Skin treatment method

Abstract

The present invention relates to a skin treatment method comprising: process 1: a process of imparting to the skin minute droplets of a liquid composition containing a polymer A and a volatile solvent B; and process 2: a process of shrinking the skin with drying of the minute droplets imparted to the skin by process 1, in which the polymer A has a deformation ratio of 0.3 to 1 as determined by method (I), and the mass of each of the minute droplets imparted to the skin in process 1 is 0.001 to 100 μg.

Description

TECHNICAL FIELD

[0001] The present application relates to a skin treatment method. BACKGROUND

[0002] As a phenomenon of aging of the skin due to aging, there are wrinkles around the eyes, around the mouth, the forehead, the neck, and the like, and relaxation of facial lines, and the like. Such a phenomenon of aging involves changes in skin tissue, a decrease in bone density, exposure to ultraviolet rays, and the like.

[0003] As a method for making wrinkles and relaxation less noticeable, there is cosmetic surgery. In surgery performed by cosmetic surgery, there are intervention surgical procedures such as a face lift surgery, and low-intervention non-surgical procedures such as injection therapy of a filler for removing wrinkles of the face, but there are cases where it is difficult to perform shape control, and there are problems such as a large physical burden on the surgeon.

[0004] Therefore, a method for improving wrinkles by a non-interventional method has been proposed.

[0005] For example, in Japanese Patent Application Publication No. 2005-200320 (Patent Document 1), a skin external agent for wrinkle improvement is described, which aims to provide a skin external agent for wrinkle improvement that is excellent in wrinkle improvement effect, usability, and use feeling, the skin external agent for wrinkle improvement containing a polymer water dispersion in which a film-forming polymer that is insoluble in water is dispersed in water, a main component of the film-forming polymer being a polyurethane having a film formation shrinkage of 20% or less and an acrylic polymer having a film formation shrinkage of 20% or less.

[0006] In Japanese Patent Application Publication No. 2006-169145 (Patent Document 2), a skin wrinkle smoothing agent and a skin wrinkle smoothing method are described, which aims to provide a skin wrinkle smoothing agent and a skin wrinkle smoothing method that exhibit a wrinkle smoothing effect in a short period of time and do not easily exert a load on other parts, the skin wrinkle smoothing agent being composed of a liquid or paste-like composition containing a polymer and a solvent or a dispersion medium, and generating a force that stretches wrinkles by shrinkage at the time of volatilization of the solvent or the dispersion medium after being applied to the skin, and the skin wrinkle smoothing method being a method in which the skin wrinkle smoothing agent is applied to the periphery of a portion of the skin having wrinkles.

[0007] In Japanese Patent Application Publication No. 2016-532482 (Patent Literature 3), a cosmetic applicator having a head and a main body for applying a skin-smoothing composition is provided with the object of providing a cosmetic applicator that can be applied to a composition capable of obtaining a balance of skin shrinkage, film softness, shrinkage elasticity, and the like, and simultaneously reducing skin wrinkles, and it is described that the head has a portion of the surface coated with a specific flocculating fiber, the skin-smoothing composition contains sodium silicate, a polyvalent silicate, and water, the flocculating fiber is capable of being brought into contact with the skin-smoothing composition, and then the skin-smoothing composition is applied to the skin in a uniform film via the flocculating fiber. SUMMARY

[0008] The present application relates to a skin treatment method, wherein, comprising:

[0009] Step 1: a step of imparting to the skin minute droplets of a liquid composition containing a polymer A and a volatile solvent B, and

[0010] Step 2: a step of shrinking the skin with drying of the minute droplets imparted to the skin by Step 1,

[0011] The polymer A has a deformation ratio of 0.3 or more and 1 or less as determined by the following Method (I),

[0012] The mass of each of the minute droplets imparted to the skin in Step 1 is 0.001 μg or more and 100 μg or less.

[0013] Method (I): The polymer A is dissolved in the volatile solvent B to prepare a polymer solution having a concentration of 10 mass%. On one side of a polyethylene sheet having a width of 20 mm x length of 100 mm x thickness of 0.03 mm, 0.005 g of the polymer solution is applied in a range of width of 20 mm x length of 50 mm from one end of the short side in the length direction in a constant temperature bath set to 40°C, and dried for 10 minutes, thereby producing a polyethylene sheet with a polymer film. The length of the polyethylene sheet in the portion applied with the polymer solution is set to L1, the length of the polyethylene sheet with a polymer film in the portion deformed due to drying of the applied solution is set to L2, and the value of L2 / L1 is set to the deformation ratio. BRIEF DESCRIPTION OF DRAWINGS

[0014] Figure 1 is a explanatory diagram of the measurement method of the deformation ratio (L2 / L1) of the polymer A by Method (I).

[0015] Figure 2 is a explanatory diagram showing an example of the mechanism of the skin shrinkage of the present application.

[0016] Figure 3is a view showing an example of a print pattern used in the application of the fine droplets in Step 1.

[0017] Figure 4 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0018] Figure 5 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0019] Figure 6 is a view schematically showing the application of the fine droplets to the skin using the print pattern shown in Figure 4 or Figure 5 is a cross-sectional view showing a state in which the fine droplets are applied to the skin by the application of the fine droplets in Step 1 using the print pattern shown in

[0020] Figure 7 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0021] Figure 8 is a photograph of the sample before and after the skin treatment in Example 13 taken from the upper surface side.

[0022] Figure 9 is a photograph of the sample before and after the skin treatment in Comparative Example 2 taken from the upper surface side.

[0023] Figure 10 is a photograph of the sample before and after the skin treatment in Example 42 taken from the upper surface side.

[0024] Figure 11 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0025] Figure 12 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0026] Figure 13 is a view showing another example of a print pattern used in the application of the fine droplets in Step 1.

[0027] Figure 14 is a photograph of the sample after the skin treatment obtained in Example 57 taken from the upper surface side. DETAILED DESCRIPTION

[0028] Rhytides are classified into epidermal types such as crows' feet, fine lines, and the like; dermal types such as UV rhytides, deep rhytides, and the like; and expression muscle types such as rhytides produced along expression muscles. Thus, there is a need for a method for improving various rhytides in a natural manner without intervention and without damaging the appearance.

[0029] In addition, among the parts of the face, the area around the eyes is a part where the skin is particularly thin, and is an area that is frequently moved due to blinking, and thus, wrinkles increase due to aging. In particular, fine lines located at the outer corner of the eye give a strong impression of aging, and thus, there is a high demand for a method for improving wrinkles at such a delicate part as the outer corner of the eye in a non-invasive manner.

[0030] However, in the technology of Patent Document 1, a skin external agent for wrinkle improvement using a specific polymer having a low film formation shrinkage rate is applied to wrinkles, and wrinkles are covered by a film that does not shrink, and thus, it is difficult to apply to a thin and delicate part such as the area around the eyes.

[0031] In the technology of Patent Document 2, although a wrinkle smoothing effect is obtained, as a method for applying a wrinkle smoothing agent to the skin, a method in which a liquid or paste-like composition is applied to the skin by a finger or a spatula or the like is used, and thus, there is room for improvement in the wrinkle improvement effect.

[0032] In the technology of Patent Document 3, it is described that a composition for smoothing the skin is attached to the skin by the above-described applicator to shrink the skin, and to smooth and flatten the defects of wrinkles and lines, and it is helpful to apply a film having a desired thickness, and it is a method in which the above-described composition is applied to the skin in a uniform film by flocculent fibers of the application head, and thus, there is a limitation in the range of application to the skin, and the wrinkle improvement effect is not sufficient.

[0033] In addition, as a surgery based on cosmetic surgery, a filler injection treatment is also used for the formation of a tear bag, but there are cases where it is difficult to perform shape control depending on the characteristics of the surgery site, and there are problems such as an increase in the burden on the body of the surgeon.

[0034] Therefore, flattening of the concave-convex of the skin surface, imparting of a three-dimensional sense that makes the concave-convex of the skin surface conspicuous, and tightening of the skin surface, or lifting of a part of the skin surface, and the like, are required to finely control the change in the shape of the outside of the skin in a non-invasive manner and without damaging the naturalness of the appearance.

[0035] The present application relates to a skin treatment method capable of finely controlling the shape of the outside of the skin in a non-invasive manner and without damaging the naturalness of the appearance, and a makeup method using the same.

[0036] The present inventors have found a skin treatment method including a step of imparting to the skin minute droplets of a liquid composition containing a polymer and a volatile solvent, and a step of shrinking the skin with drying of the minute droplets imparted to the skin by the step, in which by setting the deformation ratio of the polymer contained in the liquid composition measured by a prescribed method to a prescribed range, and setting the mass of each of the minute droplets imparted to the skin to a prescribed range, the shape of the outside of the skin can be finely controlled in a non-invasive manner and without impairing the naturalness of appearance.

[0037] That is, the present application relates to the following [1] to [3].

[0038] [1] A skin treatment method, wherein, comprising:

[0039] Step 1: a step of imparting to the skin minute droplets of a liquid composition containing a polymer A and a volatile solvent B, and

[0040] Step 2: a step of shrinking the skin with drying of the minute droplets imparted to the skin by Step 1, wherein,

[0041] the deformation ratio of the polymer A measured by the following method (I) is 0.3 or more and 1 or less,

[0042] the mass of each of the minute droplets imparted to the skin in Step 1 is 0.001 μg or more and 100 μg or less.

[0043] Method (I): The polymer A is dissolved in the volatile solvent B to prepare a polymer solution at a concentration of 10 mass%. On one side of a polyethylene sheet having a width of 20 mm x length of 100 mm x thickness of 0.03 mm, 0.005 g of the polymer solution is applied in a range of width of 20 mm x length of 50 mm from one end of the short side in the length direction, and dried in a constant temperature bath set to 40°C for 10 minutes, thereby producing a polyethylene sheet with a polymer film. The length of the polyethylene sheet of the portion applied with the above polymer solution is set to L1, the length of the polyethylene sheet with a polymer film of the portion deformed due to drying of the applied solution is set to L2, and the value of L2 / L1 is set to the deformation ratio.

[0044] [2] A cosmetic method in which the skin treatment method described in the above [1] is used for improvement of wrinkles of the skin.

[0045] [3] A cosmetic method in which the skin treatment method described in the above [1] is used for formation of relief of the skin.

[0046] According to the present application, a skin treatment method and a cosmetic method using the same can be provided, which can finely control the shape of the outside of the skin in a non-invasive manner without impairing the naturalness of appearance.

[0047] [Skin treatment method]

[0048] The skin treatment method of the present application comprises:

[0049] Step 1: a step of imparting to the skin minute droplets of a liquid composition containing a polymer A and a volatile solvent B, and

[0050] Step 2: a step of shrinking the skin with drying of the minute droplets imparted to the skin in Step 1, wherein

[0051] The polymer A has a deformation ratio of 0.3 or more and 1 or less as determined by the following Method (I),

[0052] The mass of each of the minute droplets imparted to the skin in Step 1 is 0.001 μg or more and 100 μg or less.

[0053] Method (I): The polymer A is dissolved in the volatile solvent B to prepare a polymer solution having a concentration of 10 mass%. On one side of a polyethylene sheet having a width of 20 mm x length of 100 mm x thickness of 0.03 mm, 0.005 g of the polymer solution is applied in a range of width of 20 mm x length of 50 mm from one end of the short side in the length direction, and the polyethylene sheet is dried in a constant-temperature bath set at 40°C for 10 minutes to produce a polyethylene sheet with a polymer film. The length of the polyethylene sheet in the portion applied with the polymer solution is set as LI, the length of the polyethylene sheet with a polymer film in the portion deformed due to drying of the applied solution is set as L2, and the value of L2 / L1 is set as the deformation ratio.

[0054] In addition, with respect to the length LI of the portion of the polyethylene sheet applied with the polymer solution and the length L2 of the polyethylene sheet with a polymer film, reference can be made to Figure 1 .

[0055] In addition, the "skin treatment method" in the present application means a "method of controlling the shape of the outside of the skin". The "control of the shape of the outside of the skin" includes: a change in the shape of the outside of the skin to flatten the unevenness of the skin surface, a change in the shape of the outside of the skin to make the unevenness of the skin surface prominent to impart a three-dimensional appearance, and a change in the shape of the outside of the skin to tighten the skin surface or lift a portion of the skin surface, and for example, further includes: a change in the shape of the outside of the skin to reduce wrinkles to bring the appearance age to be lower than the actual age to bring a rejuvenation effect, and a change in the shape of the outside of the skin to make wrinkles more prominent to bring the appearance age to be higher than the actual age to bring an aging effect.

[0056] The "wrinkle of skin" in the present application means unevenness and texture that appear on the surface of the skin. The wrinkle of skin is likely to appear around the eyes, around the mouth, the forehead, the neck, and the like. Small texture is fine lines, and large texture is large wrinkles, and the fine lines are generated in the outer corner of the eye, the eye, and the like, and the large wrinkles are generated due to the distribution of pores of the nasolabial folds, the cheeks, and the like.

[0057] As described later, the "improvement of the wrinkle of skin" in the present application means a method of flattening the depression of the skin that forms the wrinkle by shrinking the skin around the wrinkle with drying of the fine droplets of the above-mentioned liquid composition that are given to the skin. That is, it is a method of physically smoothing the wrinkle of the skin to flatten the unevenness of the surface of the skin, and it is a concept different from a method of applying a cosmetic or the like to the skin to cover the unevenness of the surface of the skin or to make the wrinkle optically unobvious.

[0058] In addition, as described later, the "formation of the relief of skin" in the present application means a method of making the unevenness of the surface of the skin conspicuous by three-dimensionally lifting the skin tissue by shrinking the skin with drying of the fine droplets of the above-mentioned liquid composition that are given to the skin.

[0059] In addition, as described later, the "improvement of the laxity of skin" means a method of tightening the skin or lifting a part of the surface of the skin to improve the laxity by shrinking the skin with drying of the fine droplets of the above-mentioned liquid composition that are given to the skin.

[0060] According to the present application, it is possible to provide a skin treatment method that finely controls the shape of the outside of the skin in a non-invasive manner without impairing the naturalness of the appearance. The reason is not yet determined, but it is considered as follows.

[0061] Here, reference is made to FIG. 1 that shows an example of the mechanism of the contraction of the skin according to the present application. Figure 2 The explanation is made.

