JP2021035921A - Spray agent, spray device, method for using spray agent, and method for producing spray agent - Google Patents

Abstract

To provide spray agents that are advantageous from the viewpoint of releasing an active ingredient at a desired timing while adhering to a living body for a long period of time in a state in which they are difficult to be seen.SOLUTION: A spray agent 20 of the present disclosure contains a porous material 10 and a dispersion medium 25. The porous material 10 has a porous structure 11 containing regenerated cellulose. The porous material 10 contains an active ingredient 12 that is effective for the living body in contact with the porous structure 11. The porous material 10 has a volume mean diameter of 200 μm or less. In the porous structure 11, the volume of pores having a pore diameter of 100 nm or less is 0.5 cm3/g or more and the specific surface area of the pores in the porous structure 11 is 10 m2/g or more. The content of the active ingredient 12 in the porous material 10 is 30% or more on a weight basis.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a spray agent, a spray device, a method of using the spray agent, and a method of producing the spray agent.

Conventionally, materials containing a predetermined active ingredient have been proposed for the purpose of beauty and the like. For example, Patent Document 1 describes a method for producing a film, which comprises a step of introducing a film containing substantially no active ingredient into a medium containing the active ingredient and transferring the active ingredient to the film. .. The film containing the transferred active ingredient is introduced into a carrier to prepare the composition.

Patent Document 2 describes a film for attaching to a living body, which holds a component that acts on a living body or a component that protects the living body. The bioadhesive membrane is a self-supporting membrane and is composed of regenerated cellulose having a weight average molecular weight of 150,000 or more. The film for attaching to a living body has a thickness of 20 nm or more and 1300 nm or less.

Patent Document 3 describes a cosmetic containing a plurality of microcapsules and an aqueous phase in which the plurality of microcapsules are dispersed. Microcapsules consist of a core substance and a wall substance containing the core substance. The core material is an anionic hydrophobic material and the wall material is a cationic polymer. The particle size of the microcapsules is smaller than 200 μm.

Special Table 2009-543900 International Publication No. 2018/09/362 JP-A-2018-176047

In the techniques described in Patent Documents 1 and 2, it is not assumed that a material containing an active ingredient is sprayed. The technique described in Patent Document 3 has room for reexamination from the viewpoint of releasing the active ingredient at a desired timing while adhering to the living body for a long period of time in a state where it is difficult to see. Therefore, the present disclosure provides an advantageous spraying agent from such a viewpoint.

This disclosure is
A porous material having a porous structure containing regenerated cellulose and containing an active ingredient effective for a living body in contact with the porous structure,
Containing a dispersion medium for dispersing the porous material,
The porous material has a volume mean diameter of 200 μm or less and has a volume average diameter of 200 μm or less.
The volume of the pores having a pore diameter of 100 nm or less in the porous structure is 0.5 cm ³ / g or more, and the specific surface area of the pores in the porous structure is 10 m ² / g or more.
The content of the active ingredient in the porous material is 30% or more on a weight basis.
A spray agent is provided.

The above-mentioned spraying agent is advantageous from the viewpoint of releasing the active ingredient at a desired timing while adhering to the living body for a long period of time in a state where it is difficult to see.

FIG. 1 is a diagram schematically showing an example of the spray agent of the present disclosure. FIG. 2 is a perspective view schematically showing a porous material contained in the spray agent of the present disclosure. FIG. 3 is a diagram showing an example of an X-ray diffraction pattern of natural cellulose. FIG. 4 is a diagram schematically showing an example of the spraying device of the present disclosure. FIG. 5 is a cross-sectional view schematically showing another example of the spraying device of the present disclosure. FIG. 6 is a graph showing the evaluation result of the uniformity of adhesion of the spray agent to the hair bundle. FIG. 7 is a graph showing the evaluation results of the sustainability of hair styling in Examples and Comparative Examples. FIG. 8 is a graph showing the evaluation results of the sustainability of hair styling in Examples and Comparative Examples.

(Knowledge on which this disclosure was based)
If it is possible to provide a technology capable of spraying a material containing a component effective for a living body toward the living body and allowing the material to adhere to the living body for a long period of time in a state where it is difficult to see, the convenience of the user will be enhanced. In addition, if the active ingredient is released from the material at a desired timing, the effect obtained by the active ingredient can be enhanced. For example, if the release of the active ingredient can be promoted by applying a predetermined physical stimulus such as pressure to the material, the effect obtained by the active ingredient can be exhibited at a desired timing. Patent Documents 1 to 3 do not describe such a technique. Therefore, the present inventors have made extensive studies to develop such a technique. As a result, the present inventors have an advantage in using a porous material in which the active ingredient is brought into contact with a specific porous structure containing regenerated cellulose, and adjusting the volume average diameter of the porous material within a predetermined range. The spray agent of the present disclosure was devised.

