JP4628191B2 - Solubilized collagen fiber, collagen cosmetic, method and apparatus for producing solubilized collagen fiber - Google Patents

Description

  The present invention relates to a solubilized collagen fiber that can prevent denaturation of collagen, which is easily denatured in an aqueous solution state, before use, and can be easily and quickly formulated into an aqueous solution-like cosmetic at the time of use, and a collagen cosmetic to be formulated at the time of use. The present invention relates to a method and an apparatus for producing a solubilized collagen fiber.

  The main protein that forms animal skin, tendon, bone, etc. is collagen. Collagen is a substance in which three polypeptide chains are in a helix, usually in water, dilute acid, dilute alkali, organic solvent, etc. It is insoluble. Generally, it is obtained from the skins of animals such as cows and pigs.

  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. In such applications, collagen is used in the form of an aqueous solution, but most of the collagen contained in the biomaterial is insoluble in water because crosslinks are formed between the molecules, and solubilization treatment is performed. Solubilized collagen obtained by breaking the crosslinks is used.

In the solubilization treatment, alkali or enzyme is allowed to act on insoluble collagen (see Patent Documents 1 and 2 below), and intermolecular or intramolecular cross-linking in the telopeptide at the end of the polypeptide chain of insoluble collagen or the telopeptide itself. It is considered that the binding between peptide chains is eliminated by, for example, cleaving, and solubilized so that a viscous solubilized collagen aqueous solution is obtained.
Japanese Patent Publication No. 44-1175 Japanese Examined Patent Publication No. 46-15033

  However, when used in the cosmetic field as described above, the solubilized collagen aqueous solution has the following drawbacks.

  1) The aqueous collagen solution may be denatured even at room temperature (the helix structure by the three polypeptide chains is dissolved and gelatinized), and temperature control such as refrigeration is required for storage.

  2) It easily rots in a state of a collagen aqueous solution having a high water activity, and rot easily proceeds especially in a neutral aqueous solution used for cosmetics.

  3) Since the aqueous collagen solution has a high viscosity, it tends to cause loss due to adhesion to the surroundings or remaining during filling into a container and is difficult to handle.

  Above all, the above 1) and 2) are extremely disadvantageous as cosmetics because they lower the product quality stability and extremely limit the usable period. Conventionally, it has been dealt with by low-temperature refrigeration distribution, use of special containers to prevent miscellaneous muscle contamination due to inflow of air, addition of preservatives, etc., but users also need refrigerated storage For this reason, handling is troublesome and the quality is often changed.

  The present invention provides a solubilized collagen fiber and a collagen cosmetic that can solve the above-mentioned problems and can easily use the collagen cosmetic in an aqueous solution state without being deteriorated in quality due to collagen denaturation or spoilage. This is the issue.

  Another object of the present invention is to provide a solubilized collagen fiber that can be easily and quickly formulated into an aqueous collagen solution and a method for producing the solubilized collagen fiber and a production apparatus for obtaining the collagen cosmetic. To do.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive research, and as a result, separate solubilized collagen and aqueous liquid in a dry state, and by blending them into a solubilized collagen aqueous solution at the time of use, Collagen denaturation and decay that can easily occur in an aqueous solution can be prevented, and by making the production method solubilized collagen fibers that meet certain requirements, the time required for preparation during use can be greatly reduced. As a result, the present invention has been completed.

  According to one aspect of the present invention, the solubilized collagen fiber is a solubilized collagen fiber for preparing a collagen cosmetic by dissolving in an aqueous liquid, and has an isoionic point of pH 5.0 or less, and an average fineness Is 10 dtx or less, and the gist is that the pH is 5.5 or more when dissolved in deionized water at a rate of 0.5 mass%.

  Moreover, according to one aspect of the present invention, the collagen cosmetic is combined separately with an aqueous liquid having a pH of 5.5 to 9.0 containing a buffer salt that stabilizes the pH from weakly acidic to neutral. A solubilized collagen fiber according to any one of claims 1 to 4, and the collagen content when the solubilized collagen fiber is dissolved in the aqueous liquid is combined at a ratio of 0.01 to 10% by mass. It is a summary.

  Furthermore, according to one aspect of the present invention, a method for producing a solubilized collagen fiber comprises a step of preparing a solubilized collagen having an isoionic point of pH 5.0 or less, the solubilized collagen, and the solubilized collagen fiber. A step of preparing a solubilized collagen aqueous solution having a pH greater than the isoionic point of the collagen, a spinning step of coagulating the solubilized collagen into fibers by discharging the solubilized collagen aqueous solution into an organic solvent in a filament form, and spinning A stretching process in which the solubilized collagen fiber is wound and stretched at a winding speed of 0.6 times or more the discharge speed of the solubilized collagen aqueous solution, and the moisture content of the stretched solubilized collagen fiber is 5% by mass or less. And a drying step of drying the solubilized collagen fibers after the immersion step.

  Furthermore, according to one aspect of the present invention, a device for producing a solubilized collagen fiber includes a spinning means for spinning a solubilized collagen fiber by discharging a solubilized collagen aqueous solution into an organic solvent in a thread shape, and the solubilized collagen fiber. And a solvent tank containing a hydrophilic organic solvent for immersing the stretched solubilized collagen fiber.