[0062] In the present application, in the above-mentioned liquid composition, the polymer A exists in a state of being dissolved in the volatile solvent B. Also, as shown in (i) of FIG. 2, when the fine droplets 21 of the above-mentioned liquid composition are given to the skin 22 by the process 1, as shown in (ii) of FIG. 2, the volatile solvent B contained in the fine droplets 21 starts to evaporate during the drying of the fine droplets 21 of the process 2. Figure 2 (i) of FIG. 2, when the fine droplets 21 of the above-mentioned liquid composition are given to the skin 22 by the process 1, as shown in (ii) of FIG. 2, the volatile solvent B contained in the fine droplets 21 starts to evaporate during the drying of the fine droplets 21 of the process 2. Figure 2 (i) of FIG. 2, when the fine droplets 21 of the above-mentioned liquid composition are given to the skin 22 by the process 1, as shown in (ii) of FIG. 2, the volatile solvent B contained in the fine droplets 21 starts to evaporate during the drying of the fine droplets 21 of the process 2. Figure 2arrows 23 indicate the appearance of the volatilization), depending on the temperature of the skin in contact with the end portion of the minute droplet 21, the volatile solvent B preferentially volatilizes from the end portion of the minute droplet 21, thereby generating a difference in surface tension between the end portion and the central portion of the minute droplet. As a result, a Marangoni convection 24 is generated within the minute droplet 21. Thereby, the concentration of the polymer A at the end portion of the minute droplet 21 becomes high, and the polymer A is precipitated from the end portion of the minute droplet 21, as shown in Figure 2 (iii) the end portion solidifies earlier than the central portion of the minute droplet 21, that is, solidifies by precipitation of the polymer A, and the skin 26 under the solidified coating film at the end portion 25 is fixed. Also, after the coating film at the end portion 25 solidifies, the volatile solvent B volatilizes from the central portion of the minute droplet 21, causing shrinkage of the coating film, but as shown in Figure 2 (iv) the solidified coating film at the end portion 25 is fixed to the skin, and in addition, the deformation ratio of the polymer A determined by the above-described method (I) satisfies a prescribed range, so the solidified coating film shrinks with the volatilization of the volatile solvent B, at the same time, exerts a shrinkage stress 27 on the skin. As a result, as shown in Figure 2 (v) the shrinkage stress 27 on the skin at the dry end point of the minute droplet 21 is considered to be expressed, and a high shrinkage effect on the skin is considered to be expressed.

[0063] In the present application, the mass of each of the minute droplets imparted to the skin by the process 1 is in a prescribed range, so compared with the case where the liquid composition is applied to the skin by a human finger or a spatula or the like with the same amount of imparting, the proportion of the end portion of the minute droplet to the amount of imparting of the liquid composition is increased, volatilization of the volatile solvent B from the end portion of the minute droplet in the process 2 is promoted, and thus, it is considered that the drying speed of the minute droplet imparted to the skin is accelerated, and the shrinkage effect on the skin is improved.

[0064] In addition, in the present application, by the process 1, a coating film composed of minute droplets can be formed discontinuously on the surface of the skin. Therefore, the smooth feeling of the surface of the skin on which the treatment is performed is suppressed, and for example, even in the case where the content of the polymer A in the liquid composition is low and the drying speed of the minute droplet is slow, the regular reflection of light on the surface of the skin on which the treatment is performed can be suppressed, and the expression of the shrinkage effect on the skin can be improved without impairing the naturalness of the appearance.

[0065] In addition, in the case where the liquid composition is applied to the skin by a human finger or a spatula or the like, for example, in the case where the content of the polymer A in the liquid composition is low and the drying speed of the liquid composition imparted to the skin is fast, with the generation of the above-described Marangoni convection, fine unevenness can sometimes be generated on the coating film due to Benard cells.

[0066] On the other hand, in the present application, by setting the mass of each of the minute droplets imparted to the skin by the process 1 to a prescribed amount, the size of the Benard cells generated can be limited, and thus, the unevenness of the fine concavo-convex of the coating film can be suppressed.

[0067] In addition, by forming the coating film composed of the minute droplets discontinuously on the skin surface, the normal reflection of light from the skin surface after the treatment can be suppressed, the blurring effect due to the scattering of light can be improved, and a sense of transparency can be imparted.

[0068] The skin treatment method of the present application is preferably used as a cosmetic method or a makeup method.

[0069] For example, if the skin treatment method of the present application is used as a cosmetic method or a makeup method for improving the wrinkles of the skin, the skin around the wrinkles can be contracted by the contraction mechanism of the skin, and the skin forming the wrinkles can be flattened, so that the wrinkles are not conspicuous.

[0070] In addition, if the skin treatment method of the present application is used as a cosmetic method or a makeup method for forming the relief of the skin, the skin of the portion where the concavo-convex of the skin surface is to be made conspicuous can be contracted by the contraction mechanism of the skin, and the relief of the skin can be formed by lifting the skin tissue to impart a three-dimensional sense to the skin.

[0071] Thus, by selecting the body portion to which the minute droplets of the liquid composition are to be imparted, the concavo-convex of the skin surface can be controlled.

[0072] In addition, in the present application, as described above, the end portion is solidified earlier than the central portion of the minute droplets, and thus, the so-called "coffee ring phenomenon" in which the polymer A is aggregated to the end portion of the coating film is suppressed. Therefore, by adjusting the mass of each of the minute droplets, the thickness of the coating film at the end portion can be relatively thinned, and the polymer A is further aggregated to the central portion of the coating film, and thus, by selecting the body portion to which the minute droplets are to be imparted, the central portion is contracted after the end portion is fixed during the drying of the central portion of the minute droplets, and thus, it is considered that the effect of lifting the skin is also exhibited.

[0073] Therefore, if the skin treatment method of the present application is used, not only the improvement of the wrinkles of the skin and the formation of the relief of the skin can be achieved, but also the relaxation of the skin can be improved, and the method can be applied to a cosmetic surgery for firming the skin or lifting a portion of the skin, and the like.

[0074] Thus, in the present application, by selecting the body portion to which the minute droplets of the liquid composition are to be imparted in the process 1, and by contracting the skin of the portion by the process 2, the deformation of the shape of the outside of the skin can be promoted in a non-invasive manner and finely controlled. Therefore, the method can be used as a non-invasive cosmetic plastic surgery technique or a cosmetic method for performing a non-invasive cosmetic surgery.

[0075] (Step 1)

[0076] Step 1 is a step of imparting to the skin a fine droplet of a liquid composition containing a polymer A and a volatile solvent B.

[0077] In the present application, the imparting to the skin of the fine droplet of the above-mentioned liquid composition in Step 1 includes not only the direct imparting of the fine droplet of the liquid composition to the skin surface, but also, for example, the imparting of the fine droplet of the liquid composition to the skin via a cosmetic such as a solution, an emulsion, a cream, a sheet, or the like, which is applied to the skin in advance.

[0078] < Liquid composition >

[0079] The liquid composition used in the present application contains a polymer A and a volatile solvent B.

[0080] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above-mentioned liquid composition is preferably in a liquid state at 25°C under 1 atm.

[0081] (Polymer A)

[0082] For the polymer A used in the present application, the deformation ratio (L2 / L1) determined by the above-mentioned method (I) is 0.3 or more and 1 or less. Specifically, the measurement method of the deformation ratio (L2 / L1) of the polymer A by the above-mentioned method (I) is as described in the examples. The larger the value representing the deformation ratio (L2 / L1) is, the larger the amount of shrinkage of the coating film containing the polymer A caused by drying is, and the upper limit of L2 / L1 is 1.

[0083] The deformation ratio (L2 / L1) of the polymer A determined by the above-mentioned method (I) can be adjusted by the combination of the polymer A and the volatile solvent B.

[0084] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above-mentioned deformation ratio (L2 / L1) is 0.3 or more, preferably 0.5 or more, more preferably 0.6 or more, further preferably 0.7 or more, still further preferably 0.8 or more, yet further preferably 0.85 or more, yet further preferably 0.9 or more, yet further preferably 0.95 or more, and 1 or less.

[0085] As for the polymer A, if the above-mentioned deformation ratio is satisfied, there is no particular limitation.

[0086] In the present application, the above liquid composition is imparted to the skin in the form of fine droplets by the process 1, and thus, a shrunken coating film can be discontinuously imparted on the surface of the skin. The region to which fine droplets are not imparted by the process 1 does not form a coating film, and thus, the region is preferentially deformed by the shrinkage stress during the drying process of the process 2. Therefore, the breakage and the destruction of the shrunken coating film are less likely to occur, and a polymer A having a high shrinkage force can be used for the above liquid composition, and the degree of freedom in the design of the kind of the polymer A, the content of the polymer A in the above liquid composition, and the amount of the fine droplets imparted per unit area is high.

[0087] As the basic skeleton of the polymer A, for example, there can be mentioned condensation type polymers such as polyurethane, polyester, polyether, polyurea, and the like; vinyl type polymers obtained by addition polymerization of vinyl compounds, vinylidene compounds, vinylene compounds, cyclic olefins, and the like; silicone type polymers, and the like. Among these compounds, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, one or more selected from the group consisting of vinyl type polymers and silicone polymers is preferred.

[0088] As the vinyl type monomer constituting the above vinyl type polymer used as the polymer A, it is preferred to have an anionic group or a cationic group.

[0089] As the anionic group, there can be mentioned carboxyl group (-COOM), sulfonic acid group (-SO3M), phosphoric acid group (-OPO3M2), and the like which exhibit acidity by releasing hydrogen ions by dissociation, or their dissociated ionic forms (-COO", -SO3 - , -OPO3 2- , -OPO3 - M), and the like. In the above chemical formulae, M represents a hydrogen atom, an alkali metal, ammonium, or organic ammonium.

[0090] As the vinyl type monomer having an anionic group, there can be mentioned acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, and the like.

[0091] As the cationic group, there can be mentioned primary amino group, secondary amino group, or tertiary amino group, protonic acid salts thereof, and quaternary ammonium group, and the like.

[0092] As the vinyl-based monomer having a cationic group, mention can be made of (meth)acrylic acid N,N-dialkylaminoalkyl ester in which the total number of carbon atoms of the N,N-dialkylaminoalkyl group is 4 or more and 14 or less, N,N-dialkylaminoalkyl (meth)acrylamide in which the total number of carbon atoms of the N,N-dialkylaminoalkyl group is 4 or more and 14 or less, and the like.

[0093] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above-described vinyl-based polymer is preferably a vinyl-based polymer containing a repeating unit derived from a vinyl-based monomer having an anionic group, more preferably a vinyl-based polymer containing a repeating unit derived from a vinyl-based monomer selected from one or more of acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, and salts thereof, and further preferably one or more selected from among polymethacrylic acid and sodium polystyrene sulfonate.

[0094] In the case where the above-described vinyl-based polymer contains a repeating unit derived from a vinyl-based monomer having an anionic group, the vinyl-based polymer can also be a copolymer containing a repeating unit derived from a vinyl-based monomer having an anionic group and a repeating unit derived from another monomer, but from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, it is preferably a homopolymer of a vinyl-based monomer having an anionic group.

[0095] The weight average molecular weight Mw of the above-described vinyl-based polymer is preferably 10,000 or more, more preferably 30,000 or more, and further preferably 50,000 or more, and is preferably 700,000 or less, more preferably 500,000 or less, and further preferably 300,000 or less. The above-described weight average molecular weight Mw can be measured by a gel permeation chromatography (GPC) method using polystyrene as a standard substance, and specifically can be measured by the method described in the Examples.

[0096] The above-described vinyl-based polymer can be a synthetic polymer or a commercially available product.

[0097] In the case where the above-described vinyl-based polymer is obtained by synthesis, for example, the above-described vinyl-based monomer having an anionic group and another monomer, if necessary, can be subjected to addition polymerization by a publicly known method in the presence of a polymerization initiator or the like to obtain the vinyl-based polymer.

[0098] As the commercially available product of the above-described vinyl-based polymer, mention can be made of sodium polystyrene sulfonate manufactured by Alfa Aesar, and the like.

[0099] The above-mentioned silicone-based polymer used as the polymer A is preferably a silicone polymer having a silicone structure.

[0100] The "silicone structure" in the present specification refers to a structure represented by the following general formula (I).

[0101]

[0102] In the general formula (I), R 1 independently represent a hydrocarbon group having 1 or more and 12 or less carbon atoms, and p is an integer of 1 or more.

[0103] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of versatility, R 1 is preferably an alkyl group having 1 or more and 12 or less carbon atoms or an aryl group having 6 or more and 12 or less carbon atoms, more preferably an alkyl group having 1 or more and 12 or less carbon atoms or a phenyl group, further preferably an alkyl group having 1 or more and 3 or less carbon atoms, and still further preferably a methyl group.

[0104] The above-mentioned silicone polymer can be a polymer composed only of a silicone structure, but from the viewpoint of adjusting the deformation ratio to a prescribed range and finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, it is preferably a polymer having a silicone structure on a part thereof.

[0105] In the case of a polymer having a silicone structure on a part thereof, the silicone structure can exist at any site in the main chain and the side chain in the polymer, but from the viewpoint of adjusting the deformation ratio to a prescribed range and finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, it is preferably present in the side chain.

[0106] In the case where the above-mentioned silicone structure exists in the main chain of the polymer, there is no particular limitation on the bonding form thereof, and for example, the silicone structure can exist at the terminal of the main chain of the polymer, or it can be a copolymer in which the silicone structure is bonded in a block form or a random form in the main chain of the polymer. In addition, a polymer modified by grafting a compound having the above-mentioned silicone structure can also be used.

[0107] The above-mentioned silicone polymer is preferably a silicone-modified polymer. As specific examples of the silicone-modified polymer, there can be mentioned a silicone-modified polynorbornene and the like, a silicone-modified polymer containing a norbornane structure; a silicone-modified pullulan; a silicic acid compound containing a silicone structure such as a trialkylsilyloxy silicic acid, a fluorine-modified alkylsilyloxy silicic acid, a phenyl-modified alkylsilyloxy silicic acid, and the like; a silicone dendrimer; and the like.

[0108] Silicone-modified polymer containing norbornane structure

[0109] The "norbornane structure" in the present specification means a structure represented by the following formula. As the silicone-modified polymer containing norbornane structure, a silicone-modified polymer having a repeating unit represented by the following general formula (1) or (2) is exemplified.

[0110]

[0111] As the silicone-modified polymer containing norbornane structure, a polymer having a repeating unit represented by the following general formula (1) or (2) is exemplified.