(Embodiment)
Hereinafter, embodiments of the present disclosure will be described with reference to the drawings. The following embodiments are comprehensive or specific examples. Matters such as numerical values, shapes, materials, components, arrangement of components, connection modes, and steps and step order shown in the following embodiments are examples and are described for the purpose of limiting the present disclosure. It's not a thing. The following various embodiments can be combined with each other as long as there is no conflict. In addition, among the components in the following embodiments, the components not described in the independent claims indicating the highest level concept should not be understood as essential components. In the following description, components having substantially the same function are indicated by common reference numerals, and the description may be omitted. In addition, some elements may be omitted in order to avoid overly complicated drawings.

As shown in FIG. 1, the spray agent 20 contains the porous material 10 and the dispersion medium 25. As shown in FIG. 2, the porous material 10 has a porous structure 11 containing regenerated cellulose. In addition, in the porous material 10, the active ingredient 12 effective for the living body is in contact with the porous structure 11. The dispersion medium 25 disperses the porous material 10. The porous material 10 has a volume mean diameter of 200 μm or less. The volume mean diameter is the arithmetic mean diameter Mv in the volume-based particle size distribution. The volume of the pores having a pore diameter of 100 nm or less in the porous structure 11 is 0.5 cm ³ / g or more. This volume means the total volume of pores having a pore diameter of 100 nm or less in the porous structure 11. In addition, the specific surface area of the pores having a pore diameter of 100 nm or less in the porous structure 11 is 10 m ² / g or more. The content of the active ingredient 12 in the porous material 10 is 30% or more on a weight basis. The volume of the pores having a pore diameter of 100 nm or less and the specific surface area of the pores in the porous structure 11 can be determined based on, for example, the result of measuring the porous structure 11 according to a gas adsorption method using nitrogen.

Cellulose includes natural cellulose and regenerated cellulose. As used herein, regenerated cellulose means cellulose that does not have the crystal structure I peculiar to natural cellulose. The crystal structure of cellulose can be confirmed by, for example, X-ray diffraction. FIG. 3 shows an example of an X-ray diffraction pattern of natural cellulose obtained by using CuKα rays under the conditions of 50 kV and 300 mA. In the X-ray diffraction pattern shown in FIG. 3, peaks appear in the vicinity of 14-17 ° and 23 °, which are peculiar to the crystal structure I. Regenerated cellulose often has a crystal structure II. Therefore, in the X-ray diffraction pattern of regenerated cellulose, peaks appear in the vicinity of 12 °, 20 °, and 22 °, and peaks do not appear in the vicinity of 14-17 ° and 23 °.

The regenerated cellulose present in the porous structure 11 is substantially represented by the formula (1). By "substantially", it means that 90% or more of the hydroxyl groups in glucose, which is a repeating unit in the formula (1), remain. 98% or more of the hydroxyl groups in glucose, which is a repeating unit in the formula (1), may remain. The proportion of hydroxy groups in glucose of cellulose can be quantified by various known methods such as X-ray photoelectron spectroscopy (XPS). The regenerated cellulose may have a branched structure. Regenerated cellulose does not contain artificially derivatized cellulose, but does include cellulose that has been once derivatized and regenerated. The regenerated cellulose may be uncrosslinked.

As the raw material cellulose for regenerated cellulose, cellulose derived from plants such as pulp and cotton, or cellulose produced by organisms such as bacteria can be used. It is desirable that the impurity concentration of cellulose as a raw material is 20% by weight or less.

The regenerated cellulose present in the porous structure 11 has, for example, a weight average molecular weight of 100,000 or more. As a result, in regenerated cellulose, many hydroxyl groups are present per molecular chain, and many hydrogen bonds are formed between the molecules. Therefore, the shape of the porous material 10 can be appropriately maintained without the need for a support. The weight average molecular weight of regenerated cellulose can be determined, for example, by gel permeation chromatography (GPC).