  According to the present invention, it is possible to quickly and easily prepare an aqueous collagen cosmetic composition at the time of use, and there is no risk of collagen denaturation and spoilage before use even at room temperature control. Can be provided. It is possible to formulate an optimal collagen cosmetic that meets the needs of each user using commercially available lotion and the like, and it can be widely provided to various users without subdividing product specifications.

  A solubilized collagen aqueous solution prepared by solubilization treatment of insoluble collagen obtained from animal skin becomes a solid dry product when water is removed. The denaturation start temperature of solubilized collagen in aqueous solution is very low. It is around 30 ° C for cows and pigs, and around 20 ° C for fugu, tie, etc., so it can be denatured at room temperature. The temperature is around 100 ° C., and there is no risk of denaturation during normal handling. Further, since the collagen in a dry state has a low water activity unlike an aqueous solution, there is no risk of spoilage. Therefore, if the cosmetic is composed of the cosmetic aqueous medium and the dried solubilized collagen separately, and the solubilized collagen is mixed and dissolved in the aqueous medium at the time of use, it contains collagen that has not been denatured or spoiled. It can be used as a cosmetic.

  In order to suitably use the solubilized collagen dry product as a cosmetic, it is important to dissolve it quickly after mixing with an aqueous medium. The solubilized collagen dry matter differs in ease of dissolution in an aqueous medium depending on the form of the dry matter and the type of solubilization treatment, and in order to dissolve quickly, it is necessary to devise preparation of the solubilized collagen dry matter . In the previous application (Japanese Patent Application No. 2004-121513), the applicant specifies the preparation conditions of a solubilized collagen dry product that dissolves quickly upon mixing, and dissolves the solubilized collagen fibers in an aqueous medium to be used as a collagen cosmetic. Propose to do. The collagen fibers of the prior application are prepared with a fineness of about 20 dtx (grams per 10000 m of fibers), and can be suitably used as a cosmetic by being uniformly dissolved in an aqueous solvent in about several minutes. However, from the user's point of view, it is desirable to shorten the time required for formulating cosmetics before use, and research on collagen dry matter that dissolves faster leads to fineness by devising the production conditions of collagen fibers. It was found that a collagen fiber of 10 dtx or less can be obtained, can be formulated into a uniform cosmetic within 30 seconds, and reaches a level at which dissatisfaction due to the length of the preparation time can be almost eliminated in the sensory test. The dissolution time of the collagen fibers becomes shorter as the fineness decreases, but when it becomes 10 dtx or less, it becomes significantly easier to dissolve. In this invention, it proposes about the ultrafine collagen fiber which can prepare cosmetics quickly, its manufacturing method, and its use as cosmetics.

  Hereinafter, the production of collagen fibers will be described in detail.

  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 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 such as fish as a raw material in connection with 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 5.0 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 salt water or an organic solvent. The freeze-drying method requires a production cost, and the spray-drying method can provide a suitable solubilized collagen powder at a low cost, but the production 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 convert the solubilized collagen aqueous solution into an organic solvent. It has been proposed to prepare collagen fibers by discharging them into threads and solidifying them. In this method, by fibrosis in isopropanol, the lipid is eluted from solubilized collagen containing a large amount of lipid (for example, collagen derived from pig skin contains 23.1% by mass of lipid per solid content). It is excellent in that the amount of lipid can be reduced to less than 0.1%, and is extremely useful when compared with the fact that lipid cannot be removed when fiberized in salt water using salting out coagulation. However, in the method of the previous application, there is a limit in forming thinner collagen fibers, and it is difficult to produce fibers of 10 dtx or less. In addition, when producing a fine collagen fiber having a fineness of about 10 dtx, there is a problem that when the fiber is dried, the fibers adhere and fuse together to form a lump. In this application, the manufacturing method with which the fine collagen fiber whose fineness is 10 dtx or less can be obtained simply is proposed. In this production method, it is possible to produce fine collagen fibers having a fineness of 10 dtx or less by drawing solubilized collagen fibers to be spun during coagulation. Furthermore, by adding a step of immersing the spun collagen fibers in a hydrophilic organic solvent before drying, residual water in the collagen fibers can be removed while preventing the collagen fibers from being dried. Hereinafter, the manufacturing method of a solubilized collagen fiber is demonstrated.

  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 water content is about 15% by mass or less, preferably 10% by mass or less. When the water content is high, the collagen does not coagulate suitably.