[0112]

[0113] In the general formula (1), R 2 independently represent an alkyl group having 1 or more and 12 or less carbon atoms, and X is a group represented by the following general formula (i). a is an integer of 1 or more and 3 or less, and b is an integer of 0 or more and 2 or less.

[0114]

[0115] In the general formula (i), R 1 is the same as described above, and c is an integer of 1 or more and 5 or less.

[0116]

[0117] In the general formula (2), R 1 , R 2 and b are the same as described above, and d is an integer of 2 or more and 5 or less.

[0118] In the general formula (1), R 2 independently represent an alkyl group having 1 or more and 12 or less carbon atoms, and X is a group represented by the following general formula (i). a is an integer of 1 or more and 3 or less, and b is an integer of 0 or more and 2 or less.

[0119] In the general formula (i), R 1 is the same as described above, and c is an integer of 1 or more and 5 or less. is an alkyl group having 1 or more and 12 or less carbon atoms or an aryl group having 6 or more and 12 or less carbon atoms, and more preferably an alkyl group having 1 or more and 12 or less carbon atoms or a phenyl group, and further preferably an alkyl group having 1 or more and 3 or less carbon atoms, and more further preferably a methyl group. c is an integer of 1 or more and 5 or less, and from the viewpoint of general use, c is preferably 1. That is, X is preferably a trimethylsiloxy group.

[0120] In General Formula (1), a is an integer of 1 or more and 3 or less, and for example, a polymer in which a repeating unit of a = 2 and a repeating unit of a = 3 are mixed can also be present. From the viewpoint of general applicability, a is preferably 3. b is an integer of 0 or more and 2 or less, and from the same viewpoint as described above, b is preferably 0, 1, or a combination thereof, and more preferably 0.

[0121] In General Formula (2), R 1 , R 2 , and b are the same as described above. d is an integer of 2 or more and 5 or less, and from the viewpoint of general applicability, d is preferably 2. In the cyclic silicone structure in General Formula (2), from the same viewpoint as described above, R 1 and R 2 are preferably methyl, and d is 2 or 3. That is, the cyclic silicone structure in General Formula (2) is preferably a structure represented by the following Formula (2-1) or (2-2).

[0122]

[0123] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of general applicability, the proportion of the repeating unit represented by General Formula (1) or (2) in the norbornane structure-containing silicone-modified polymer is preferably 10% or more, more preferably 30% or more, and further preferably 50% or more, of the total number of repeating units in the polymer, and is preferably 100% or less, more preferably 95% or less, further preferably 90% or less, and more further preferably 70% or less.

[0124] The norbornane structure-containing silicone-modified polymer can also have, in addition to the repeating unit represented by General Formula (1) or (2), a repeating unit represented by the following General Formula (3).

[0125]

[0126] In General Formula (3), R 3 to R 6 each independently represent a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having a carbon atom number of 1 or more and 10 or less, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglycerol group, or an alkoxy silyl group. Two groups selected from R 3 to R 6 may also be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboxy imide group, or an acid anhydride group. b is the same as described above.

[0127] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of general use, the proportion of the repeating unit represented by General Formula (3) in the organosilicon-modified polymer containing a norbornane structure is preferably 90% or less, more preferably 70% or less, and further preferably 50% or less, of the total number of repeating units in the polymer. In addition, in the case of containing the repeating unit represented by General Formula (3), the proportion of the repeating unit represented by General Formula (3) is preferably 5% or more, more preferably 10% or more, and further preferably 30% or more, of the total number of repeating units in the polymer.

[0128] The proportion of the repeating unit represented by General Formula (1) to (3) in the organosilicon-modified polymer containing a norbornane structure can be obtained by 1 H-NMR measurement.

[0129] The organosilicon-modified polymer containing a norbornane structure is preferably an organosilicon-modified poly-norbornene, and more preferably an organosilicon-modified poly-norbornene represented by the following Formula (4).

[0130]

[0131] In Formula (4), e, f are the number of repeating units, and each independently represent an integer of 1 or more.

[0132] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of general use, the molar ratio (e / f) of e and f in Formula (4) is preferably 20 / 80 to 90 / 10, more preferably 30 / 70 to 80 / 20, further preferably 50 / 50 to 70 / 30, more further preferably 55 / 45 to 70 / 30, and more further preferably 55 / 45 to 65 / 35.

[0133] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of general use, the number average molecular weight Mn of the organosilicon-modified polymer containing a norbornane structure is preferably 50,000 or more, more preferably 100,000 or more, and further preferably 200,000 or more, and is preferably 2,000,000 or less, more preferably 1,500,000 or less, further preferably 800,000 or less, more further preferably 600,000 or less, and more further preferably 400,000 or less.

[0134] The above number average molecular weight Mn can be measured by a gel permeation chromatography (GPC) method using polystyrene as a standard substance, and specifically can be measured by the method described in the Examples.

[0135] As the organosilicon-modified polymer containing a norbornane structure, for example, an organosilicon-modified cyclic olefin monomer containing a norbornane structure or capable of forming a norbornane structure is subjected to addition polymerization by a known method.

[0136] For example, if it is an organosilicon-modified polymer containing a norbornane structure having a repeating unit represented by General Formula (1) or (2), it can be obtained by subjecting a cyclic olefin monomer represented by General Formula (1a) or (2a) below to addition polymerization. Also, it can be that, in the addition polymerization, a cyclic olefin monomer represented by General Formula (3a) below is subjected to copolymerization.

[0137]

[0138] In General Formula (1a), R 2 , X, a, and b are the same as described above.

[0139]

[0140] In General Formula (2a), R 1 , R 2 , b, and d are the same as described above.

[0141]

[0142] In General Formula (3a), R 3 ~R 6 , and b are the same as described above.

[0143] In the case where the cyclic olefin monomer represented by General Formula (3a) is subjected to copolymerization, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of versatility, the amount used is preferably 90 mol% or less, more preferably 70 mol% or less, and further preferably 50 mol% or less, based on 100 mol% of the total monomers used in the polymerization, and is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 30 mol% or more.

[0144] As the organosilicon-modified polynorbornene represented by Formula (4) above, it can be obtained by subjecting tris(trimethylsiloxy)silylnorbornene represented by Formula (4a) below and norbornene to addition copolymerization.

[0145]

[0146] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the molar ratio in the copolymer of tris(trimethylsiloxy)silylnorbornene and norbornene 〔tris(trimethylsiloxy)silylnorbornene / norbornene〕 is preferably 20 / 80 or more, more preferably 30 / 70 or more, further preferably 50 / 50 or more, and still further preferably 55 / 45 or more, and is preferably 90 / 10 or less, more preferably 80 / 20 or less, further preferably 70 / 30 or less, and still further preferably 65 / 35 or less.

[0147] Note that the repeating units shown in General Formulae (1) to (3) and Formula (4) each represent a 2,3-addition structural unit of a cyclic olefin monomer as a raw material monomer, but can also include a repeating unit that becomes a 2,7-addition structural unit by addition polymerization of the cyclic olefin monomer.

[0148] As the organosilicon-modified polymer containing a norbornane structure, a (norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer is preferable, which is a compound described as NORBORNENE / TRIS(TRIMETHYLSILOXY) SILYLNORBORNENE COPOLYMER in the INCI Name (International Cosmetic Ingredient Dictionary and Handbook, 16th edition, Volume 2, 2016, p. 2274).

[0149] As a commercially available organosilicon-modified polymer containing a norbornane structure, "NBN-30-ID" (isododecane solution of a (norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer) manufactured by Shin-Etsu Chemical Co., Ltd., and the like can be given.

[0150] [Organosilicon-modified pullulan]

[0151] As the organosilicon-modified pullulan, a pullulan having an organosilicon structure in a side chain can be given, and specifically, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance and the viewpoint of general use, an organosilicon-modified pullulan in which at least a part of hydrogen atoms of OH groups in the pullulan is substituted with a group represented by General Formula (5) below is preferable.

[0152] -Z 1 -SiX a R 2 3-a (5)

[0153] In General Formula (5), Z 1 is a single bond or a divalent organic group. R2 X, a are the same as described above, from the same viewpoint as described above, X is preferably trimethylsiloxy, and a is preferably 3.

[0154] In General Formula (5), from the same viewpoint as described above, Z 1 is preferably a divalent organic group, more preferably a divalent group represented by General Formula (5-1) or (5-2) below, and further preferably a divalent group represented by General Formula (5-2) below.

[0155]

[0156] In General Formulae (5-1) and (5-2), R 11 is an alkylene group having 1 or more and 10 or less carbon atoms, and examples thereof include methylene, ethylene, trimethylene, propylene, butylene, and the like. From the same viewpoint as described above, among these examples, ethylene, trimethylene, and propylene are preferred, and trimethylene or propylene is more preferred.

[0157] As commercially available organosilicon-modified pullulan, "TSPL-30-ID" (isododecane solution of tri (trimethylsiloxy) silanylpropyl carbamoyl amylopectin), "TSPL-30-D5" (cyclopentasiloxane solution of tri (trimethylsiloxy) silanylpropyl carbamoyl amylopectin), and the like manufactured by Shin-Etsu Chemical Co., Ltd. can be given.

[0158] [Silicic acid compound containing organosilicon structure]

[0159] As the silicic acid compound containing an organosilicon structure used in the present application, a silicate compound having an organosilicon structure at a terminal can be given, and examples thereof include trialkylsiloxy silicic acid, fluorine-modified alkylsiloxy silicic acid, phenyl-modified alkylsiloxy silicic acid, and the like.

[0160] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance and the viewpoint of versatility, the alkyl group in the trialkylsiloxy silicic acid is preferably an alkyl group having 1 or more and 10 or less carbon atoms, more preferably an alkyl group having 1 or more and 4 or less carbon atoms, and further preferably a methyl group. As a specific example of the trialkylsiloxy silicic acid, trimethylsiloxy silicic acid can be given.

[0161] As the fluorine-modified alkylsiloxy silicic acid, a compound in which at least a part of the hydrogen atoms of the alkyl group in the trialkylsiloxy silicic acid is replaced with a fluorine atom can be given. As a specific example thereof, trifluoropropyldimethylsiloxy silicic acid, trifluoropropyldimethyl / trimethylsiloxy silicic acid, and the like can be given.

[0162] As the phenyl-modified alkylsiloxy silicic acid, for example, phenylpropyldimethylsiloxy silicic acid, phenylpropyldimethyl / trimethylsiloxy silicic acid, and the like can be given.

[0163] Among the silicic acid compounds containing a silicone structure, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, one or more selected from the group consisting of trialkylsiloxy silicic acid and fluorine-modified alkylsiloxy silicic acid is preferable.

[0164] As the commercially available silicic acid compounds containing a silicone structure, "KF-7312J", "KF-7312K", "KF-7312T", "KF-7312L", "X-21-5249", "X-21-5250", "KF-9021", "X-21-5595", "X-21-5616", "KF-9021L", "X-21-5249L", "X-21-5250L", and the like of Shin-Etsu Chemical Co., Ltd. (trimethylsiloxy silicic acid (solution)), "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyl dimethyl / trimethylsiloxy silicic acid), "XS66-B8636" (polydimethylsiloxane solution of trifluoropropyl dimethyl / trimethylsiloxy silicic acid), "SilShine 151" (phenylpropyl dimethylsiloxy silicic acid) of Momentive Performance Materials Japan LLC, and the like can be used.

[0165] [Silicone dendrimer]

[0166] As the silicone dendrimer, for example, a vinyl-based polymer having a siloxane dendrimer structure on a side chain can be mentioned. From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and the viewpoint of versatility, specifically, the siloxane dendrimer structure is preferably a group represented by the following general formula (6).

[0167]

[0168] In general formula (6), R 1 is the same as described above. Z 2 is a single bond or a divalent organic group. X 1 is a group represented by the following general formula (6-1) when i = 1, and i is an integer of 1 or more and 10 or less representing the level of the group.

[0169]

[0170] In general formula (6-1), R 1 is the same as described above, and R 12 is an alkyl group having 1 or more and 10 or less carbon atoms. Z 3 is an alkylene group having 2 or more and 10 or less carbon atoms. X i+1is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, or a group represented by General Formula (6-1), a i is an integer of 0 to 3.

[0171] In General Formula (6), Z 2 is a single bond or a divalent organic group, from the viewpoint of general use, it is preferable to be a divalent organic group, and more preferable to be a divalent group represented by General Formula (6-2), (6-3), or (6-4).

[0172]

[0173] In General Formula (6-2), (6-3), and (6-4), R 13 is an alkylene group having 1 to 10 carbon atoms, and examples include methylene, ethylene, trimethylene, propylene, butylene, and the like, and from the viewpoint of general use, it is preferable to be ethylene, trimethylene, or propylene. R 14 is an alkyl group having 1 to 10 carbon atoms, and examples include methyl, ethyl, propyl, butyl, and from the same viewpoint as above, it is preferable to be methyl. R 15 is an alkylene group having 1 to 10 carbon atoms, and examples include methylene, ethylene, trimethylene, propylene, butylene, and the like, and from the same viewpoint as above, it is preferable to be ethylene. q is an integer of 0 to 4, and r is 0 or 1.

[0174] As the vinyl-based polymer having the above-described siloxane dendrimer structure in the side chain, a polymer having a repeating unit derived from a monomer represented by General Formula (7) below can be given.

[0175]

[0176] In General Formula (7), R 1 and X 1 are the same as above. Y is a group containing a vinyl bond, and examples include a vinyl group, a 2-propenoyloxyethyl group, a 3-propenoyloxypropyl group, a 2-methacryloyloxyethyl group, a 3-methacryloyloxypropyl group, a 4-vinylphenyl group, a 3-vinylphenyl group, a 4-(2-propenyl)phenyl group, a 3-(2-propenyl)phenyl group, a 2-(4-vinylphenyl)ethyl group, a 2-(3-vinylphenyl)ethyl group, an allyl group, and a 5-hexenyl group. Among these, from the viewpoint of general use, it is preferable to be a (meth)acryloyl group or a vinyl group, and more preferable to be a (meth)acryloyl group.