When the weight average molecular weight of the regenerated cellulose is large, the viscosity of the solution containing the regenerated cellulose becomes high, and it is difficult to prepare the porous material 10. Therefore, the weight average molecular weight of the regenerated cellulose may be 1,000,000 or less, 500,000 or less, or 300,000 or less. When the weight average molecular weight of the regenerated cellulose is 1,000,000 or less, the porous material 10 can be easily produced. When the weight average molecular weight of the regenerated cellulose is 500,000 or less, the porous material 10 can be more easily produced. When the weight average molecular weight of the regenerated cellulose is 300,000 or less, the variation in the thickness of the porous material 10 is small.

Regenerated cellulose may be present in the porous structure 11, and the porous structure 11 may contain components other than regenerated cellulose such as unavoidable impurities, raw materials, and other additive materials. The content of regenerated cellulose in the porous structure 11 can be, for example, 10% or more on a weight basis.

Since the porous material 10 has a volume average diameter of 200 μm or less, it is possible to suppress a feeling of discomfort such as roughness after the spray agent 20 is attached to the living body by spraying.

The porous material 10 preferably has a volume mean diameter of 100 μm or less. As a result, the spray agent 20 can be sprayed more appropriately. The porous material 10 more preferably has a volume mean diameter of 50 μm or less. As a result, after the porous material 10 adheres to the user's living body by spraying the spray agent 20, the porous material 10 can be attached naturally so that the user himself / herself does not know that the porous material 10 is attached. In addition, the dispersed state of the porous material 10 in the spray agent 20 is stable. The porous material 10 has, for example, a volume mean diameter of 0.1 μm or more. As a result, a large amount of the porous material 10 containing many active ingredients 12 easily adheres to the living body, and the user can easily obtain a good usability. The porous material 10 has, for example, preferably a volume mean diameter of 1 μm or more. In this case, more active ingredients can be attached to the living body, which is useful.

In the regenerated cellulose contained in the porous structure 11, cellulose having many hydrogen bonds in the molecule forms a structure at the molecular level. Therefore, even if the specific surface area of the pores having a pore diameter of 100 nm or less in the ^{porous structure 11 is as high as 10 m 2} / g or more, the porous structure 11 has high strength. As a result, the porous structure 11 is stable even if the content of the active ingredient 12 in the porous material 10 is adjusted to 30% or more on a weight basis.

In the porous structure 11, since the volume of the pores having a pore diameter of 100 nm or less and the specific surface area of the pores are adjusted to the above ranges, it is difficult for a large amount of the active ingredient 12 to be released in a short time, which is effective. Sustained release of component 12 can be realized. On the other hand, when a physical stimulus such as an external force is applied to the porous material 10, the active ingredient 12 can be released from the porous material 10 at a desired timing. In the porous structure 11, when the volume and the specific surface area of the pores having a pore diameter of 100 nm or less are in the above ranges, the flow resistance of the active ingredient 12 moving toward the outside of the porous structure 11 tends to increase. .. Therefore, when a large concentration gradient occurs in the environment in which the porous material 10 is arranged, or when a predetermined physical stimulus is applied to the porous material 10, the active ingredient 12 from the porous material 10 Release is promoted.

The volume of the pores having a pore diameter of 100 nm or less in the porous structure 11 is preferably 1 cm ³ / g or more. In addition, the specific surface area of the pores having a pore diameter of 100 nm or less in the porous structure 11 is preferably 50 m ² / g or more. According to such a configuration, a larger amount of the active ingredient can be released at a desired timing.

The upper limit of the volume of the pores having a pore diameter of 100 nm or less in the porous structure 11 is not limited to a specific value. The volume of the pores having a pore diameter of 100 nm or less in the porous structure 11 is, for example, 10 cm ³ / g or less. The upper limit of the specific surface area of the pores having a pore diameter of 100 nm or less in the porous structure 11 is not limited to a specific value. The specific surface area of the pores having a pore diameter of 100 nm or less in the porous structure 11 is, for example, 1000 m ² / g or less.

Examples of physical stimuli applied to the porous material 10 to promote the release of the active ingredient 12 are irradiation of light of a predetermined wavelength such as pressure, temperature change, frictional force, wind, and ultraviolet light. Pay attention to the case of using pressure or frictional force as a physical stimulus. Since the porous structure 11 has many pores having a pore diameter of 100 nm or less, the active ingredient 12 remains in the porous material 10 in a state where no pressure or frictional force is applied to the porous material 10. On the other hand, when pressure or frictional force is applied to the porous material 10, the active ingredient 12 is released according to the magnitude of the pressure or frictional force. Pay attention to the case of using temperature change as a physical stimulus. For example, by raising the temperature of the environment of the porous material 10, the active ingredient 12 becomes easy to flow, and the active ingredient 12 is released from the porous material 10. Pay attention to the case of using light irradiation as a physical stimulus. For example, when the porous material 10 is irradiated with ultraviolet rays by using a component that is denatured by ultraviolet rays and easily flows as the active ingredient 12, the active ingredient 12 is released from the porous material 10. As described above, regardless of which physical stimulus is used, the structure of the porous structure 11 makes it easy for the active ingredient 12 to stay in the porous material 10 in the absence of physical stimulus, and the physical stimulus is applied. In the state, the active ingredient 12 is easily released.