When the solubilized collagen aqueous solution is discharged into an organic solvent and solidified using a nozzle or the like, the collagen is formed into a fiber (that is, spun). 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 0.05 to 1 mm. The average fineness is about 10 to 100 dtx (value measured at 20 ° C. and 65% RH using a fineness meter) by discharging into an organic solvent through a hole of about 0.05 to 0.3 mm. Solubilized collagen fibers are formed. The thickness of the 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 When the nozzle hole diameter is too small, the liquid flow resistance increases and an excessive discharge pressure is applied to the nozzle. Moreover, the collagen fibers spun free from the nozzle shrink in the length direction of the fibers during coagulation, and the length becomes less than about 0.6 times, and the fineness becomes higher than when discharging, The method of reducing the nozzle hole diameter or reducing the concentration of the collagen aqueous solution has a limit in reducing the fineness. As a method for solving this, there is a method in which collagen fibers spun in a solvent are wound up at a speed of about 0.6 times or more the discharge speed. As a result, the fiber is stretched against contraction in the fiber direction by the pulling force applied to the collagen fiber being spun, and a thin fiber of 10 dtx or less can be prepared. However, since the fiber is cut when the winding speed is too high, the ratio (draft) of the winding speed to the discharge speed is adjusted to 1.5 or less and stretched. Taking these into consideration, the preferred conditions for spinning collagen fibers having an average fineness of 10 dtx or less are as follows: the concentration of the aqueous collagen solution is 3 to 7% by mass, preferably 3.5 to 5% by mass, and the nozzle hole diameter is 0.05 to It is about 0.18 mm, preferably about 0.09 to 0.11 mm, and the draft can be 0.6 or more and 1.5 or less, preferably 1.0 to 1.2. In such a range, the formula: T = 100 · r ² cd / D (where T is the fineness (dtx), r is the nozzle hole radius (mm), C is the concentration (mass%) of the collagen aqueous solution, and d is Each condition can be set based on the specific gravity of collagen (g / ml) and D indicates a draft). 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 fiber is aseptically dried by air drying or vacuum distillation using aseptic air to remove residual water, and a solubilized collagen fiber that can be suitably used for cosmetics is obtained. In the case of thin fibers, when they are dried in a state where the fibers are in contact with each other, they adhere to each other and bind to each other, and actually become a fiber mass. This is because the residual moisture in the collagen fiber redissolves the coagulated collagen due to the organic solvent first evaporating during drying. The thinner the fiber, the more noticeable the adhesion. In order to prevent this, in the present application, the solubilized collagen fibers before drying are immersed in a hydrophilic organic solvent. By contacting with the hydrophilic organic solvent, the moisture in the collagen fibers is diffused into the organic solvent and replaced with the organic solvent, so that the water content is reduced and the amount of the organic solvent is increased. Thus, fiber adhesion 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 during the drying of collagen fibers, it is effective to use a solvent having a boiling point close to that of water, or a solvent azeotropic with water. Isopropanol etc. are mentioned. 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 centrifugal dehydrating the solubilized collagen fiber immediately before dipping in the organic solvent is effective in reducing the exchange frequency of the dipped organic solvent.

  Solubilized collagen fibers obtained by dipping in an organic solvent and then drying contain about 10 to 20% by mass of water even in the standard state (20 ± 2 ° C., humidity 65 ± 2%), but the denaturation temperature is high, and the cow In pig-derived collagen, the temperature is around 100 ° C.

  The closer the pH of the solubilized collagen fiber is to the pH of the aqueous liquid used to prepare the cosmetic, the easier it is to dissolve in the aqueous liquid. Therefore, it is desirable that the pH of the solubilized collagen aqueous solution used for spinning is close to the pH of the cosmetic aqueous solution. In general, since cosmetics are weakly acidic to neutral, considering this, it is preferable that the pH of the solubilized collagen aqueous solution is higher than the isoionic point, and when adjusted to a pH of 5.5 or higher, the spun collagen fibers are Since it dissolves quickly in commercially available lotions and serums, collagen can be easily blended into cosmetics that are optionally used by users. About the upper limit of the pH of the solubilized collagen aqueous solution, it is sufficient that the pH of the cosmetic does not exceed 9.0 when the collagen fiber is finally dissolved in an aqueous solvent to form a cosmetic. However, in order to reduce the pH variation of the cosmetics due to the addition of collagen fibers, the pH is preferably 8.0 or less. When the alkali used for adjusting the pH of the spinning collagen aqueous solution is only NaOH, the viscosity of the solubilized collagen aqueous solution tends to increase. The increase in viscosity makes it difficult to feed liquid from the tank containing the aqueous collagen solution to the nozzle, and to pass through the nozzle when discharging the aqueous collagen solution from the small-diameter hole as described above. In this regard, it is preferable to add an inorganic salt such as sodium sulfate or an organic acid salt such as sodium lactate to adjust the pH because an increase in viscosity is suppressed. 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, It remains inside the fiber or adheres in powder form when the collagen fiber is dried. This point is solved by using a salt that is soluble in an organic solvent. Specifically, by using alcohol as an organic solvent for spinning and using a salt that dissolves in alcohol such as sodium lactate 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.

  Since the solubilized collagen fiber produced according to the above-described production method is thin, the solubility in water is very good, and the dissolution rate in an aqueous liquid when used as a cosmetic is dramatically improved. In the range where the average fineness is about 10 dtx or less, dissolution (uniform dispersion) is possible within 30 seconds. Therefore, it is preferable to spin an aqueous collagen solution adjusted to pH 5.5 or more, preferably about pH 5.5 to 10.0, more preferably about pH 6.5 to 8.0. Solubilized collagen fibers spun from a solubilized collagen aqueous solution 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). This is different from the case of spinning from a collagen aqueous solution having a pH lower than the isoionic point of the solubilized collagen (when the fiber is dissolved, the pH becomes 4.0 to 4.5), so only the dissolution rate in water near neutrality is obtained. And can be easily distinguished by the pH when dissolved.

  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.