[0177] The vinyl-based polymer having the above-described siloxane dendrimer structure in the side chain can further include a repeating unit derived from a vinyl-based monomer other than the monomer represented by General Formula (7). As the vinyl-based monomer, other than the monomer represented by General Formula (7) having a group including a vinyl bond, for example, (meth)acrylic acid, an alkyl (meth)acrylate, a hydroxyalkyl (meth)acrylate, an aromatic ring-containing (meth)acrylate, a fatty acid vinyl ester, a (meth)acrylamide, styrene or a derivative thereof, etc. can be cited, and one or two or more kinds thereof can be used. Of these examples, from the viewpoint of versatility, a (meth)acrylic monomer such as (meth)acrylic acid, an alkyl (meth)acrylate, a hydroxyalkyl (meth)acrylate, an aromatic ring-containing (meth)acrylate, etc. is preferred.

[0178] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the content of the repeating unit derived from the monomer represented by General Formula (7) in the vinyl-based polymer having the above-described siloxane dendrimer structure in the side chain is preferably 0.1% by mass or more, more preferably 10% by mass or more, and further preferably 20% by mass or more, and is preferably 100% by mass or less, with respect to the total repeating units in the vinyl-based polymer.

[0179] The vinyl-based polymer having the above-described siloxane dendrimer structure in the side chain is more preferably an acrylic polymer. That is, as the preferred organosilicon dendrimer, an acrylic polymer having a siloxane dendrimer structure in the side chain (hereinafter, both are referred to as "acrylic organosilicon dendrimer") is used. The acrylic organosilicon dendrimer is a polymer including a repeating unit derived from the monomer in which Y in General Formula (7) is a (meth)acryl group, and can further include a repeating unit derived from a (meth)acrylic monomer other than the monomer represented by General Formula (7).

[0180] As commercially available organosilicon dendrimers, "FA 4001 CMSilicone Acrylate" (a cyclopentasiloxane solution of an acrylate-polytrimethylsiloxy methacrylate copolymer) and "FA 4002 ID Silicone Acrylate" (an isododecane solution of an acrylate-polytrimethylsiloxy methacrylate copolymer), etc., acrylic organosilicon dendrimers manufactured by Dow Corning Toray Co., Ltd. can be cited.

[0181] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above-mentioned silicone polymer is preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, trifluoropropyl dimethyl / trimethylsiloxy silicic acid, and acrylic silicone dendrimer, more preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, and trifluoropropyl dimethyl / trimethylsiloxy silicic acid.

[0182] As described above, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, polymer A is preferably one or more selected from the group consisting of a silicone polymer having a structure represented by the above general formula (I) and a vinyl-based polymer containing a repeating unit derived from a vinyl-based monomer having an anionic group, more preferably a silicone-modified polymer and a vinyl-based polymer containing a repeating unit derived from a vinyl-based monomer selected from one or more of acrylic acid, methacrylic acid, maleic acid, styrene sulfonic acid, and salts thereof, further preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, trifluoropropyl dimethyl / trimethylsiloxy silicic acid, acrylic silicone dendrimer, polymethacrylic acid, and sodium polystyrene sulfonate, more further preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, trifluoropropyl dimethyl / trimethylsiloxy silicic acid, polymethacrylic acid, and sodium polystyrene sulfonate.

[0183] In addition, in the present application, it is preferable that the effect produced by the fine control of the shape of the outside of the skin be favorably continued even in the case where external force or physical deformation or the like is received in a state where the coating film is formed on the skin by the process 2. From this viewpoint, polymer (A) is preferably a silicone polymer having a structure represented by the above general formula (I), more preferably a silicone-modified polymer, further preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, trifluoropropyl dimethyl / trimethylsiloxy silicic acid, and acrylic silicone dendrimer, more further preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, trimethylsiloxy silicic acid, and trifluoropropyl dimethyl / trimethylsiloxy silicic acid, more further preferably one or more selected from the group consisting of silicone-modified polynorbornene, silicone-modified pullulan, and trifluoropropyl dimethyl / trimethylsiloxy silicic acid, more further preferably one or more selected from the group consisting of silicone-modified polynorbornene and silicone-modified pullulan, more further preferably silicone-modified polynorbornene, more further preferably silicone-modified polynorbornene represented by the above formula (4).

[0184] In the present application, even in the case where the content of the polymer A in the above liquid composition is low, and the liquid composition is a composition in which the concentration of the polymer A is relatively dilute, by imparting to the skin in the form of fine droplets, the skin contractive action can be exhibited without impairing the naturalness of the appearance. In addition, in the case where the method of imparting the fine droplets to the skin is a method using the inkjet method or the nanodispensing method described later, by adjusting the formulation such that the content of the polymer A in the liquid composition is low, the viscosity of the liquid composition can be reduced, the ejection property of the liquid composition can be improved, and high-precision patterning printing can be performed. From this viewpoint, the content of the polymer A in the above liquid composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, more further preferably 5% by mass or more, more further preferably 7% by mass or more, more further preferably 10% by mass or more, and, on the other hand, preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, more further preferably 15% by mass or less.

[0185] (Volatile solvent B)

[0186] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the liquid composition used in the present application contains a volatile solvent B.

[0187] For the volatile solvent B, the evaporation rate after evaporation for 30 minutes under the conditions of 40°C, 60% RH at 1 atm is preferably 5% or more. By the evaporation rate of the volatile solvent B being in the above range, the drying speed of the fine droplets of the liquid composition in Step 2 can be increased, the shrinkage of the coating film can be accelerated, and the effect of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance can be improved.

[0188] From this viewpoint, the above evaporation rate of the volatile solvent B is more preferably 14% or more, further preferably 18% or more, more further preferably 25% or more, more further preferably 30% or more, more further preferably 45% or more, more further preferably 55% or more, more further preferably 60% or more, more further preferably 65% or more, more further preferably 70% or more, more further preferably 80% or more, and more further preferably 95% or more. On the other hand, the upper limit is 100%.

[0189] For the above evaporation rate, 0.5 g of a sample is placed in a glass dish having a diameter of 40 mm, and left to stand at 40°C for 30 minutes under the conditions of 60% RH at 1 atm to evaporate it. The mass of the sample before evaporation is set as W0 (g), and the mass of the sample after evaporation is set as W1 (g), and the value of 〔(W0-W1) / W0〕x100 is calculated, which is denoted as the evaporation rate. The larger this value, the faster the evaporation speed.

[0190] Specifically, the above-mentioned volatility can be measured by the method described in the examples.

[0191] As for the volatile solvent B, one kind alone or two or more kinds simultaneously can also be used.

[0192] The volatile solvent B can be appropriately selected from a water-soluble solvent or a non-water-soluble solvent depending on the kind of the polymer A. "Water-soluble" means a solubility in water of more than 1 w / w%, and "non-water-soluble" means a solubility in water of 1 w / w% or less.

[0193] The volatile solvent B is preferably one or more kinds selected from the group consisting of water, a fatty alcohol having 2 or more and 4 or less carbon atoms, a volatile hydrocarbon oil, and a volatile silicone oil, and more preferably one or more kinds selected from the group consisting of water (volatility 100%), ethanol (volatility 100%), isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methylpolymethylsiloxane, and dimethylpolysiloxane having a dynamic viscosity of less than 5 mm 2 / s at 25°C.

[0194] As for the dynamic viscosity at 25°C, it can be measured by a Ubbelohde viscometer according to ASTM D 445-46T or JIS Z 8803.

[0195] In the case where the polymer A is a silicone polymer having the structure represented by the above general formula (I), the volatile solvent B is preferably a non-water-soluble solvent, and more preferably one or more kinds selected from the group consisting of a volatile hydrocarbon oil and a volatile silicone oil, and further preferably one or more kinds selected from the group consisting of isododecane (volatility 33%), hexamethyldisiloxane (volatility 100%), methylpolymethylsiloxane, and dimethylpolysiloxane having a dynamic viscosity of less than 5 mm 2 / s at 25°C.

[0196] In the case where the polymer A is a vinyl-based polymer containing a repeating unit derived from a vinyl-based monomer having an anionic group, the volatile solvent B is preferably a water-soluble solvent, and more preferably one or more kinds selected from the group consisting of water and a fatty alcohol having 2 or more and 4 or less carbon atoms.

[0197] As the commercially available products of hexamethyldisiloxane and dimethylpolysiloxane having a dynamic viscosity of less than 5 mm 2 / s at 25°C, there can be mentioned "KF-96L-0.65cs" (hexamethyldisiloxane, dynamic viscosity 1.0 mm 2 / s) and "TMF1.5" (octamethyltrisiloxane, dynamic viscosity 1.0 mm 2KF-96L-1.5cs" (decamethyltetrasiloxane, dynamic viscosity 1.5 mm 2 KF-96L-2cs" (dodecamethylpentasiloxane, dynamic viscosity 2.0 mm 2 KF-995" (decamethylcyclopentasiloxane, dynamic viscosity 4.0 mm 2 "SH200C Fluid 1.5cs" manufactured by Dow Corning Toray Co., Ltd., "TSF451-0.65" manufactured by Momentive Performance Materials Japan Co., Ltd., "BELSIL DM 0.65" manufactured by Wacker Asahikasei Silicone Co., Ltd., and the like.

[0198] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the content of the component (B) in the above liquid composition is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, still further preferably 20% by mass or more, yet further preferably 25% by mass or more, yet further preferably 35% by mass or more, yet further preferably 45% by mass or more, yet further preferably 50% by mass or more, yet further preferably 60% by mass or more, yet further preferably 70% by mass or more, yet further preferably 80% by mass or more, and, from the viewpoint of the degree of freedom in the formulation of the liquid composition, is preferably 99.9% by mass or less, more preferably 99.5% by mass or less, further preferably 99% by mass or less, still further preferably 97% by mass or less, yet further preferably 95% by mass or less.

[0199] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the product of the volatility (%) of the volatile solvent B and the content (% by mass) of the volatile solvent B in the above liquid composition divided by 100 [〔volatility (%) x content (% by mass)〕 / 100] is preferably 5 or more, more preferably 20 or more, further preferably 35 or more, still further preferably 40 or more, yet further preferably 45 or more, yet further preferably 60 or more, yet further preferably 70 or more, and is preferably 99.9 or less.

[0200] From the viewpoint of finely controlling the shape of the skin surface without impairing the natural appearance, the mass ratio (A / B) of the content of the polymer A to the volatile solvent B (hereinafter, referred to as "content mass ratio (A / B)") in the above liquid composition is preferably 0.05 or more, more preferably 0.07 or more, and further preferably 0.1 or more, and from the viewpoint of adjusting the viscosity of the liquid composition so that the liquid composition is excellent in the impartability of fine droplets, it is preferably 0.3 or less, more preferably 0.25 or less, and further preferably 0.2 or less.

[0201] (Other components)

[0202] The liquid composition used in the present application can contain, in addition to the polymer A and the volatile solvent B, other components which are usually formulated in cosmetics and the like, as long as the effects of the present application are not impaired. As such components, for example, components other than the polymer A and the volatile solvent B, such as oil agents, surfactants, water-soluble polymers, antioxidants, ultraviolet absorbers, ultraviolet scatterers, vitamin agents, preservatives, pH adjustors, fragrances, cosmetic components, pharmaceutical components, plant extractives, moisturizers, coloring agents, cooling agents, antiperspirants, bactericides, preservatives, skin activators, and the like, can be mentioned. One kind of each of these components can be used alone or two or more kinds of each of these components can be used in combination.

[0203] [Non-volatile oil]

[0204] The liquid composition used in the present application can contain a non-volatile oil as an oil agent other than the volatile solvent B. The non-volatile oil refers to an oil having a volatility of less than 5% as described above.

[0205] As the non-volatile oil, ester oils, silicone oils, hydrocarbon oils, higher fatty acids, higher alcohols, and the like which are liquid at 25°C under 1 atm can be mentioned.

[0206] As the non-volatile oil which is liquid, for example, monoester oils such as isononyl isotridecyl ester; diester oils such as diisostearyl polyglyceryl ester, di(cholstanol / behenyl alcohol / octyldodecanol) lauroyl glutamate, di(octyldodecanol / phytosteryl / behenyl) lauroyl glutamate; triester oils such as tri(octanoic acid / decanoic acid / myristic acid / stearic acid) glyceryl ester; and the like can be mentioned. 2 Silicone oils such as dimethylpolysiloxane having a dynamic viscosity of 5 mm2 / s or more at 25°C; hydrocarbon oils such as liquid paraffin, hydrogenated polyisobutylene, light liquid isohydrocarbon, heavy liquid isohydrocarbon, liquid petrolatum, squalane, pristane, squalene, isohexadecane; higher fatty acids having 12 or more and 22 or less carbon atoms; higher alcohols having 12 or more and 28 or less carbon atoms; and the like can be mentioned.

[0207] The liquid composition described above can also contain a non-volatile oil that is solid at 25°C under 1 atmosphere of pressure, within a range that does not hinder the effects of the present application.

[0208] As the non-volatile oil that is solid, mention can be made of solid ester oils such as glyceryl monostearate, glyceryl monomyristate, and the like; solid silicone oils such as alkyl-modified silicones, polyether-modified silicones, and the like; solid hydrocarbon oils such as petrolatum and the like; solid higher alcohols such as cetyl alcohol, stearyl alcohol, behenyl alcohol, and the like; solid higher fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, 12-hydroxystearic acid, lanolin fatty acid, and the like.

[0209] In the case where the liquid composition used in the present application contains a non-volatile oil, the content of the non-volatile oil in the liquid composition is preferably 0.3% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.7% by mass or more, from the viewpoint of improving the impartability of the fine droplets to the skin, and is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less, and still further preferably 3% by mass or less, from the viewpoint of finely controlling the shape of the skin exterior without impairing the naturalness of the appearance, and from the viewpoint of suppressing stickiness when imparted to the skin.

[0210] [Cross-linking silicone resin]

[0211] The liquid composition used in the present application can also contain a cross-linking silicone resin, within a range that does not hinder the effects of the present application.

[0212] As the cross-linking silicone resin described above, mention can be made of cross-linking silicone resins cross-linked by divinyl dimethyl polysiloxane (vinyl dimethicone), phenyl vinyl dimethyl polysiloxane (phenyl vinyl dimethicone), PEG-10 diallyl ether, PEG-15 diallyl ether, and the like. Specifically, mention can be made of (polydimethylsiloxane / vinyl dimethicone) cross-linked polymer, (vinyl dimethicone / methicone silsesquioxane) cross-linked polymer, (vinyl dimethicone / lauryl dimethicone) cross-linked polymer, (polydimethylsiloxane / (PEG-10 / 15)) cross-linked polymer, (PEG-15 / lauryl dimethicone) cross-linked polymer, (polydimethylsiloxane / phenyl vinyl dimethicone) cross-linked polymer, and the like.

