (20 ° C., humidity 65%). Next, take out the fiber sheet, soak in deionized water to the extent that the sheet is sufficiently immersed, pick it up with tweezers, wait 30 seconds for the dripping to settle, spread it on a flat plate without water absorption, place it on a constant temperature The moisture content [%, 100 × (moisture content mass−dry mass) / dry mass] is determined from the dry mass before moisture content of the fiber sheet and the measured moisture content, and stored in a constant humidity chamber. And the change with time was examined. The results are shown in Table 1.

(Table 1)
Change in moisture content of fiber sheet over time
Fiber sheet Dry mass Moisture content (%)
(G) 0 min 10 min 20 min 30 min 40 min 50 min Sample 1 0.066 2203 2112 1991 1885 1794 1703
Sample 2 0.080 2688 2575 2500 2413 2325 2250
Sample 3 0.133 419 366 321 261 223 178
Sample 4 0.062 1771 1658 1561 1481 1384 1271
Sample 5 0.078 1122 1055 954 848 737 632
Sample 6 0.070 753 658 562 475 379 272
Control 1 0.062 1158 1077 981 884 784 674
Control 2 0.068 718 621 529 442 346 240

Apparently from the results in Table 1, the sheet impregnated with the aqueous collagen solution (sample 3) has an extremely low moisture content as compared to the non-collagen-containing non-woven fabric (sample 4, control 1). It can be seen that the rate is reduced and the pack cosmetics cannot perform satisfactory functions. Compared with this, in the case of the sheets (samples 1 and 2) in which the solubilized collagen fibers are implanted, the moisture content is about twice that of the nonwoven fabric, and the moisture content is maintained high over time. Moisturizing function is high, and it is very effective as a pack cosmetic. This is presumably because the solubilized collagen is a fiber, so that the surface of the cotton fiber of the nonwoven fabric does not have a film that inhibits water absorption, and the water absorption and water retention ability of both the nonwoven fabric and the collagen fiber are exhibited. Similarly, when planted on a woven fabric (sample 5), the water absorption and water retention ability are remarkably increased as compared with the case without planting (sample 6, control 2).

(Sample 7)
Using the solubilized collagen cotton prepared in Example 1, solubilized collagen cotton and rayon cotton were put into a carding machine at a ratio of 10% by mass of the solubilized collagen cotton, and uniform mixed fibers I got a sliver. This was subjected to needle punching to dense the fibers to obtain a non-woven fiber sheet having a basis weight of 48 g / m ² .

(Samples 8 and 9)
Sample 2 (solubilized collagen cotton: 20% by mass, 52 g / m ² ) was repeated by repeating the same operation as Sample 5 except that the ratio of solubilized collagen cotton and rayon cotton to be charged into the carding machine was changed. A nonwoven fabric fiber sheet of Sample 9 (solubilized collagen cotton: 27% by mass, 57 g / m ² ) was obtained.

<Composition of cosmetics>
1,2-pentanediol 5.0% by mass, glycerin 5.0% by mass, 1,3-butylene glycol 3% by mass, sodium citrate 0.66% by mass, citric acid 0.03% by mass and the balance being sterilized water An aqueous liquid for cosmetics (pH about 6.6) was prepared.

  The fiber sheets of Samples 5 to 7 were each cut into a 4 cm × 5 cm rectangle, soaked with 2 ml of the above cosmetic aqueous solution, and applied to the skin. After 30 minutes, the fiber sheet was peeled from the skin, and the presence or absence of peeling residue on the skin was examined. As a result, there was no peeling residue in any of the samples, and the peeled sheet kept its shape completely.

(Sample 10)
A bundle of solubilized collagen fibers was produced by repeating the same operation except that the discharged fibers were not taken up in the production of the solubilized collagen fibers of Example 1, and the yields of the obtained fibers were almost the same. However, the average fineness was 10.4 dtx. The obtained bundle of solubilized collagen fibers was cut into a length of 35 mm and defibrated using a hand card machine to prepare collagen cotton.