  Thin collagen fibers with an average fineness of about 10 dtx or less have troubles such as troublesome collection of spilled fibers when they are in the short fiber state, but they are easy to handle when they are cottony lumps. , And can be easily performed. In order for the collagen fiber to become cottony, it is important that the fiber has a length of a certain length or more, or that entanglement is imparted by crimping. The length of non-crimped collagen fibers capable of forming collagen cotton is about 2.5 cm or more. However, in consideration of weighing accuracy at the time of separation, it is 10 cm or less, preferably 3.5 cm or less. In the case of a crimped fiber, it is cotton-like even if it is quite short, and it is sufficient that the length is at least 10 mm. In order to form an easy-to-handle collagen cotton, the collagen fibers need only be naturally crimped, and the crimp rate is preferably about 5 to 20%. When the spun solubilized collagen fiber is dried without tension and without tension, the collagen fiber is crimped by natural crimping and can be suitably crimped. When dried under a tensile load, the fibers become straight with no crimp, and the dried collagen fibers are subjected to mechanical bending such as twisting the fibers, passing the fibers between gears, or between the gears. It can also be crimped by adding.

  Collagen cotton, in which fine collagen fibers with an average fineness of about 10 dtx or less are loosely entangled, is smooth with little friction, is highly flexible, and has a high recovery force against compression, so that it is extremely tactile. As the fineness of the fibers constituting the cotton increases, the friction increases and the flexibility and the resilience to compression also decrease.

  One embodiment of a production method capable of easily producing collagen cotton will be described below.

  First, a solubilized collagen aqueous solution is prepared according to the above, and in spinning, by using a showerhead-like nozzle having a large number of discharge holes, winding at a winding speed higher than the discharge speed while discharging into an organic solvent, A bundle of many solubilized collagen fibers drawn to 10 dtx or less is formed. This is dipped 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. The fiber bundle is defibrated while being cut to an appropriate length to obtain a solubilized collagen cotton.

  Alternatively, in the production of the above-described solubilized collagen cotton, drying can be performed while applying a tensile load to obtain a bundle of straight fibers, and the fiber bundle can be defibrated while cutting so that the fiber length is about 2.5 cm or more. Good. Even collagen fibers of the same thickness are dissolved in an aqueous solvent faster than those defibrated in a cotton form than those in a fiber bundle.

  Since the obtained solubilized collagen cotton can be easily separated as necessary, it may be provided as a cotton lump as a product. However, if it is individually packaged in units of about 10 mg as a single use, it is easy and clean. It is easy to use and has good portability.

  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 example, 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 aqueous collagen solution discharged from the organic solvent S1 is configured to be able to move horizontally in the organic solvent S1 along the length direction of the first solvent tank 3 to the other end side.

  In the manufacturing apparatus 1 of FIG. 1, when the piston of the piston tank 5 is pressed by compressed air and the gear pump 9 is operated, the solubilized collagen aqueous solution A is supplied from the piston tank 5 to the nozzle 7. It is discharged from the hole into the organic solvent S1 in the first solvent tank 3. By contact with the organic solvent S1, coagulation proceeds from the outer peripheral surface of the discharged solubilized collagen toward the inside and the fiber is made into a fiber while extending in the horizontal direction, whereby a plurality of collagen fibers are spun into a bundle from the nozzle 7. Is done. The bundle of elongating solubilized collagen fibers F is pulled up from the organic solvent S <b> 1 via the pulley on the other end side of the first solvent tank 3, and taken up by the take-up roll 11. At this time, by setting the take-up speed of the take-up roll 11 to be equal to or higher than the discharge speed of the nozzle 7, the solubilized collagen fiber F to be spun is stretched during coagulation and the fine fiber having an average fineness of 10 dtx or less. It becomes. It takes a certain amount of time to solidify the collagen, and it is desirable to maintain contact with the organic solvent at least while the outer periphery solidifies, that is, during spinning and stretching. The time required for coagulation varies depending on the fineness of the fiber to be spun, but in the case of the solubilized collagen fiber of the present invention, it is generally about 8 seconds, and the contact between the collagen fiber being spun and the organic solvent S1 is maintained during this time. Thus, the dimensions of the first solvent tank 3 are set. For example, when the winding speed is about 5 m / min, the length of the first solvent tank is about 70 cm or more.

  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 fibers do not adhere to each other and can be formulated into a cosmetic. Solubilized collagen fibers that can be suitably used are obtained. At this time, if 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 the fiber is not crimped by a tensile load, if the fiber length is 2.5 cm or more, there is entanglement, and a solubilized collagen cotton can be obtained by defibration of a fiber bundle having an appropriate length.

  As the solubilized collagen fibers are spun, the water content of the organic solvent S1 and the hydrophilic organic solvent S2 increases. Therefore, the water content is maintained below a predetermined value by replacing the organic solvent S1 and the hydrophilic organic solvent S2 with new solvents. There is a need to. The solvent exchange may be performed using a pump or the like, but can be automated by controlling supply and discharge of the solvent to the solvent tank using a measurement device and a drive control device that detect the moisture content of the solvent. Further, the water in the solubilized collagen fiber F pulled up from the first solvent tank 3 is slightly discharged out of the fiber when it is pressed against the take-up roll 11 as it is stretched, but the take-up roll 11 and the second solvent Since a pressing means such as a roller is provided between the tank 13 and the solubilized collagen fiber F is lightly squeezed, it can be further removed, so that the increase in water content of the hydrophilic organic solvent S2 in the second solvent tank 13 is alleviated and the frequency of solvent exchange Can be reduced.