[0213] As commercially available products of the cross-linking silicone resin, mention can be made of the KSP series, the KMP series, the KSG series, and the like, of Shin-Etsu Chemical Co., Ltd.

[0214] In the case where the liquid composition used in the present application contains the cross-linking type silicone resin, the content of the cross-linking type silicone resin in the liquid composition is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and further preferably 0.7% by mass or more from the viewpoint of improving the impartability of the fine droplets to the skin, and is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance.

[0215] In the case where the liquid composition contains other components in addition to the polymer A and the volatile solvent B, the total content of the polymer A and the volatile solvent B in the liquid composition is preferably 80% by mass or more, more preferably 85% by mass or more, further preferably 90% by mass or more, and more further preferably 95% by mass or more from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance. The upper limit of the total content of the polymer A and the volatile solvent B in the liquid composition is 100% by mass.

[0216] In the case where the liquid composition contains other components in addition to the polymer A and the volatile solvent B, the mass ratio (A / other components) of the content of the polymer A with respect to the content of the other components (hereinafter, both are referred to as "content mass ratio (A / other components)") in the liquid composition is preferably 1 or more, more preferably 2 or more, and further preferably 3 or more from the viewpoint of suppressing the formation of a smooth feeling of smoothness on the entire surface of the skin subjected to the treatment, and is preferably 20 or less, more preferably 17 or less, and further preferably 15 or less from the viewpoint of improving the shrinking action of the skin without impairing the naturalness of the appearance.

[0217] The viscosity at 35°C of the liquid composition is preferably 1 mPa-s or more, more preferably 1.5 mPa-s or more, and further preferably 2 mPa-s or more from the viewpoint of suppressing the formation of a smooth feeling of smoothness on the entire surface of the skin subjected to the treatment, and is preferably 20 mPa-s or less, more preferably 15 mPa-s or less, and further preferably 10 mPa-s or less from the viewpoint of performing high-precision patterning printing. The viscosity at 35°C of the liquid composition can be measured using an E-type viscometer "TV-25" (manufactured by Tokimec, Inc., using a standard cone rotor 1° 34' x R24 at a rotation speed of 50 rpm).

[0218] <Imparting of fine droplets>

[0219] If the method of applying the fine droplets of the liquid composition in Step 1 to the skin is a method capable of applying the fine droplets to the desired area of the skin in such a manner that the mass of each droplet becomes within a prescribed range, there is no particular limitation. For example, methods such as a method of applying fine droplets of a liquid composition by pattern printing used in a printing system, a method of spraying fine droplets of a liquid composition from above a portion of the skin that has been masked using a spray device (sprayer) or the like, and the like can be cited. Among these, a method using pattern printing used in a printing system is preferred. If this pattern printing is used, it is possible to control the mass of each droplet of the fine droplets of the liquid composition, the amount of application per unit area of the fine droplets, the application area, and the like in Step 1, and it is possible to control the contraction of the skin in Step 2 planarly or in three dimensions. In addition, by designing the printing pattern used, it is possible to design the shape of the skin after treatment in advance. In addition, if this pattern printing is used, it is possible to improve the reproducibility of the skin treatment, and thus the skin treatment method of the present application can also be applied as a cosmetic surgery in a non-invasive cosmetic surgery technique or a cosmetic salon or the like. Among these, from the viewpoint of non-invasiveness, reproducibility, and ease of skin treatment, the skin treatment method of the present application is preferably applied to a cosmetic method in which a cosmetic surgery is performed.

[0220] As the pattern printing used in the present application, on-demand printing such as an inkjet method, a dispensing method, and the like; analog printing such as screen printing, flexographic printing, gravure printing, offset printing, and the like can be cited, and can be selected and used in accordance with the viscosity and the like of the liquid composition.

[0221] On-demand printing is a plateless method that does not require a plate, and is a method of printing in a state in which the skin is not contacted.

[0222] Analog printing is a method of printing in a state in which the skin is contacted.

[0223] Among these methods, on-demand printing can spray fine droplets of a liquid composition and apply a desired amount of fine droplets to a desired area of the skin, can control the mass of each droplet of the fine droplets, the amount of application per unit area of the fine droplets, the application area, and the like, and makes it easy to control the shape of the skin in detail. From this viewpoint, the method of applying fine droplets to the skin in Step 1 is preferably a method of applying fine droplets to the skin by spraying the above liquid composition by one or more methods selected from an inkjet method and a dispensing method.

[0224] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the mass of each of the fine droplets in Step 1 is preferably 0.001 μg or more, more preferably 0.005 μg or more, further more preferably 0.01 μg or more, still further more preferably 0.02 μg or more, yet further more preferably 0.03 μg or more, and 100 μg or less, preferably 50 μg or less, more preferably 30 μg or less, further more preferably 10 μg or less, yet further more preferably 7 μg or less, yet further more preferably 5 μg or less, and yet further more preferably 3 μg or less.

[0225] As for the mass of each of the fine droplets, in the case where, for example, the method of imparting the fine droplets is a method of jetting the liquid composition to impart the fine droplets to the skin, the mass can be calculated from the average diameter of the fine droplets jetted to the skin, or from the change in the mass of the liquid composition when a certain prescribed number of fine droplets are jetted.

[0226] In addition, in the case where the method of imparting the fine droplets is a method performed by printing with a plate, the mass can be calculated from the size of the holes or cells formed in the plate or the like.

[0227] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the imparted amount per unit area of the fine droplets in Step 1 is preferably 0.1 mg / cm 2 More preferably, 0.2 mg / cm 2 Further more preferably, 0.3 mg / cm 2 Yet further more preferably, 0.5 mg / cm 2 Yet further more preferably, 0.7 mg / cm 2 More preferably, 3 mg / cm 2 More preferably, 2 mg / cm 2 Further more preferably, 1.5 mg / cm 2 More preferably, 1.5 mg / cm

[0228] The interval between the fine droplets imparted to the skin by Step 1 (the distance between the centers of adjacent fine droplets) is preferably 0.01 mm or more, more preferably 0.03 mm or more, further more preferably 0.05 mm or more, yet further more preferably 0.1 mm or more, yet further more preferably 0.3 mm or more, and yet further more preferably 0.5 mm or more, and 2 mm or less, more preferably 1.5 mm or less, further more preferably 1 mm or less.

[0229] Note that, in the case where the minute droplets of the liquid composition are imparted to the skin in process 1 by the composition printing, the interval between the minute droplets can be adjusted by the printing pitch.

[0230] The average diameter of the minute droplets imparted to the skin by process 1 is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more, and is preferably 500 μm or less, more preferably 450 μm or less, further preferably 400 μm or less, and still further preferably 350 μm or less.

[0231] In the case where the minute droplets of the liquid composition are imparted to the skin in process 1 by the composition printing using a printing system, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, and particularly the wrinkle improvement effect, the ratio of the interval between the minute droplets imparted by process 1 (printing pitch) to the average diameter of the minute droplets (printing pitch / average diameter of the minute droplets) is preferably 0.3 or more, more preferably 0.7 or more, and further preferably 1 or more, and is preferably 3 or less, more preferably 2.5 or less, and further preferably 2 or less.

[0232] In addition, from the viewpoint of the relief formation effect on the skin, the ratio of the interval between the minute droplets imparted by process 1 (printing pitch) to the average diameter of the minute droplets (printing pitch / average diameter of the minute droplets) is preferably 0.3 or more, more preferably 0.7 or more, and further preferably 1 or more, and is preferably 3 or less, more preferably 2.5 or less, and further preferably 2 or less, and still further preferably 1.5 or less.

[0233] As for the interval between the minute droplets and the average diameter of the minute droplets imparted to the skin, the measurement can be performed by observation using an optical microscope, 20 points are measured for the measurement object, and the average value thereof is calculated to obtain the value.

[0234] In the case where the method of imparting the minute droplets in process 1 is the inkjet method, as the ejection method of the inkjet, either of a thermal type and a piezoelectric type can be used.

[0235] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the applied voltage of the ejection head of the inkjet is preferably 5 V or more, more preferably 10 V or more, and further preferably 15 V or more, and is preferably 50 V or less, more preferably 45 V or less, and further preferably 40 V or less.

[0236] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the driving frequency of the ejection head of the inkjet is preferably 1 kHz or more, more preferably 3 kHz or more, and is preferably 300 kHz or less, more preferably 150 kHz or less, further preferably 90 kHz or less, and still further preferably 50 kHz or less.

[0237] In the case where the method of imparting the minute droplets in the process 1 is the nanodispensing method, as the ejection method of the nanodispensing, an ejection method capable of ejecting the liquid composition to the print object in a non-contact manner is preferable, and an ejection method using a piezoelectric element is more preferable.

[0238] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the applied voltage of the ejection head of the nanodispensing is preferably 5 V or more, more preferably 10 V or more, and further preferably 15 V or more, and is preferably 100 V or less, more preferably 80 V or less, and further preferably 60 V or less.

[0239] From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the driving frequency of the ejection head of the nanodispensing is preferably 1 Hz or more, more preferably 5 Hz or more, and is preferably 30 kHz or less, more preferably 10 kHz or less, further preferably 5 kHz or less, and still further preferably 1 kHz or less.

[0240] In the process 1, the minute droplets of the liquid composition can also be imparted to the entire surface of the desired imparting region of the skin, but from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the contraction of the skin can be controlled by adjusting the print pattern, the number of prints, the order of imparting the minute droplets, and the like, and the control of the shape of the outside of the skin can be easily performed.

[0241] As for the print pattern used in the patterning printing of the process 1, it can be designed in consideration of the contraction of the skin corresponding to the shape of the outside of the skin after the treatment, and for example, a print pattern in a triangular lattice shape, a square lattice shape, a rectangular lattice shape, or a honeycomb lattice shape can be used.

[0242] In addition, a print pattern made according to the individual mound shape of the skin subjected to the treatment can also be used. For example, in the case where the minute droplets are imparted to each mound of the skin, as the minute droplets imparted to each mound dry, the skin contracts, and thus, a shape in which each mound protrudes can be formed, and the difference in relief between the mound of the convex portion and the furrow of the concave portion can be increased. As a result, the sharpness of the texture of the skin can be increased, and the appearance of the skin can be improved favorably.

[0243] In the case of the method of imparting the minute droplets of the process 1 by the pattern printing, the pattern printing can be printing to impart the desired amount of the minute droplets to the desired entire area of the skin by one printing, or can be printing to impart the desired amount of the minute droplets to the desired area of the skin by dividing into a plurality of printings, but from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, it is preferable to be printing to impart the desired amount of the minute droplets to the desired area of the skin by dividing into a plurality of printings. Thereby, it is possible to control the amount of the liquid composition imparted to each imparted area of the skin, and adjust the shrinking action of the skin.

[0244] Note that, in the case of performing the pattern printing a plurality of times, it is preferable to perform the process 2 in each printing. Thereby, the minute droplets imparted by each printing are dried each time, the mixing of the minute droplets with each other is prevented, and the skin treatment capable of being finely controlled can be performed.

[0245] Even in the case of imparting the minute droplets uniformly over the entire surface of the imparted area, by adjusting the area to which the minute droplets are imparted and the order of the imparting, the skin treatment capable of being finely controlled can be performed.

[0246] For example, in the case where the printed pattern is a square lattice shape, there are: Figure 3 a method (1) of imparting the minute droplets in the order of the numbers illustrated in each lattice of the printed pattern in the square lattice shape as illustrated; and Figure 4 and Figure 5 a method (2) of imparting the minute droplets to the spaced lattices after imparting the minute droplets while spacing the imparted lattices in the order of the numbers illustrated in each lattice of the printed pattern in the square lattice shape as illustrated. Of these, from the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above method (2) is preferable. Thereby, it is possible to further improve the shrinking action of the skin in proportion to the amount of the polymer A imparted. As a reason for embodying such an effect, it is considered as follows: by imparting the minute droplets to the area imparted with spacing, it is possible to lower the vapor pressure of the volatile solvent B around the minute droplets after being imparted to the skin, promote the drying of the minute droplets, and in addition, as illustrated in the cross-sectional view of Figure 6 , the skin is fixed by the imparting of the first minute droplets (illustrated as numbers 1 and 2 in Figure 6 ), and the skin is shrunk, and therefore, the imparting of the minute droplets to the spaced area is continued by the imparting of the second minute droplets (illustrated as numbers 9 and 10 in Figure 6 ), whereby the skin fixed by the imparting of the first minute droplets is further subjected to the shrinking action.

[0247] In this invention, by adjusting not only the mass of each microdroplet and the amount of microdroplets applied per unit area, but also the number or density of microdroplets applied in a direction orthogonal to the desired skin contraction direction, the order in which microdroplets are applied, and the drying conditions of the microdroplets, it is possible to control the direction of skin contraction and the amount of skin contraction.

[0248] For example, in use Figure 7 In the case of the rectangular grid-like printed pattern shown, as the first micro-droplet is applied, through step 1, micro-droplets are continuously applied in the longitudinal direction in the order of numbers 1 to 8 as shown, over a relatively long distance. Then, the micro-droplets are applied in the order of numbers 9 to 16 as shown, with a gap equal to one column of grid space. Since micro-droplets numbered 1 to 16 are applied continuously in the longitudinal direction, the shrinkage caused by the evaporation of volatile solvent B is the same as when the micro-droplets are applied to the entire surface. On the other hand, with a gap equal to one column of grid space in the transverse direction, the volatile solvent B evaporates more easily, and the shrinkage degree of micro-droplets numbered 1 to 16 is approximately equal to that when micro-droplets are applied individually. Next, micro-droplets numbered 17 to 32 are applied through the gaps. Most of the volatile organic solvent B contained in the microdroplets numbered 1-16 has evaporated. Therefore, the evaporation of volatile solvent B contained in the microdroplets numbered 17-32 is hardly hindered, and the lateral contraction of the skin is approximately the same as when the microdroplets are applied individually. Consequently, the longitudinal contraction of the skin is the same as when the entire surface is applied; however, the lateral contraction of the skin is stronger than when the entire surface is applied.

[0249] If the skin treatment method of the present invention is used in this way, the degree of freedom to control the degree and direction of skin contraction becomes greater.

[0250] The skin treatment method of the present invention, by selectively applying micro-droplets to the body parts, can finely control the shape of the skin's exterior without compromising the naturalness of its appearance. Preferably, the skin treatment method of the present invention is applied to methods for improving skin wrinkles or as a cosmetic method for creating skin contours.