The shape of the porous material 10 is not limited to a specific shape as long as the porous material 10 has a volume mean diameter of 200 μm or less. In the porous material 10, for example, even if the ratio (B / A) of the dimension B of the porous material 10 in the direction perpendicular to the thickness direction of the porous material 10 to the thickness A of the porous material 10 is 2 or more. Good. As a result, the porous material 10 can be stably attached to the living body for a long period of time without using an adhesive component. A rash can be prevented by not using an adhesive component. In addition, the regenerated cellulose present in the porous structure 11 is excellent in biocompatibility. Therefore, the burden on the living body of the porous material 10 is small, and the porous material 10 can be used for a long period of time. In the present specification, the dimension B is the distance between the pair of parallel straight lines when the porous material 10 in a plan view is sandwiched between the pair of parallel straight lines. The values of the thickness A and the dimension B of the porous material 10 can be determined, for example, by the result of the particle size distribution measurement of the porous material 10. For example, among a plurality of peaks appearing in the particle size distribution, the value of the peak corresponding to the smallest particle size can be regarded as the thickness A, and the value of the peak corresponding to the larger particle size can be regarded as the dimension B. In addition, biocompatibility means that reactions such as rash and inflammation are unlikely to occur in a living body, particularly in the skin.

The upper limit of the ratio B / A of the dimension B to the thickness A is not limited to a specific value. The ratio B / A of the dimension B to the thickness A is, for example, 1000 or less.

The porous structure 11 has, for example, an elastic modulus of 1 GPa or less. As a result, the porous material 10 is appropriately deformed by pressure or frictional force, and the active ingredient 12 is likely to be released from the porous material 10. In the present specification, the elastic modulus means a tensile elastic modulus. The tensile elastic modulus of the porous material 10 can be measured according to, for example, Japanese Industrial Standards (JIS) K7127: 1999.

The elastic modulus of the porous structure 11 is, for example, 0.01 GPa or more.

Cellulose is a material that exhibits high affinity for both hydrophilic and hydrophobic materials. Therefore, both the hydrophilic material and the hydrophobic material can be appropriately attached to the porous structure 11 containing the regenerated cellulose. Therefore, the porous material 10 can contain many kinds of active ingredients 12. As described above, since the porous structure 11 contains regenerated cellulose, it exhibits amphipathic properties. In addition, many hydrogen bonds are likely to occur in the porous structure 11. Therefore, the porous material 10 tends to contain a large amount of the active ingredient 12. As a result, the content of the active ingredient 12 in the porous material 10 can be adjusted to 30% or more on a weight basis. The content of the active ingredient 12 in the porous material 10 may be 50% or more on a weight basis. In this case, a larger amount of the active ingredient 12 can be supplied to the living body. The content of the active ingredient 12 in the porous material 10 is, for example, 99.9% or less on a weight basis.

The active ingredient 12 may be present near the center of the porous material 10 in the thickness direction, or may be present near the surface of the porous material 10.

The active ingredient 12 is not limited to a specific ingredient. The active ingredient 12 may be an ingredient for hair care that conditions the hair, may be an ingredient for hair styling, and brings beauty effects such as moisturizing, whitening, and anti-aging to the skin. It may be an ingredient. Examples of ingredients for at least one of hair care and hair styling include avocado oil, olive oil, cacao butter, beef fat, saflower oil, soybean oil, sunflower oil, sunflower oil, macadam nut oil, camellia oil, wheat germ oil, mountain tea flower oil, Tea seed oil, evening primrose oil, tea tree oil, balm oil, palm oil, manuka oil, horse fat, cotton seed oil, mokuro, moringa oil, carnauba wax, palm oil, lanolin, setanol, stearyl alcohol, behenyl alcohol, isopropyl myristate, liquid paraffin , Vaseline, squalane, polyoxyethylene lanolin, polyoxyethylene lanolin alcohol ether, keratin, keratin protein derivative, collagen protein derivative, silk protein derivative, soybean protein derivative, cationized cellulose, cationized guar gum, dimethylpolysiloxane, amino-modified silicone , Polyether silicone, glycerin, propylene glycol, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, distearyldimethylammonium chloride, diethylaminoethylamide stearate, oxybenzone, synoxate, phenyl salicylate, paraaminobenzoic acid ester, dipotassium glycyrrhizinate, cicon extract, Examples include zinc bilithion, viroctone olamine, sulfurous blaze, salicylic acid, hydrolyzed keratin, hydrolyzed collagen, hydrolyzed silk, malic acid, and trehalose.