  In addition, when the organic solvent S1 in the first solvent tank 3 is gently flowed at a constant speed, the diffusion of water from the collagen aqueous solution is stabilized, and the homogeneity of the spun fibers is improved. For example, the organic solvent is supplied / discharged using a pump or the like so that the organic solvent S1 flows at a constant speed in the forward direction or the reverse direction with respect to the discharge direction of the collagen aqueous solution, and the organic solvent discharged from the first solvent tank 3 If it comprises so that it may return to the 1st solvent tank 3 after removing water in a filtration membrane etc., stable spinning can be performed continuously. Furthermore, as a modification of the above-described embodiment, instead of spinning in a solvent tank, it is also possible to perform spinning in which an organic solvent is sprayed and solidified on a solubilized collagen aqueous solution discharged from a nozzle. However, when a force in a direction crossing the ejection direction is applied to the collagen aqueous solution, the spinning collagen fibers are cut, so it is necessary to pay attention to the spraying direction and spraying form of the organic solvent so as not to cut the fibers.

  If the solubilized collagen cotton obtained by the above-mentioned method is brought into contact with and mixed with an aqueous liquid for cosmetics, it quickly dissolves into a collagen cosmetic. The aqueous liquid may be a liquid mainly composed of water such that the pH in a state in which collagen is dissolved deviates from the isoionic point of collagen, and may be basically only water. 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 5 to 9.0, the dissolution 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, and when the collagen fiber is prepared using the solubilized collagen aqueous solution containing the electrolyte, the 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 and urea, 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 And oils and fats such as olive oil, fatty acids and the like, and various functional ingredients 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 0.01 to 10% 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 above-mentioned aqueous liquid, commercially available lotions and cosmetic liquids are also included in the aqueous liquid, and the solubilized collagen fibers and cotton in the present application dissolve quickly in the commercially available lotions and cosmetic liquids. Therefore, the user can easily prepare a collagen cosmetic by selecting a lotion or a cosmetic liquid according to his / her preference and combining it with collagen fibers or cotton. In other words, it is possible to provide the user with a collagen cosmetic material that satisfies the user's needs in a fresh state as needed, and it can be formulated into a suitable cosmetic material according to the skin quality of the user. Cold storage as in conventional collagen cosmetics is also unnecessary, and the time required for preparation of the cosmetics is short, so there is no time limit for use and it can be used in a timely manner according to the needs of the user.

  The collagen cosmetic after being dissolved is easily denatured like a normal collagen cosmetic in an aqueous solution state. However, since the treatment using alcohol as the organic solvent in the preparation of the solubilized collagen fibers described above has a bactericidal effect on collagen, the solubilized collagen fibers obtained by drying with sterile air are not contaminated with various bacteria. In addition, the solubilized collagen in the dry state can significantly reduce the growth of bacteria and fungi compared to the solution in the solution state, so that the preservative treatment during distribution can be reduced. Therefore, it is also possible to use cosmetics that hardly contain components other than collagen such as preservatives.

  Furthermore, since the aqueous liquid for cosmetics is separated from highly nutritive collagen, the amount of preservatives can be reduced and the preservative treatment can be reduced. In addition, since the aqueous liquid is easier to sterilize than collagen, it is not necessary to add a preservative by sterilizing the aqueous liquid and filling it aseptically.

  The solubilized collagen fiber or cotton of the present invention can be sold alone or can be provided by being enclosed in a separate container together with an aqueous cosmetic liquid. By packaging each use amount, it eliminates the need for weighing during use, so it is provided by encapsulating one solubilized collagen fiber or cotton in a container with a scale indicating the required amount of aqueous liquid. In this case, the measurement when the user prepares the cosmetic using a lotion or the like is simple, and a suitable cosmetic is always obtained. In addition, when an aqueous liquid and solubilized collagen fiber or cotton are individually sealed in a soft container having two storage compartments that are interrupted by a partition piece that can be broken by applying light force, the partition piece is broken to break these pieces. Can be dissolved by contacting and mixing, so that it can be used easily and there is no need to adjust the mixing ratio.

  Below, the cosmetics of this invention and its manufacture are demonstrated in detail with reference to an Example.

  A sample of solubilized collagen fiber was prepared according to the following, and the time required for dissolution was measured. 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, the pH of the supernatant was measured, and the value was taken as the isoionic point (see the method described in JW Janus, AW Kenchington and AG Ward, Research, 4247 (1951). did).

(Sample 1)
<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 in a sealed container at 25 ° C. 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. The neutralized skin piece was taken out and squeezed to remove the liquid. After stirring for 30 minutes using about 8000 g of a lactic acid aqueous solution having a pH of 5.0, 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.

<Manufacture of solubilized collagen fibers>
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, applied to a horizontal bar, blown with aseptic air in a state where no tension is applied under no load, and the average fineness is reduced. A bundle of solubilized collagen fibers having natural crimps at 3.7 dtx (excluding 10 m at both ends of the fiber) was obtained (isoionic point: pH 4.9). 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 of this solubilized collagen fiber dissolved in deionized water was 7.1. Further, the amount of lipid in the solubilized collagen fiber was measured according to the hexane extraction method of JIS K6503: (2001) 5.6 “Oil and Fat” and found to be less than 0.1% by mass.

<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.

  Cut the above-mentioned bundle of solubilized collagen fibers into a length of 35 mm, partly defibrate them using a hand card machine to prepare collagen cotton, and each of the fiber bundles and cotton as collagen samples, Used in the preparation of cosmetics.