[0251] In the case of a method for improving skin wrinkles, it is preferable to apply tiny droplets of a liquid composition to the periphery of the wrinkles in step 1. As the tiny droplets dry in the subsequent step 2, the skin around the wrinkles contracts, smoothing out the depressions in the wrinkled skin and making the wrinkles less noticeable. In this case, by adjusting the mass of each droplet and the amount of liquid composition applied according to the size and depth of the wrinkles in step 1, it can be applied to various types of wrinkles and body parts without particular limitations. It is particularly preferred as a method for improving fine lines at the outer corners of the eyes.

[0252] Herein, the "wrinkle peripheral portion of the skin" in the present specification is distinguished from the inside of the wrinkle, i.e., the concave portion of the skin surface and the concave portion of the texture. Note that, in the case where the skin treatment method of the present application is used as a method for improving the wrinkle of the skin, the fine droplets of the liquid composition are not limited to application to the wrinkle peripheral portion of the skin, but can be imparted to the inside of the wrinkle as well, as long as the effect is obtained.

[0253] From the viewpoint of obtaining the effect of making the wrinkle less noticeable, it is preferable that, in the wrinkle peripheral portion, as the region to which the fine droplets of the liquid composition are imparted, at least a portion of the region intersecting the direction of the wrinkle is included. The direction of the wrinkle refers to the direction in which the texture extends. This is because, by imparting the fine droplets of the liquid composition to the region intersecting the direction of the wrinkle, the skin of the portion in which the wrinkle is generated is stretched, making the wrinkle less noticeable.

[0254] As the region intersecting the direction of the wrinkle, it is preferable that the region along the direction of the wrinkle is included, and the region can be only one side of the wrinkle or both sides. In particular, it is more preferable that the fine droplets of the liquid composition are imparted to the region sandwiching both sides of the wrinkle. This is because, by doing so, the skin of the portion in which the wrinkle is generated is stretched from both sides of the wrinkle, and the wrinkle can be made less noticeable.

[0255] In addition, for example, in the case where the direction of the wrinkle is not parallel to the direction of gravity, such as the case of the crow's feet, it is preferable that the region to which the liquid composition is applied (the region intersecting the direction of the wrinkle) includes the region of the upper side of the wrinkle. The "direction of gravity" herein refers to the direction in which the gravity acts when a person is standing upright, and the "upper side" refers to the direction opposite to the direction of gravity. By applying the composition to at least the region of the upper side of the wrinkle, the skin of the portion in which the wrinkle is generated is stretched upward, and the wrinkle can be made less noticeable. From the same viewpoint as above, in the case where the direction of the wrinkle is not parallel to the direction of gravity, it is more preferable that the region to which the liquid composition is applied is the region sandwiching the upper side and the lower side of the wrinkle, and the region of the upper side of the wrinkle is a wider range than the region of the lower side of the wrinkle.

[0256] In addition, in the case where the skin treatment method of the present application is used as a method for forming the relief of the skin, it is preferable that, in Step 1, the fine droplets of the liquid composition are imparted to the portion in which the concave and convex of the skin surface are to be made noticeable. By this, with the drying of the fine droplets in the subsequent Step 2, the skin tissue is stereoscopically lifted by the contraction of the skin of the portion in which the concave and convex of the skin surface are to be made noticeable, and the relief shape in which the skin is bulged is formed, and thus the concave and convex of the skin surface can be made noticeable and a stereoscopic impression can be imparted.

[0257] In the case where the skin treatment method of the present application is used as a method for forming a relief of the skin, the application of the fine droplets of the liquid composition can be performed without particular limitation at the application site by adjusting the mass of each of the fine droplets, the amount of application of the liquid composition, and the like in accordance with the size and range of the desired relief, and is preferably used as a method for improving the shape of the tear trough.

[0258] In the method for improving the shape of the tear trough, in Figures 11-13 A schematic view of the case where the print pattern used is a rectangular lattice is shown in

[0259] In the method for improving the shape of the tear trough, as the method for applying the fine droplets of Step 1, for example, there can be mentioned: Figure 11 a method (3) in which the fine droplets are applied from the end to the center in the order of the numbers illustrated in each lattice of the print pattern in a rectangular lattice as shown in Figure 12 a method (4) in which the fine droplets are applied spirally from the outer periphery to the center of the rectangular lattice in the order of the numbers illustrated in each lattice of the print pattern in a rectangular lattice as shown in

[0260] In addition, there can be mentioned a method (5) in which, although the fine droplets are applied spirally as in the above-described method (4), the fine droplets are applied while being spaced as shown in Figure 13 After the fine droplets are applied while being spaced, the fine droplets are applied to the spaced lattices from the back. From the viewpoint of finely controlling the shape of the outside of the skin without impairing the naturalness of the appearance, the above-described method (5) is preferred. By this, the skin can be made to swell more in proportion to the amount of application of the polymer A. The reason for this effect is considered to be that, by applying the fine droplets to the spaced regions, the vapor pressure of the volatile solvent B around the fine droplets after being applied to the skin can be reduced, and the drying of the fine droplets can be promoted, and in addition, as shown in Figure 13 the skin is fixed and shrunk by the application of the first fine droplets, and then the fine droplets are applied to the spaced regions by the application of the second fine droplets, whereby the skin that has been fixed by the application of the first fine droplets is further subjected to the shrinking action.

[0261] Note that, for the sake of convenience, Figures 11-13 The print pattern shown in is an example of a print pattern in which the number of fine droplets to be applied is 45, but the actual print pattern is formed of finer and more fine droplets, and as described above, by applying the fine droplets from the outside to the inside of the region to be applied in Step 1, the center of the region to be applied swells, and a relief shape that swells in a tear trough shape can be formed.

[0262] (Step 2)

[0263] Process 2 is a process of shrinking the skin with drying of the fine droplets imparted to the skin by process 1.

[0264] In the present application, fine droplets each of which has a mass within a prescribed range are imparted by process 1, and thus, the drying conditions of the fine droplets in process 2 are not particularly limited, and the drying can be sufficiently performed by natural drying at the temperature of the skin. In addition, from the viewpoint of accelerating the drying, air blow drying, warm air drying, or the like can also be performed.

[0265] In the case where warm air drying is performed, the temperature at the time of drying is not particularly limited, and is preferably 35°C or higher, more preferably 40°C or higher, further preferably 50°C or higher, and still further preferably 55°C or higher, and is preferably 80°C or lower, more preferably 70°C or lower, and further preferably 65°C or lower.

[0266] The drying time is preferably 5 minutes or longer, more preferably 7 minutes or longer, and further preferably 10 minutes or longer, and is preferably 30 minutes or shorter, and more preferably 20 minutes or shorter.

[0267] After process 2, the coating film formed on the skin by process 2 can be removed as needed, or the coating film formed on the skin by process 2 can not be removed, and makeup can be performed on the coating film.

[0268] In the present application, the skin is shrunk with drying of the fine droplets in process 2, and the papillary layer under the skin is deformed, and the return of the deformed papillary layer is slowly generated, and thus, even after the coating film formed on the skin by process 2 is removed, the effect generated by the mechanism of the above-described shrinkage of the skin can be enjoyed. From this viewpoint, after the coating film formed on the skin by process 2 is performed for a prescribed time, the coating film can be removed before makeup is performed, to perform the makeup.

[0269] Example

[0270] Hereinafter, the present application will be described by way of examples, but the present application is not limited to the scope of the examples. In addition, in the present examples, various measurements were performed by the following methods.

[0271] (Number average molecular weight Mn and weight average molecular weight Mw)

[0272] The number average molecular weight Mn and the weight average molecular weight Mw of the polymer were measured by a gel permeation chromatography (GPC) method using polystyrene as a standard material under the following conditions.

[0273] Measurement device: HLC-8320 GPC (manufactured by TOSOH CORPORATION)

[0274] Column: K-806L (manufactured by Shodex), 2 in series

[0275] Detector: RI

[0276] Eluent: 1 mmol / L-Farmin DM20 (manufactured by Kowa Co., Ltd.) / CHCI3

[0277] Flow rate: 1.0 mL / min

[0278] Column temperature: 40°C

[0279] (Deformation ratio)

[0280] As the method (I), the deformation ratio of the polymer A was obtained by the method shown below.

[0281] First, the polymer A was dissolved in the volatile solvent B to prepare a polymer solution having a concentration of 10 mass%. In this case, the polymer solution was prepared so that the concentration of the polymer A in the polymer solution was 10 mass%. Figure 1 (a) A polymer solution 0.005 g was applied to a range of width (W) 20 mm x length (LI) 50 mm from one end la of the short side of the polyethylene sheet 1 toward the length direction of the polyethylene sheet 1 in a range of width (W) 20 mm x length (L0) 100 mm x thickness 0.03 mm of the polyethylene sheet 1 (LL film, manufactured by Enshu-kasei Co., Ltd.) shown in (a), and dried in a thermostat set to 40°C for 10 minutes to produce a polyethylene sheet 1' with a polymer film. Figure 1 (a) A polymer solution 0.005 g was applied to a range of width (W) 20 mm x length (LI) 50 mm from one end la of the short side of the polyethylene sheet 1 toward the length direction of the polyethylene sheet 1 in a range of width (W) 20 mm x length (L0) 100 mm x thickness 0.03 mm of the polyethylene sheet 1 (LL film, manufactured by Enshu-kasei Co., Ltd.) shown in (a), and dried in a thermostat set to 40°C for 10 minutes to produce a polyethylene sheet 1' with a polymer film.

[0282] Here, Figure 1 (b) is a schematic view of the polyethylene sheet 1' in which a part thereof is deformed (crimped) by shrinkage of the polymer film containing the polymer A when the polymer solution applied to the polyethylene sheet 1 is dried to form a polymer film.

[0283] The length of the polyethylene sheet 1 to which the above polymer solution was applied was set to LI (50 mm), and the length of the polyethylene sheet 1' with a polymer film in which a part thereof was deformed (crimped) by drying of the applied polymer solution was set to L2, and the value of L2 / L1 was calculated, and this value was set as the deformation ratio of the polymer A. Note that L2 was set as the average of the values measured on both long edges of the polyethylene sheet 1' with a polymer film.

[0284] (Volatility)

[0285] A sample 0.5 g was placed in a glass dish having a diameter of 40 mm, and left to stand on a hot plate set to 40°C for 30 minutes under an environment of 60% RH under 1 atm to volatilize. The mass of the sample before volatilization was set to W0 (g), the mass of the sample after volatilization was set to Wi (g), and the value of [(W0-W1) / W0] x 100 was set as the volatility (%). The larger this value, the faster the volatilization speed.

[0286] Preparation Example 1 (Preparation of polymethacrylic acid solution)

[0287] Into a glass reaction vessel, polymethacrylic acid (manufactured by FUJIFILM Wako Pure Chemical Corporation, special grade) 300 g, ethanol (manufactured by FUJIFILM Wako Pure Chemical Corporation, grade 1) 1.5 L, and 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by FUJIFILM Wako Pure Chemical Corporation, grade 1) 1.73 g as a polymerization initiator were put, and polymerization was performed at 65°C for 4 hours. The obtained polymer solution was added dropwise into acetone 20 L, and reprecipitation was performed. The precipitate was recovered by filtration, and dried at 65°C under a reduced pressure of 10 kPa for 12 hours or more to obtain polymethacrylic acid. The weight average molecular weight of the obtained polymethacrylic acid was 170,000.

[0288] The obtained polymethacrylic acid was dissolved in ethanol (manufactured by FUJIFILM Wako Pure Chemical Corporation, grade 1) to prepare a polymethacrylic acid solution having a concentration of 10 mass%.

[0289]

[0290] Examples 1 to 39

[0291] (Step 1)

[0292] Using the liquid compositions and conditions shown in Tables 1 to 4, the area of 5.6 mm in length and 10.4 mm in width of the artificial skin model "Bioskin outer corner wrinkle model" (manufactured by Beaulax Corporation, product number: No. 145-2 wrinkle level 4) as a replica sample of skin was subjected to pattern printing to impart minute droplets of the liquid composition. Note that the pattern printing was performed on the wrinkle peripheral portion, avoiding the deep wrinkle portion of the outer corner of the wrinkle model formed on the replica sample.

[0293] The pattern printing device used a piezoelectric jet dispenser "PICO Pulsar SD" (manufactured by Nordson EFD), and as the liquid assembly, "FLUID ASSY Pulsar MST 3.0S F0E05" (opening 50 μm, ball size 3.0S) was used. Note that the movement of the dispensing used "PRO4" manufactured by Nordson Corporation.

[0294] Note that the mass of the minute droplets of each drop shown in Tables 1 to 4 was calculated from the change in the mass of the liquid composition at the time of ejection of the minute droplets. The average diameter of the minute droplets and the printing pitch were obtained by the following method: by using an optical microscope, 20 points of the measurement object were measured, and the average value was calculated as the measurement value. The printing pattern shown in Tables 1 to 4 is as follows. ​

[0295] Printed pattern 1 : As shown in Figure 3 the drawing, using a square lattice pattern, from the end of the pattern, in the lateral direction, the microdroplets are imparted in the order of the numbers shown in the drawing, and printing is performed on the entire surface of the printed area.

[0296] Printed pattern 2 : As shown in Figure 4 the drawing, using a square lattice pattern, from the end of the pattern, in the lateral direction, the regions of every other lattice are imparted with microdroplets in the order of the numbers shown in the drawing, and then the regions of every other lattice not imparted with microdroplets are imparted with microdroplets, and printing is performed. In the longitudinal direction of the lattice, printing is performed adjacently without intervals.

[0297] Printed pattern 3 : As shown in Figure 5 the drawing, using a square lattice pattern, from the end of the pattern, in the lateral and longitudinal directions, the regions of every other lattice are imparted with microdroplets in the order of the numbers shown in the drawing, and then the regions of every other lattice not imparted with microdroplets are imparted with microdroplets, and printing is performed.

[0298] (Step 2)

[0299] Next, the artificial skin model imparted with the microdroplets is dried in a constant temperature chamber set to 40°C for 10 minutes. The wrinkle improvement effect is evaluated by the method shown below. The results are shown in Tables 1 to 4.

[0300] Note that in the case where the number of times of printing is plural, Step 2 is performed for each time of printing.

[0301] Comparative Example 1

[0302] The liquid composition shown in Table 1 is changed, and otherwise, the wrinkle improvement effect is evaluated in the same manner as in Example 1. The results are shown in Table 1.