  Using each of the above-described collagen cotton and the collagen cotton obtained in Example 1 as a sample, using the aqueous cosmetic liquid prepared in Example 2, the time until the solubilized collagen fibers were completely dissolved was measured as follows. did.

  First, 1 g of an aqueous solution was added to 10 mg of solubilized collagen cotton on the palm of the palm and blended with a fingertip to dissolve, and the time until the solubilized collagen sample was completely dissolved was measured. For each sample, the measurement was repeated 5 times, and the minimum value, maximum value, average value, and median value were obtained from the obtained measurement values. As a result, in the collagen cotton of Example 1, the minimum value = 12 seconds, the maximum value = 33 seconds, the average value = 20 seconds, the median value = 17 seconds, and in the collagen cotton of Sample 8, the minimum value = 20 seconds, Maximum value = 62 seconds, average value = 30 seconds, and median value = 23 seconds.

The collagen cotton of Sample 1 and Sample 10 was subjected to a friction test to examine the average friction coefficient and the average deviation of the friction coefficient. In addition, a compression test was conducted to examine the compression work and compression resilience. As a result, in the collagen cotton of Sample 1, the average friction coefficient = 0.1665, the average deviation of the friction coefficient = 0.01015, the compression work = 0.543 N · m / m ² , and the compression resilience = 65.3%. In the collagen cotton of Sample 10, the average friction coefficient = 0.0265, the average deviation of the friction coefficient = 0.176, the compression work = 1.93 N · m / m ² , and the compression resilience = 54.1%.

  From the above results, it is clear that the smaller the fineness of the solubilized collagen fiber, the more flexible the cotton is and the better the touch is, and it can be widely applied to the processing of fiber sheets and a sheet with a good texture can be produced.

(Sample 11)
In the production of the solubilized collagen fiber of Example 1, a sodium sulfate aqueous solution having a concentration of 17 mass% and a pH of about 11 was placed in the first solvent tank 3 instead of isopropanol, and the same operation was repeated to obtain a solubilized collagen aqueous solution. Spinning by coagulation with an inorganic salt. The solidified solubilized collagen fibers are not immersed in the second solvent phase, but are immersed in a crosslinking treatment solution having an epoxy crosslinking agent concentration of 0.3% by mass, a sodium sulfate concentration of 15%, and a pH of 10 to 11 at 25 ° C. for 24 hours. And insolubilized. The insolubilized collagen fibers are taken out, washed with running water, immersed in a surfactant treatment solution to prevent adhesion, and then blown with aseptic air to sufficiently dry, so that the average fineness is 3.7 dtx (however, A bundle of insoluble collagen fibers (excluding 10 m at both ends of the fibers) was obtained. The fiber bundle was twisted and subjected to natural crimping, then cut to about 35 mm and defibrated using a hand cart machine to obtain insoluble collagen cotton.

Using the above-described insoluble collagen cotton and the solubilized collagen cotton obtained in Example 1, the solubilized collagen cotton and the insoluble collagen cotton were put into a carding machine at a ratio of 10% by mass of the solubilized collagen cotton. A uniform mixed fiber sliver was obtained. This was subjected to needle punching to dense the fibers, and a nonwoven fabric fiber sheet having a basis weight of 68 g / m ² was obtained.

  The fiber sheet was cut into a shape for the eye pack and stored in a constant temperature and humidity chamber in the same manner as in Example 1 and then impregnated with deionized water, and the moisture content was examined by mass measurement. As a result, the dry mass was 0.19 g, the moisture content immediately after soaking was 1480%, and the moisture content after 50 minutes was 971%.

(Samples a to k)
According to the blending ratio shown in Table 2, solubilized collagen fibers (6.5 dtx, fiber length 5 cm), heat-sealing fibers (PET, trade name: Melty 4000, manufactured by Unitika Ltd.) and base fibers (R: fineness) A roller card machine (model number: SC-360DR, manufactured by Daiwa Kiko Co., Ltd.) is mixed by mixing 3.2 dtx, short rayon fiber having a fiber length of 5 cm, B: fineness 3.4 dtx, cupra short fiber having a fiber length of 2-4 cm. It was made into a sheet so as to have a basis weight as shown in Table 2, and hot-pressed under the conditions described in Table 2 using a hot press machine (single-sided heating, model number: HP-612CD, manufactured by Hashima Corporation) (in the table) “× 2 times” means that the front and back surfaces were heated one by one by turning over).