  On the palm of the hand, 1 g of the above aqueous solution was added to 10 mg of collagen sample and dissolved by fingertips, and the time until the collagen sample was completely dissolved was measured. About each sample, measurement was repeated 5 times and the minimum value, the maximum value, the average value, and the median value were calculated | required from the obtained measured value. The results are shown in Table 1.

(Sample 2)
In the preparation of the solubilized collagen aqueous solution of Sample 1, the amount of added water was changed to adjust the collagen concentration to 5.1 mass%, the pH of the solubilized collagen aqueous solution was adjusted to pH 6.9, and the production of the solubilized collagen fibers A bundle of solubilized collagen fibers was produced by repeating the same operation as Sample 1 except that the draft (ratio of the winding speed to the discharge speed) was changed to 0.60, and the yield of the obtained fibers was almost the same. However, the average fineness was 7.3 dtx. The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 7.3.

  A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, The time until the collagen sample was completely dissolved was measured in the same manner as Sample 1 in the preparation of cosmetics. The results are shown in Table 1.

(Sample 3)
In the production of the solubilized collagen fiber of Sample 2, the same operation as Sample 2 was performed except that the nozzle hole diameter was 0.05 mm and the draft (ratio of winding speed to discharge speed) was changed to 0.64. When a bundle of solubilized collagen fibers was repeatedly produced, the yield of the obtained fibers was almost the same, but the average fineness was 2.5 dtx. The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 7.3.

  A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, The time until the collagen sample was completely dissolved was measured in the same manner as Sample 1 in the preparation of cosmetics. The results are shown in Table 1.

(Sample 4)
In the preparation of the solubilized collagen aqueous solution of Sample 1, the amount of added water was changed to adjust the collagen concentration to 5.0%, and the pH of the solubilized collagen aqueous solution was adjusted to pH 7.1. When the bundle of solubilized collagen fibers was produced by repeating the same operation except that the fibers were not wound up, the yield of the obtained fibers was almost the same, but the average fineness was 10.4 dtx. The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 7.5.

  A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, The time until the collagen sample was completely dissolved was measured in the same manner as Sample 1 in the preparation of cosmetics. The results are shown in Table 1.

(Sample 5)
The same procedure was repeated except that the nozzle was changed to one having a hole diameter of 0.18 mm (number of holes: 700) in the production of the solubilized collagen fiber of Sample 4, and the bundle of solubilized collagen fibers was not wound up. Was produced, the yield of the obtained fibers was almost the same, but the average fineness was 22.4dtx. The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 7.5.

  A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, The time until the collagen sample was completely dissolved was measured in the same manner as Sample 1 in the preparation of cosmetics. The results are shown in Table 1.

(Sample 6)
In the preparation of the solubilized collagen aqueous solution of Sample 1, the amount of water added to the solubilized collagen was reduced to reduce the collagen concentration to 6 mass% (pH: 6.7, sodium lactate content: 1.6 mass) %).

  Using the above-described solubilized collagen aqueous solution, the solubilized collagen fibers were discharged in the same manner as Sample 5 without discharging the solubilized collagen aqueous solution from a nozzle having a hole diameter of 0.25 mm (hole number: 700). When the bundle was manufactured, the yield of the obtained fibers was almost the same, but the average fineness was 41 dtx. The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 6.9.

  A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, The time until the collagen sample was completely dissolved was measured in the same manner as Sample 1 in the preparation of cosmetics. The results are shown in Table 1.

(Table 1)
Time required for dissolution of solubilized collagen (seconds)
Minimum value Maximum value Average value Median value
Sample 3 (2.5dtx)
Fiber bundle 10 12 11 11
Cotton 8 12 10 11
Sample 1 (3.7 dtx)
Fiber bundle 15 33 21 18
Cotton 12 33 20 17
Sample 2 (7.3dtx)
Fiber bundle 27 33 30 30
Cotton 18 23 21 22
Sample 4 (10.4dtx)
Fiber bundle 37 80 51 40
Cotton 20 62 30 23
Sample 5 (22.4dtx)
Fiber bundle 85 195 139 144
Cotton 62 116 93 88
Sample 6 (41.0dtx)
Fiber bundle − − − −
Cotton − − − −

In Sample 6, neither the fiber bundle nor cotton was completely dissolved in the aqueous liquid within 5 minutes, and a suitable cosmetic was not obtained.

  In any case of fiber bundles and cotton, when the fineness of the solubilized collagen fiber is reduced, the time required for dissolution is drastically reduced. However, in the range larger than 10 dtx, the time required for dissolution differs between the fiber bundle and cotton, and the difference decreases as the fineness decreases, and at 10 dtx or less, there is almost no difference between the fiber bundle and cotton. That is, solubilized collagen fibers of 10 dtx or less quickly dissolve even in a fiber bundle that is not defibrated. Comparing this result with the sponge collagen described in Japanese Patent No. 2840954, it is clear that the dissolution time of the solubilized collagen fibers is extremely short in this application.

(Sample 7)
In the production of the solubilized collagen fiber of Sample 1, solubilization is performed by repeating the same operation except that a weight is applied to both ends of the bundle and a tensile load is applied when drying the fiber bundle pulled up from the second solvent tank. A bundle of collagen fibers was obtained. The obtained solubilized collagen fibers were straight fibers without crimps.

  The obtained bundle of solubilized collagen fibers was cut to a length of 10 to 35 mm, and the cut fiber bundles were each defibrated using a hand card machine to prepare collagen cotton.