[0303] Comparative Example 2

[0304] Using the liquid composition 1 shown in Table 1, using a microsyringe (manufactured by Hamilton), a microdroplet having a mass of 30,000 μg per drop is imparted to the above artificial skin model "Bioskin outer corner wrinkle model" (Step 1'), and then, in the same manner as in Example 1, the microdroplet is dried (Step 2). Next, the wrinkle improvement effect is evaluated by the method shown below. The results are shown in Table 1.

[0305] < Evaluation >

[0306] (Quantitative evaluation of wrinkle improvement effect)

[0307] Using the evaluation samples obtained in the examples and comparative examples, as a quantitative evaluation of the wrinkle improvement effect on the outer corner of the eye, image evaluation was performed using an image analysis software (ImageJ, manufactured by National Institutes of Health, USA).

[0308] First, using a standard light source device "Macbeth judge II" (light source: D65 lamp) (manufactured by X-Rite), the evaluation samples obtained in the examples and comparative examples were placed in the center of a standard light source room, and photographed using a digital camera.

[0309] Next, after converting the photographed image into an 8-bit gray scale image using ImageJ, the area in which the wrinkle model was formed (horizontal 2280 pixels x vertical 2790 pixels) was selected, and the histogram data of the density was extracted. The obtained data was converted into 256 gray scales from 0 to 255, and the number of pixels corresponding to each density was calculated. As the density value, the darker part was close to 0, and the brighter part was close to 255. In addition, the total number of the obtained data exceeded 10,000 pixels, and therefore, the number of pixels per 10,000 pixels was converted, and the first digit after the decimal point was rounded off to the nearest integer.

[0310] In the above photographing process, in order to improve the reliability of the image evaluation, in the case where a pixel indicating 0 or 255 was detected in the value of the histogram of the density, if it was 0, it was considered that the light source was in an excessively dark state, and if it was 255, it was considered that the light source was in an excessively bright state, and the light source was adjusted. In the photographing of the evaluation samples obtained in the examples and comparative examples, it was confirmed that no pixel indicating a value in the range of 0 to 5 and 235 to 255 was observed.

[0311] In addition, in order to confirm the individual difference of each artificial skin model used, the number of pixels was measured under the same exposure conditions, and the average value and the deviation amplitude were calculated, and it was confirmed that the deviation amplitude from the average value was within the range of ± 5% in all areas. Furthermore, with respect to the artificial skin model before the skin treatment, the photographing was performed using a digital camera by the same method as the evaluation samples obtained in the examples and comparative examples, the photographed image was converted into an 8-bit gray scale image using ImageJ, and the number of pixels per 10,000 pixels was converted.

[0312] The obtained data was respectively totaled in the number of pixels in the range of 0 to 20 of the density, the number of pixels in the range of 0 to 30 of the density, and the number of pixels in the range of 0 to 40 of the density.

[0313] From the appearance of the skin, the wrinkles are conspicuous in the dark part observed, and the total number of pixels in the range of the density concentration of 0 to 20 becomes the most important index of the wrinkles. Therefore, as an index indicating the degree of reduction of the wrinkles, the ratio of the total number of pixels after the skin treatment to that before the skin treatment in the range of the density concentration of 0 to 20 is calculated as the improvement rate (1) (%) of the wrinkles, and is used for the evaluation. The smaller the value of the improvement rate (1) of the wrinkles, the more the wrinkles are reduced, and the more excellent the wrinkle improvement effect at the outer corner of the eye is indicated.

[0314] In addition, from the total number of pixels before and after the skin treatment in the range of the density concentration of 0 to 30 and in the range of the density concentration of 0 to 40, the improvement rate (2) (%) of the wrinkles and the improvement rate (3) (%) of the wrinkles are respectively calculated in the same manner as the improvement rate (1) (%) of the wrinkles, and these results are also used for the evaluation. The smaller the value of the improvement rate (2) of the wrinkles and the improvement rate (3) of the wrinkles, the more the wrinkles are reduced, and the more excellent the wrinkle improvement effect at the outer corner of the eye is indicated.

[0315] (Quantitative evaluation of the persistence of the wrinkle improvement effect)

[0316] The degree of the improvement effect of the fine wrinkles at the outer corner of the eye of the evaluation sample obtained in the examples and the comparative examples is qualitatively evaluated by visual observation.

[0317] [evaluation criteria]

[0318] 5: The fine wrinkles at the outer corner of the eye are not at all observed, and the appearance after the treatment is also natural.

[0319] 4: The fine wrinkles at the outer corner of the eye are considerably thinned, and the appearance after the treatment is also natural.

[0320] 3: The fine wrinkles at the outer corner of the eye are slightly thinned, and the appearance after the treatment is also natural.

[0321] 2: The fine wrinkles at the outer corner of the eye are hardly thinned, and there is not much change from before the treatment.

[0322] 1: The fine wrinkles at the outer corner of the eye are not at all thinned or the fine wrinkles are increased from before the treatment, and the appearance after the treatment is unnatural.

[0323] (Quantitative evaluation of the persistence of the wrinkle improvement effect)

[0324] Using the evaluation sample obtained in the examples and the comparative examples, as the quantitative evaluation of the persistence of the wrinkle improvement effect at the outer corner of the eye, the evaluation sample is given a deformation, and the image evaluation is performed by the same method as the above quantitative evaluation of the wrinkle improvement effect.

[0325] As for the evaluation sample, the sample was left for 10 minutes in an environment of 25°C, 50% RH, whereby the temperature and humidity of the sample were adjusted, and the evaluation sample was wound around a resin-made cylinder having a diameter of 80 mm and a smooth surface for 1 second in such a manner that the printed surface on which the treatment was performed was directed outward. The evaluation sample was returned to a flat state again for 1 second, and the above operation was set to one time, and the deformation operation was performed 100 times.

[0326] Next, using the evaluation sample to which the deformation was imparted, image evaluation was performed by the same method as the quantitative evaluation of the wrinkle improvement effect described above.

[0327] As with the quantitative evaluation of the wrinkle improvement effect described above, from the appearance of the skin, the place where the wrinkles were observed to be darker was conspicuous, and the total pixel count in the range of the density concentration of 0 to 20 became the most important index of the wrinkles. Therefore, as an index of the persistence of the wrinkle improvement effect, the ratio of the total pixel count of the skin after the treatment to the total pixel count of the skin before the treatment, which was contained in the range of the density concentration of 0 to 20, was calculated as the persistent improvement rate (4) (%) of the wrinkles, and was used for evaluation. The smaller the value of the persistent improvement rate (4) of the wrinkles, the more excellent the persistence of the improvement effect of the wrinkles at the outer corner of the eye.

[0328] In addition, from the total pixel counts of the skin before and after the treatment, which were contained in the range of the density concentration of 0 to 30 and the range of the density concentration of 0 to 40, the persistent improvement rate (5) (%) of the wrinkles and the persistent improvement rate (6) (%) of the wrinkles were respectively calculated as with the persistent improvement rate (4) (%) of the wrinkles, and these results were also used for evaluation. The smaller the values of the persistent improvement rate (5) of the wrinkles and the persistent improvement rate (6) of the wrinkles, the more excellent the persistence of the improvement effect of the wrinkles at the outer corner of the eye.

[0329] In addition, in the quantitative evaluation of the persistence, it is preferable that the difference [persistent improvement rate (4) of the wrinkles - improvement rate (1) of the wrinkles] of the above-mentioned improvement rate (1) of the wrinkles and the persistent improvement rate (4) of the wrinkles be small. The smaller the difference, the more the improvement of the wrinkles after the first treatment can be maintained in a good state even if subjected to external force or sudden deformation. Therefore, the value of the difference [persistent improvement rate (4) of the wrinkles - improvement rate (1) of the wrinkles] is also shown in Tables 1 to 4. Similarly, as for the difference of the above-mentioned improvement rate (2) of the wrinkles and the persistent improvement rate (5) of the wrinkles, and the difference of the above-mentioned improvement rate (3) of the wrinkles and the persistent improvement rate (6) of the wrinkles, it is preferable that the values of the differences be small.

[0330] Details of the ingredients used in the examples and comparative examples shown in each table are as follows.

[0331] Note that the blending amount (mass %) of each of the other ingredients shown in each table is as described above.

[0332] *1: "NBN-30-ID" (isododecane solution of (norbornene / tris(trimethylsiloxy)silylnorbornene) copolymer (molar ratio (e / f) = 60 / 40 in the following formula (4), Mn = 360,000) manufactured by Shin-Etsu Chemical Co., Ltd., active ingredient concentration: 30 mass%) was dried at 50°C under reduced pressure for 12 hours, and the obtained solid content was used.

[0333]

[0334] *2: "TSPL-30-ID" (isododecane solution of tris(trimethylsiloxy)silylpropyl carbamoyl amylopectin, active ingredient concentration: 30 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was dried at 50°C under reduced pressure for 12 hours, and the obtained solid content was used.

[0335] *3: "XS66-B8226" (cyclopentasiloxane solution of trifluoropropyl dimethyl / trimethylsiloxy silicic acid, active ingredient concentration: 50 mass%) manufactured by Momentive Performance Materials Japan KK was dried at 50°C under reduced pressure for 12 hours, and the obtained solid content was used.

[0336] *4: "X-21-5595" (isododecane solution of trimethylsiloxy silicic acid, active ingredient concentration: 60 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was dried at 50°C under reduced pressure for 12 hours, and the obtained solid content was used.

[0337] *5: The polymethacrylic acid obtained in Preparation Example 1.

[0338] *6: Polystyrene sulfonic acid sodium (manufactured by Alfa Aesar, weight average molecular weight: 70,000).

[0339] *7: "KP-550" (isododecane solution of graft copolymer composed of acrylic acid polymer and dimethyl polysiloxane, active ingredient concentration: 40 mass%) manufactured by Shin-Etsu Chemical Co., Ltd. was dried at 50°C under reduced pressure for 12 hours, and the obtained solid content was used.

[0340] *8: "KF-96L-0.65cs" manufactured by Shin-Etsu Chemical Co., Ltd.

[0341] *9: "Cosmall 42V" manufactured by Nisshin OilliO Co., Ltd.

[0342] *10: "Salacos 913" manufactured by Nisshin OilliO Co., Ltd.

[0343] *11: "Salacos 334" manufactured by Nisshin OilliO Co., Ltd.

[0344] *12: "Eldew CL-301" manufactured by Ajinomoto Co., Ltd.

[0345] *13: "Eldew PS-306" manufactured by Ajinomoto Co., Ltd.

[0346] *14: "Parleam EX" manufactured by NOF Corporation.

[0347] *15: "Nomcoat W" manufactured by Nissin Oillio Co., Ltd.

[0348] *16: Shin-Etsu Chemical Industry Co., Ltd. manufactures "KF-96A-6cs".

[0349] *17: Shin-Etsu Chemical Industry Co., Ltd. manufactures "KSP-100".

[0350] *18: Shin-Etsu Chemical Co., Ltd. manufactures "KSG-42A" (isododecane solution, active ingredient concentration 20% by mass).

[0351] *19: Shin-Etsu Chemical Co., Ltd. manufactures "KSG-210" (dimethylpolysiloxane (dynamic viscosity 6mm)). 2 (Solution, active ingredient concentration 25% by mass).

[0352] *20: Shin-Etsu Chemical Co., Ltd. manufactures "KSG-320" (isododecane solution, active ingredient concentration 25% by mass).

[0353] *21: "TREFIL E-506S" manufactured by Toray Corning Co., Ltd.

[0354] *22: Shin-Etsu Chemical Co., Ltd. manufactures "KSG-16" (dimethylpolysiloxane (dynamic viscosity 6mm)). 2 (Solution, active ingredient concentration 25% by mass).

[0355]

[0356] As shown in Table 1, compared with Comparative Examples 1 and 2, the fine lines at the outer corners of the eyes in Examples 1 to 15 were less noticeable both quantitatively and qualitatively, and the appearance after treatment was also good.

[0357] Regarding the wrinkle improvement effect, the results of Example 13 are presented in... Figure 8 The results of Comparative Example 2 are shown in [the diagram]. Figure 9 As shown in the image. Figure 8 (8a) and Figure 9 (9a) are photos of the area around the wrinkles before skin treatment. Figure 8 (8b) and Figure 9(9b) are photographs of the periphery of the wrinkle after the skin treatment. As is apparent from Figure 8 the photograph, in Example 13, the fine lines of the periphery of the wrinkle were not apparent; in contrast, as is apparent from Figure 9 the photograph, in Comparative Example 2, unnatural wrinkle-like appearance was newly formed on the surface of the coating film, and fine unevenness was generated on the surface of the coating film.

[0358] [Table 2]

[0359]

[0360] As is apparent from Table 2, in Examples 16 to 21, regardless of the kind of polymer A or the change in the volatile solvent B, the fine lines of the outer corner of the eye were not apparent quantitatively and qualitatively.

[0361] [Table 3]

[0362]

[0363]

[0364] [Table 4]

[0365]

[0366]

[0367] As is apparent from Tables 3 and 4, in Examples 22 to 39, regardless of the addition of any component, the fine lines of the outer corner of the eye were not apparent quantitatively and qualitatively.

[0368] Examples 40 to 54 and Comparative Example 3

[0369] (Step 1)

[0370] Using the liquid composition and conditions shown in Table 5, the area of 5.6 mm in length and 10.4 mm in width of the artificial skin model "Bioskin outer corner of the eye wrinkle model" (manufactured by Beaulax Co., Ltd., product number: No. 145-2 wrinkle level 8) as a replica sample of the skin was subjected to pattern printing, and fine droplets of the liquid composition were imparted. Note that the pattern printing was performed in such a manner as to follow both ends of the deep wrinkle portion along the outer corner of the eye.

[0371] In Examples 40 to 51, as the patterning printing device, a device in which a portable inkjet printer "KGKJET HQ1000H" (manufactured by Kijiyaku Sangyo Co., Ltd.) was modified so as to be able to control the printing pitch using "PRO4" manufactured by Nordson Corporation was used. For the ink cartridge "TK403 Black-CS cartridge" (manufactured by Kijiyaku Sangyo Co., Ltd.), the inside thereof was washed with ion-exchange water and ethanol, filled with ion-exchange water having an electric conductivity of 0.6 μS / cm or less, the ion-exchange water ejected from the inkjet head was collected, and after confirming that the electric conductivity became 1.0 μS / cm or less, the inside thereof was emptied and dried using a vacuum drier, and then used.