  The water absorption, water retention, easiness of drying and strength of the obtained fiber sheet were measured in accordance with the following, and the tactile sensation and dissolution feeling were evaluated by a sensory test. Further, the fiber sheet was cut into a face shape using a cutting machine, and the presence or absence of fluffing in the cut portion was examined. Evaluation was made in three stages: “A”: None, “B”: Slightly present, “C”: Present. . The results are shown in Table 2.

(Water absorption rate)
Cut the fiber sheet to make a test piece, measure the dry mass, soak it in water contained in a container to absorb water, and after 1 minute, pull up the test piece with tweezers and lightly water off the container wall. Then, the mass of the test piece was measured, and the percentage (% by mass) of the absorbed water relative to the dry weight of the fiber sheet was calculated as the water absorption by taking the difference from the dry weight.

(Water retention)
A fiber sheet is cut into 4 cm × 5 cm to prepare a test piece, and after measuring the dry mass, it is immersed in water in a container to absorb water for 10 minutes, and the test piece is lifted from water and held for 10 seconds (falling water) ) To measure the mass. The test piece was returned to water to absorb water again, pulled up from the water, held for 60 seconds (falling water), and then weighed again. The water retention amounts H1 and H2 of the test piece after 10 seconds and 60 seconds were calculated as the difference between the post-falling mass of the test piece and the dry mass, and the falling rate (mass%) = [1- (H2 / H1)]. X100 was calculated and used as a standard for evaluating water retention.

(Ease of drying)
Cut the fiber sheet into 4cm x 5cm, make a test piece, measure the dry mass, soak in water in a container to absorb water for 1 minute, pull up the test piece with tweezers and lightly water on the container wall Was put on a stainless steel dish whose mass was measured in advance, and the mass W0 was measured. Thereafter, the stainless steel petri dish on which the test piece is placed is floated on the water of a constant temperature bath having a water temperature of 35 ° C., and after 10 minutes, the stainless steel petri dish is taken out and wiped off the moisture on the outside, and the mass W1 is measured. ) = [(W1-W0) / W0] × 100 was used as a standard for evaluating the ease of drying.

(Strength)
A fiber sheet is cut into 1.5 cm × 4 cm to prepare a test piece, immersed in water (20 ± 2 ° C.) in a container, and after 3 minutes, the test piece is pulled up with tweezers and placed on Kimwipe (trademark). Then, the test piece was horizontally mounted on a measurement adapter (for food tension) of a rheometer (NRM-2010J-CW, manufactured by Fudo Kogyo Co., Ltd.) so that the water could not be dripped. A tensile load was applied and the sample was pulled at a speed of 6 cm / min. The cutting load (g) at which the top peak was obtained was measured and divided by the basis weight (g / m ² ) to obtain the basis weight per unit area (simple tensile strength).

(Feel)
The feel of the fiber sheet was evaluated by a sensory test with 10 panelists. Evaluation was made into a three-level evaluation of “A”: good, “B”: normal, and “C”: hard.

(Elution feeling)
The slimy feeling due to the eluted collagen when the aqueous cosmetic liquid prepared in Example 2 was included in a fiber sheet and applied to the skin was evaluated by a sensory test with 10 panelists. Evaluation was made into five grades of "-": few, "-": slightly small, "good", "+": somewhat large, "++": many.

(Measurement results and evaluation)
From the results of samples a to f, it can be seen that the use of heat-bonded fibers can suppress fuzz at the fiber sheet cutting part, and the heat-bonded fibers of 20% by mass or more can provide a fiber sheet having suitable strength without fuzz. . The increase in heat-fusible fibers stiffens the tactile feel of the fiber sheet. Factors that affect the tactile feel of the sheet include the type of base fiber (see samples g and h), the basis weight of the sheet and the amount of heat received by the heat press Since there is also a degree of fusion, see sample i), it can be appropriately adjusted according to conditions.