  Each of the obtained collagen cottons was once stored in a sachet and then taken out again to examine the presence or absence of fibers (loss) remaining in the sachet. In addition, as an index of ease of grouping, the presence or absence of fiber waste when collagen cotton was handled was examined. The results are shown in Table 2.

(Sample 8)
A solubilized collagen fiber bundle was obtained by the same operation as Sample 1. This fiber bundle was cut into a length of 30 mm and defibrated using a hand card machine to prepare collagen cotton.

  The obtained collagen cotton was examined in the same manner as in Sample 7 for the loss of fiber and the loss of fiber waste. The results are shown in Table 2.

(Table 2)
State of solubilized collagen cotton
Fiber length Fiber loss Waste removal Appearance
Sample 7
10mm Yes Yes Near fiber scrap 15mm Yes Yes Near fiber scrap 20mm Yes Yes Near fiber scrap 25mm Yes Almost none Orientation tends to be biased 30mm Yes Almost none Orientation tends to be biased 35mm Yes No Orientation easily biased sample 8
30mm almost none none flexible cotton

According to Table 2, in the case of a straight collagen fiber that does not crimp, if the fiber length is 20 mm or less, the appearance is close to fiber waste, and since it has low entanglement, it is easy to fall off, and it is difficult to form good cotton. It turns out that it is better to make the fiber length 25 mm or more in order to process straight fibers into easy-to-handle cotton. Since the crimped collagen fiber has entanglement properties, it is easy to form soft and swollen cotton, and the lower limit of the fiber length that makes good cotton is shorter than that of a straight fiber.

  For collagen cotton made of solubilized collagen fibers with a fiber length of 30 mm prepared in Sample 8 of Example 2, using a commercially available lotion or cosmetic liquid as an aqueous cosmetic liquid, the same as in Example 1 The cosmetic preparation was prepared by the method, the time required for dissolving the collagen cotton was measured, and the solubility in the skin lotion and the cosmetic liquid was examined. The results are shown in Table 3. In the solubility in the table, “A” indicates that the median time required for dissolution is 20 seconds or less, and “B” indicates that it exceeds 20 seconds and is 30 seconds or less.

(Table 3)
Solubility in skin lotion and serum
Product pH Solubility pH after dissolution
Lotion 1 4.52 B 5.46
Lotion 2 5.34 B 6.19
Lotion 3 5.75 A 5.87
Lotion 4 5.80 A 5.84
Lotion 5 5.82 A 5.93
Lotion 6 6.10 A 6.36
Lotion 7 6.10 A 6.20
Lotion 8 6.40 A 6.46
Lotion 9 6.45 A 6.60
Lotion 10 6.58 A 6.60
Lotion 11 6.70 A 6.81
Lotion 12 7.22 A 7.16
Lotion 13 7.70 A 7.55
Lotion 14 7.97 A 7.95
Essence 1 5.90 B 6.77
Essence 2 6.10 A 6.40
Essence 3 6.13 B 6.51

As can be seen from Table 3, collagen cotton dissolves quickly in both commercial lotions and serums in the pH range of 4.5 to 8.0. However, although the lotion 1 and the lotion 2 having low pH did not become transparent, there was no problem in practical use in a uniformly dispersed state.

(Sample 9)
<Preparation of aqueous solution of solubilized collagen>
As in Sample 1, the salted skin of pigs was cut into pieces and lime pickled. The obtained skin piece was applied to a chopper having a pore diameter of 16 mm, and then made into a paste with a grinder (mass colloider, manufactured by Masuko Sangyo Co., Ltd.). The pasty pig skin was degreased with ethanol and dried. An amount of 100 g was separated from the dried product, 1900 g of deionized water was added, and hydrochloric acid was added while stirring with a mixer to adjust the pH to 3.0. To this, 20 g of acidic protease preparation (Denapsin 2P, manufactured by Nagase ChemteX Corporation) was added, and the mixture was stirred at 25 ° C. for 24 hours to solubilize collagen. 2N sodium hydroxide is added to the obtained solubilized collagen aqueous solution to adjust the pH to 9 to 10, and then 40 g of succinic anhydride is dissolved in acetone and added to adjust the pH to 9 to 10 at 10 ° C. The reaction (succinylation) was carried out for 2 hours. After completion of the reaction, the pH of the reaction solution was adjusted to 4.5 using hydrochloric acid to precipitate collagen. This was centrifuged at 3000 G for 10 minutes to collect the precipitate, washed with ethanol and dried to obtain a succinylated dried solubilized collagen. A portion of 60 g is separated from this dried product, and 29 g of sodium lactate and 1920 g of water are added and stirred, solubilized collagen aqueous solution (pH 6.8, sodium lactate concentration: 1.2% by mass) with a collagen concentration of 4.5% by mass. )

<Manufacture of solubilized collagen fibers>
When a solubilized collagen fiber was produced using the above-described solubilized collagen aqueous solution by the same apparatus and operation as in Sample 1, 50 g of bundles of solubilized collagen fibers having an average fineness of 4.1 dtx (isoionic point: pH 4.5) ) The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 7.2.

<Composition of cosmetics>
A bundle of solubilized collagen fibers obtained is cut into a length of 35 mm, a part thereof is defibrated using a hand card machine to prepare collagen cotton, and each of the fiber bundle and cotton as a collagen sample, In the same manner as in Example 1, it was used for the preparation of cosmetics, and the time until the collagen sample was completely dissolved was measured. As a result, the median value of the five measurements was 20 seconds (fiber bundle) and 19 seconds (cotton).