[0372] In Examples 52 to 54 and Comparative Example 3, as the patterning printing device, the piezoelectric jet dispenser described above was used as in Example 1.

[0373] Note that the mass of each of the fine droplets, and the average diameter of the fine droplets and the printing pitch shown in Table 5 were obtained by the same method as described above. The respective numbers of the printed patterns shown in Table 5 were also as described above.

[0374] (Step 2)

[0375] Next, the artificial skin model to which the fine droplets were imparted was dried in a constant-temperature bath set to 40°C for 10 minutes. The wrinkle improvement effect and the persistence of the wrinkle improvement effect were evaluated by the same method as described above. The results are shown in Table 5.

[0376] Note that in the case where the number of printing is plural, Step 2 is performed for each of the plural times of printing.

[0377]

[0378]

[0379] As is clear from Table 5, in Examples 40 to 54, the fine lines at the outer corner of the eye were not easily noticeable, both quantitatively and qualitatively, as compared with Comparative Example 3.

[0380] As for the wrinkle improvement effect, the results of Example 42 are shown in Figure 10 . Figure 10 (10a) is a photograph of the wrinkle peripheral portion of the sample before skin treatment, Figure 10 (10b) is a photograph of the wrinkle peripheral portion after skin treatment. As is clear from Figure 10 , in Example 42, the fine lines in the portion surrounded by the white frame were not noticeable.

[0381] <Formation of tear bags>

[0382] Examples 55 to 69 and Comparative Example 4

[0383] (Step 1)

[0384] Using the liquid composition and conditions shown in Table 6, as a replica sample of skin, a silver-faced artificial leather (manufactured by IDEATEX JAPAN Co., Ltd., trade name: Supplale PBZ13001) cut into a width of 3 cm and a length of 4 cm was subjected to patterning printing on an area of 30 mm in the vertical direction and 20 mm in the horizontal direction of the skin texture reproduction surface, and minute droplets of the liquid composition were imparted.

[0385] In Examples 55 to 66, as the patterning printing device, the above-described portable inkjet printer used in Example 40 and the above-described ink cartridge were used, and, like in Example 40, the ink cartridge was used after being cleaned and dried.

[0386] In Examples 67 to 69 and Comparative Example 4, as the patterning printing device, the above-described piezoelectric jet dispenser was used, like in Example 1.

[0387] Note that the mass of each drop of the minute droplets, and the average diameter of the minute droplets and the printing pitch shown in Table 6 were obtained by the same method as described above. The printing patterns shown in Table 6 are described below.

[0388] Printing Pattern 4: As shown in Table 6, a rectangular lattice pattern was used, and minute droplets were imparted in the vertical direction in the order of the numbers shown in the figure from the end of the pattern, and printing was performed on the entire surface of the printing area. Figure 11

[0389] Printing Pattern 5: As shown in Table 6, a rectangular lattice pattern was used, and minute droplets were imparted spirally to the area of each lattice in the order of the numbers shown in the figure from the end of the pattern, and printing was performed. Figure 12

[0390] Printing Pattern 6: As shown in Table 6, a rectangular lattice pattern was used, and minute droplets were imparted spirally to the area of each lattice in the order of the numbers shown in the figure from the end of the pattern, and minute droplets were imparted to the area of each lattice to which no minute droplet had been imparted every time after 1 minute droplet was imparted, and printing was performed. Figure 13

[0391] (Step 2)

[0392] Next, the artificial skin model to which the minute droplets had been imparted was dried in a constant-temperature bath set to 40°C for 10 minutes. Using the obtained evaluation sample, the tear pocket formation effect was evaluated by the method shown below. The results are shown in Table 6.

[0393] Note that in the case where the number of printing times is plural, Step 2 is performed for each printing.

[0394] Comparative Example 5​​​

[0395] Using the liquid composition shown in Table 6, as a replica sample of skin, to a silver face style artificial leather (manufactured by IDEATEX JAPAN Co., Ltd., trade name: Supplale PBZ13001) cut into a width of 3 cm and a length of 4 cm, using the above-mentioned microsyringe, fine droplets were applied (step 1') on the skin texture reproduction surface in such a manner that the mass of each droplet becomes 30,000 μg, and the artificial leather to which the fine droplets were applied was dried in a constant temperature chamber set to 40°C for 10 minutes (step 2).

[0396] However, with drying of the fine droplets of the liquid composition applied to the artificial leather, deformation was applied to the wrinkle model of the artificial leather, and a fine unevenness was generated on the surface of the coating film, and a desired undulating shape in which the artificial leather swells was not obtained.

[0397] Using the obtained evaluation sample, the tear bag forming effect was evaluated by the following method. The results are shown in Table 6.

[0398] < EVALUATION >

[0399] (Evaluation of tear bag forming effect by visual observation)

[0400] The degree of the tear bag forming effect of the evaluation sample obtained in the examples and comparative examples was visually observed, and the evaluation was performed by 5 evaluators in accordance with the following evaluation criteria, by 5 points each, and the total value of the obtained scores is shown in Table 6. The higher the total value, the better the tear bag was formed.

[0401] [ Evaluation Criteria ]

[0402] 5: A very large tear bag-like undulating shape was obtained, and the appearance was also natural.

[0403] 4: A large undulating shape as a tear bag was obtained, and the appearance was also natural.

[0404] 3: A slightly large undulating shape as a tear bag was confirmed, and the appearance was also almost not a problem.

[0405] 2: Slight swelling deformation was confirmed, but the undulating shape as a tear bag was insufficient, the appearance was unnatural, and there was a problem in practical use.

[0406] 1: Almost no swelling deformation was observed.

[0407]

[0408] From Table 6, it was found that: compared to Comparative Examples 4 and 5, Examples 55 to 69 could form a tear bag-like undulating shape in which the artificial leather swells well.

[0409] As for the tear pouch forming effect, the result of Example 57 is shown in Figure 14 . Figure 14 (14b) is a photograph in which an auxiliary line indicating a convex portion is marked on the photograph of (14a). As is apparent from Figure 14 (14b), in Example 57, a relief shape in which a portion in which skin treatment is performed along the auxiliary line is bulged is formed. Figure 14

[0410] [Industrial applicability]

[0411] According to the skin treatment method of the present application, the shape of the outside of the skin can be finely controlled in a non-invasive manner and without impairing the naturalness of appearance, and thus the skin treatment method of the present application can be used for improvement of wrinkles of the skin, formation of a relief shape of the skin, or improvement of sagging.

[0412] [Explanation of symbols]

[0413] 1 polyethylene sheet;

[0414] 1a one end of the short side of the polyethylene sheet 1;

[0415] 1' polyethylene sheet with a polymer film;

[0416] 2 portion to which a polymer solution is applied;

[0417] 21 fine droplets;

[0418] 22 skin.​

Claims

1. A skin treatment method for non-therapeutic purposes, wherein comprises: Process 1: a process of imparting to the skin minute droplets of a liquid composition containing a polymer A and a volatile solvent B, and Process 2: a process of shrinking the skin with drying of the minute droplets imparted to the skin by Process 1, the polymer A is one or more selected from the group consisting of silicone polymers having a structure represented by the following general formula (I), and vinyl-based polymers, In General Formula (I), R 1 each independently represents a hydrocarbon group having 1 or more and 12 or less carbon atoms, and p is an integer of 1 or more. the deformation ratio of the polymer A, measured by the following Method (I), is 0.3 or more and 1 or less, the volatile solvent B is one or more selected from the group consisting of water, aliphatic alcohols having 2 or more and 4 or less carbon atoms, volatile hydrocarbon oils, and volatile silicone oils, the method of imparting the minute droplets to the skin in Process 1 is a method of imparting the minute droplets in the order of the numbers illustrated in each cell of a print pattern shown in one of the figures selected from the group consisting of Fig. 3, Fig. 4, Fig. 5, Fig. 7, Fig. 11, Fig. 12, and Fig. 13, in one or more selected from the group consisting of an inkjet method and a dispensing method, the mass of each of the minute droplets imparted to the skin in Process 1 is 0.001 μg or more and 30 μg or less, the average diameter of the minute droplets imparted to the skin by Process 1 is 10 μm or more and 450 μm or less, the interval between the minute droplets imparted to the skin by Process 1 is 0.01 mm or more and 2 mm or less, Method (I): A polymer A was dissolved in a volatile solvent B to prepare a polymer solution having a concentration of 10 mass%; the polymer solution was applied to one side of a polyethylene sheet having a width of 20 mm x a length of 100 mm x a thickness of 0.03 mm in an amount of 0.005 g in a range of a width of 20 mm x a length of 50 mm from one end of the short side in the length direction, and dried in a thermostat set to 40°C for 10 minutes, whereby a polyethylene sheet with a polymer film was prepared; the length of the polyethylene sheet in the portion to which the polymer solution was applied was set to LI, the length of the polyethylene sheet with a polymer film in the portion deformed due to drying of the applied solution was set to L2, and the value of L2 / L1 was set to the deformation ratio.

2. The skin treatment method for non-therapeutic purposes according to claim 1, wherein 3. The skin treatment method for non-therapeutic purposes according to claim 1, wherein The amount of the microdroplets in process 1 per unit area is 0.1 mg / cm2in terms of the amount of the polymer A 2 The above and 3 mg / cm2 2 The following. the average diameter of the minute droplets imparted to the skin by Process 1 is 10 μm or more and 400 μm or less.

4. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the ratio of the interval between the minute droplets imparted by Process 1, i.e., the print interval, to the average diameter of the minute droplets is print interval / average diameter of the minute droplets = 0.3 or more and 3 or less.

5. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the volatile solvent B has a volatility of 5% or more after being left to volatilize at 40°C and 60% RH for 30 minutes under 1 atm.

6. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein ​ The volatile solvent B is one or more selected from the group consisting of water, ethanol, isododecane, hexamethyldisiloxane, methylpolymethylsiloxane, and dimethylpolysiloxane having a dynamic viscosity of less than 5 mm 2 / s at 25°C.

7. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the content of the polymer A in the liquid composition is 0.1 mass% or more and 30 mass% or less.

8. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the content of the volatile solvent B in the liquid composition is 1 mass% or more and 99 mass% or less.

9. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the product of the volatile rate of the volatile solvent B and the content of the volatile solvent B in the liquid composition divided by 100 is (volatile rate x content) / 100 = 5 or more and 99.9 or less, wherein the unit of the volatile rate is % and the unit of the content of the volatile solvent B in the liquid composition is mass%.

10. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the mass ratio A / B of the content of the polymer A to the content of the volatile solvent B in the liquid composition is 0.05 or more and 0.3 or less.

11. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the total content of the polymer A and the volatile solvent B in the liquid composition is 80 mass% or more and 100 mass% or less.

12. The skin treatment method for non-therapeutic purposes according to claim 1, wherein the vinyl-based monomer constituting the vinyl-based polymer has an anionic group or a cationic group.

13. The skin treatment method for non-therapeutic purposes according to claim 1, wherein the vinyl-based polymer is one or more selected from the group consisting of polymethacrylic acid and sodium polystyrene sulfonate.

14. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein the silicone polymer is one or more selected from the group consisting of a norbornane structure-containing silicone-modified polymer, a silicone-modified pullulan, a silicic acid compound having a silicone structure, and a silicone dendrimer.

15. The skin treatment method for non-therapeutic purposes according to claim 14, wherein the norbornane structure-containing silicone-modified polymer is a polymer having a repeating unit represented by the following general formula (1) or (2), In General Formula (1), R 2 each independently represents an alkyl group having 1 to 12 carbon atoms, X represents a group represented by General Formula (i) below, a is an integer of 1 to 3, and b is an integer of 0 to 2. In general formula (I), R 1 c is an integer of 1 or more and 5 or less, and the same applies to the definition in general formula (I). In General Formula (2), R 1 R is the same as the definition in General Formula (1), R 2 b is the same as the definition in General Formula (1), and d is an integer of 2 or more and 5 or less.

16. The skin treatment method for non-therapeutic purposes according to claim 15, wherein the cyclic silicone structure in the general formula (2) is a structure represented by the following formula (2-1) or (2-2), 。 17. The skin treatment method for non-therapeutic purposes according to claim 15, wherein the proportion of the repeating unit represented by the general formula (1) or (2) in the norbornane structure-containing silicone-modified polymer is 10% or more and 100% or less of the total number of repeating units in the polymer.

18. The skin treatment method for non-therapeutic purposes according to claim 15, wherein the norbornane structure-containing silicone-modified polymer has, in addition to the repeating unit represented by the general formula (1) or (2), a repeating unit represented by the following general formula (3), In General Formula (3), R 3 ~R 6 each independently represents a substituent selected from a hydrogen atom, a halogen atom, an alkyl group having a carbon atom number of 1 or more and 10 or less, an alkenyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, and a halogenated hydrocarbon group, or an oxetanyl group, an alkoxycarbonyl group, a polyoxyalkylene group, a polyglycerol group, or an alkoxysilyl group; b is the same as defined in General Formula (1).

19. The skin treatment method for non-therapeutic purposes according to claim 18, wherein In General Formula (3), two groups selected from R 3 ~R 6 may be bonded to each other to form an alicyclic structure, an aromatic ring structure, a carboxy imide group, or an anhydride group.

20. The skin treatment method for non-therapeutic purposes according to claim 18, wherein The proportion of the repeating unit represented by general formula (3) in the organosilicon-modified polymer containing a norbornane structure is 5% or more and 90% or less of the total number of repeating units in the polymer.

21. The skin treatment method for non-therapeutic purposes according to claim 14, wherein The number average molecular weight Mn of the organosilicon-modified polymer containing a norbornane structure is 50,000 or more and 2,000,000 or less.

22. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein Further containing a non-volatile oil.

23. The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 3, wherein Further containing a cross-linking type organosilicon resin.

24. A cosmetic method for non-therapeutic purposes, wherein The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 23 is used for improvement of wrinkles of the skin.

25. The cosmetic method for non-therapeutic purposes according to claim 24, wherein In the process 1, the minute droplets of the liquid composition are imparted to the wrinkle peripheral portion of the skin.

26. A cosmetic method for non-therapeutic purposes, wherein The skin treatment method for non-therapeutic purposes according to any one of claims 1 to 23 is used for formation of relief of the skin.

27. Use of the skin treatment method for non-therapeutic purposes according to any one of claims 1 to 23 in a cosmetic surgery.

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