  In the fiber sheet of sample a, when the heating temperature of the hot press was changed to 150 ° C. and the pressure was changed to 30 kPa, fuzz at the cut portion was not seen, but the odor of collagen was generated by heat. For this reason, an increase in heating temperature and pressure promotes thermal fusion, but overheating deteriorates collagen, so it is desirable to set the temperature below 150 ° C.

  The fiber sheets of samples a to k are suitable as the content of solubilized collagen, but the elution feeling may be reduced. This is considered to be because the moisture retention of collagen cannot be fully enjoyed due to water falling due to low water retention. According to Table 2, since the water drop rate of the fiber sheet generally has a correlation with the proportion of the mass of the base fiber, it depends on the material of the base fiber, but the base fiber is blended by about 30% by mass or more. Then, even if the content of solubilized collagen is set to a small value, a fiber sheet having appropriate water retention can be obtained accurately. Since such a sheet does not drip and is difficult to dry, a feeling of use as a pack cosmetic is suitable.

From the above, the blending ratio of each fiber in the fiber sheet composed of the solubilized collagen fiber, the heat-sealing fiber, and the base fiber is 10 to 40 mass of the solubilized collagen fiber from the viewpoint of the sheet shape retention and the moisturizing function after collagen dissolution. From the standpoint of suppressing fluff, about 20% by mass or more of the heat-fusible fiber is appropriate, and about 30% by mass or more of the base fiber is appropriate from the viewpoint of water retention. In terms of the feeling of use as a pack cosmetic, the proportion of solubilized collagen fibers is preferably 20 to 30% by mass.

The schematic block diagram which shows an example of the apparatus for manufacturing the solubilized collagen fiber in this invention.

Explanation of symbols

1 production equipment, 3 first solvent tank, 5 piston tank, 7 nozzle,
9 gear pump, 11 take-up roll, 13 second solvent tank,
S1 organic solvent, S2 hydrophilic organic solvent, A solubilized collagen aqueous solution,
F Solubilized collagen fiber

Claims (7)

An aqueous solution of a solubilized collagen having an isoionic point of 5.0 or less obtained by solubilizing insoluble collagen and a base fiber insoluble in water and water-absorbing is solubilized collagen having a pH of 5.5 to 10.0. A pack cosmetic comprising a fiber sheet made of a solubilized collagen fiber obtained by discharging into a hydrophilic organic solvent as an aqueous solution in a thread form and solidifying into a fiber form. The fiber sheet is a fiber mixture obtained by mixing base fibers (70 mass% to 90 mass%) and solubilized collagen fibers (30 mass% or less to 10 mass% or more) or a nonwoven fabric composed of the fiber mixture. The pack cosmetic according to claim 1 . 3. The pack cosmetic according to claim 2, wherein a part of the base fiber of the fiber sheet according to claim 2 is replaced with a heat-sealing fiber that becomes a resin binder insoluble in water . A pack cosmetic obtained by pressing the fiber sheet according to claim 3 at a temperature of 90 to 150 ° C and a pressure of 5 to 50 kPa for 5 to 10 seconds .           5. The pack makeup according to claim 1, wherein the base fiber is a fiber selected from cotton fiber, hemp fiber, Japanese paper fiber, silk fiber, animal hair fiber, rayon and insoluble collagen fiber. Fee. By supplying the aqueous liquid for pack cosmetics to the fiber sheet according to any one of claims 1 to 5, the aqueous liquid is absorbed and held by the base fiber without being inhibited, and the solubilized collagen fiber is dissolved. A pack cosmetic comprising a solubilized collagen aqueous solution whose pH deviates from the isoionic point of solubilized collagen, and the solubilized collagen is applied to the skin while maintaining moisture retention of the skin . The pack cosmetic according to claim 6, wherein the aqueous liquid contains a buffer salt that stabilizes the pH from weakly acidic to neutral, so that the pH is adjusted to 5.5 to 9.0. .

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