(Samples 10 and 11)
<Preparation of aqueous solution of solubilized collagen>
The collagen concentration was 4.4% by mass, sodium lactate, except that the pH of the solubilized collagen aqueous solution was adjusted to pH 4.0 (Sample 10) or pH 7.8 (Sample 11). A solubilized collagen aqueous solution having a concentration of 1.2% by mass was obtained.

<Manufacture of solubilized collagen fibers>
When the solubilized collagen fiber was produced using the above-described solubilized collagen aqueous solution in the same manner as Sample 1, 50 g of bundles of solubilized collagen fibers having an average fineness of 3.7 dtx (isoionic point: pH 4.9) was obtained.

<Composition of cosmetics>
Using the obtained bundle of solubilized collagen fibers, a fiber bundle and cotton were prepared in the same manner as in Sample 1, and each time was measured until it was completely dissolved in the aqueous cosmetic liquid. In Sample No. 11, the sample was not dissolved within 5 minutes, and in Sample 11, it was 19 seconds (fiber bundle) and 10 seconds (cotton) (median value). The pH of the 0.5 mass% solution in which the solubilized collagen fibers of Sample 10 were added to deionized water and dissolved over time was 4.2. The pH of a 0.5 mass% solution of sample 11 in which the solubilized collagen fibers were dissolved in deionized water was 8.2.

(Sample 12)
<Preparation of aqueous solution of solubilized collagen>
The solubilized collagen aqueous solution prepared in the same manner as Sample 1 was subjected to succinylation in the same manner as Sample 9 except that the pH was adjusted to 4.0 with hydrochloric acid after the succinylation reaction to obtain a dried succinylated collagen. After adding water and sodium lactate, a small amount of lactic acid is added to adjust pH, solubilized collagen aqueous solution having a collagen concentration of 4.5% by mass (pH 5.5, sodium lactate concentration: 1.2% by mass) Got.

<Manufacture of solubilized collagen fibers>
When the solubilized collagen fiber was produced using the above-described solubilized collagen aqueous solution by the same apparatus and operation as in Sample 1, 50 g of bundles of solubilized collagen fibers having an average fineness of 4.0 dtx (isoionic point: pH 4.0). ) The pH of a 0.5 mass% solution of this solubilized collagen fiber dissolved in deionized water was 5.5.

<Composition of cosmetics>
Using the obtained bundle of solubilized collagen fibers, fiber bundles and cotton were prepared in the same manner as in Example 1, and each of the time until complete dissolution in the aqueous cosmetic liquid was measured. Second (fiber bundle) and 10 seconds (cotton) (median).

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 (10)

A solubilized collagen fiber for preparing a collagen cosmetic by dissolving in an aqueous liquid, having an isoionic point of pH 5.0 or less, an average fineness of 10 dtx or less, and 0.5% by mass in deionized water Solubilized collagen fiber having a pH of 5.5 or more and 10.0 or less when dissolved at a ratio of   The solubilized collagen fiber according to claim 1, wherein the average fiber length is 2.5 cm or more.   The solubilized collagen fiber according to claim 1 or 2 having crimps.   The solubilized collagen fiber according to any one of claims 1 to 3, which is entangled in cotton.   The solubilized collagen fiber according to any one of claims 1 to 4, which is combined with an aqueous liquid having a pH of 5.5 to 9.0 containing a buffer salt that stabilizes the pH from weakly acidic to neutral. And a collagen cosmetic that is combined at a ratio of 0.01 to 10% by mass when the solubilized collagen fiber is dissolved in the aqueous liquid. A step of preparing a solubilized collagen having an isoionic point of pH 5.0 or less, a step of preparing a solubilized collagen aqueous solution containing the solubilized collagen and having a pH of 5.5 to 10.0, and the solubilized collagen A spinning process in which an aqueous solution is discharged into an organic solvent in the form of a thread to solidify and solubilize solubilized collagen; A stretching step of winding and stretching at a speed, a step of immersing the stretched solubilized collagen fiber in a hydrophilic organic solvent having a water content of 5% by mass or less, and drying for drying the solubilized collagen fiber after the soaking step And a process for producing a solubilized collagen fiber.   The solubilized collagen aqueous solution has a collagen content of 7% by mass or less and a pH of 5.5 or more. In the spinning step, the solubilized collagen aqueous solution is discharged from the discharge holes having a pore diameter of about 0.18 mm or less. The solubilized collagen fiber according to claim 6, which is discharged into a solvent and spun at an average fineness of 1 to 15 dtx, and a ratio of the winding speed to the discharging speed in the stretching step is greater than 1 and 1.5 or less. Manufacturing method.   The method for producing a solubilized collagen fiber according to claim 6 or 7, wherein, in the drying step, the solubilized collagen fiber is crimped by drying without substantially applying a tensile load to the solubilized collagen fiber.   The method for producing a solubilized collagen fiber according to claim 6 or 7, further comprising a step of applying a tensile load to the solubilized collagen fiber during the drying step.   In the spinning step, a plurality of the solubilized collagen fibers are spun into a bundle, and after the drying step, the bundle of the solubilized collagen fibers is cut into a predetermined length; The method for producing a solubilized collagen fiber according to any one of claims 6 to 9, further comprising a step of defibrating the solubilized collagen fiber into a cotton shape.

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