On the other hand, as examples of ingredients that bring beauty effects such as moisturizing, whitening, and anti-aging to the skin, Arabic gum, tragacant gum, galactan, guar gum, carob gum, karaya gum, carrageenan, pectin, canten, quince seed (malmero), algae colloid ( Cassou extract) and plant-derived polymers such as starch derived from rice, corn, potatoes, or wheat, microorganism-derived polymers such as xanthan gum, dextran, succinoglucan, and burran, collagen, casein, albumin, gelatin, etc. Animal-derived polymers, bio-derived polymers such as hyaluronic acid, mutin, chondroitin sulfate, and soluble collagen, polyethylene glycol, sorbitol, xylitol, multitose, sodium dl-pyrrolidone carboxylate, sodium lactate, trimethylglycine, retinol, retinal, Represented by vitamin A such as retinoic acid, thiamine, riboflavin, pyridoxin, pyridoxamine, vitamin B such as folic acid, vitamin D such as ergocalciferol and cholecalciferol, α-tocopherol (vitamin E) phylloquinone, and vitamin K of menaquinone. Vitamin A derivatives such as vitamins, tretinoin and retinol palmitate, vitamin C derivatives such as glyceryl ascorbic acid and ascorbic tetrahexyldecanoate, vitamin E derivatives such as α-tocopherol acetate, α-tocopherylquinone, and α-tocopherol succinate. , Tranexamic acid, arbutin, hydroquinone, kodiic acid, potassium 4-methoxysalicylate, polyphenols such as tranexamic acid, lucinol, ellagic acid and anthocyanin, disodium 3-succinyloxyglycyrrhetinate, rutin, minoxidil, finasteride, cepharanthin, and pyrrolidone carboxylic Acid is mentioned.

The porous structure 11 may further contain a cationic substance. In other words, the cationic material can be one of the components of the porous structure 11. Hair tends to be positively charged due to friction or the like. When the hair is positively charged, it is difficult to perform proper hair styling. The presence of the cationic substance in the porous structure 11 prevents the cation derived from the cationic substance from positively charging the hair when the porous material 10 is attached to the hair. As a result, the desired hairstyle is likely to be maintained for a long period of time.

Cationic substances are not limited to specific substances. The cationic material is preferably biocompatible. Examples of biocompatible cationic substances are cationic polymers, metal ions such as sodium ions, potassium ions, and zinc ions, materials containing metal ions, and cationic surfactants. Examples of cationic polymers are chitosan, cationized cellulose, and polyamines. Examples of cationized cellulose are hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether and hydroxyethyl cellulose hydroxypropyltrimethylammonium chloride ether.

The content of the cationic substance in the porous structure 11 is not limited to a specific value. Its content is, for example, 0.01% or more and 90% or less on a weight basis. When the content of the cationic substance in the porous structure 11 is 0.01% by weight or more, the charge on a specific part of the living body such as hair can be reduced. The content of the cationic substance in the porous structure 11 is preferably 1% by weight or more. In this case, the charge on a specific part of the living body such as hair can be reduced more reliably. When the content of the cationic substance in the porous structure 11 is 90% by weight or less, the content of regenerated cellulose in the porous structure 11 can be adjusted to 10% by weight or more. Therefore, the porous structure 11 tends to have high strength due to the many hydrogen bonds of the regenerated cellulose. Therefore, even if the volume of the pores having a pore diameter of 100 nm or less in the porous structure 11 is 0.5 cm ³ / g or more and the specific surface area of the pores is 10 m ² / g or more, the porous structure 11 is porous. The quality structure 11 has sufficient strength.

The dispersion medium 25 is not limited to a specific type of substance as long as the porous material 10 is dispersed. The dispersion medium 25 is typically a substance that is safe for the living body. The dispersion medium 25 may be hydrophilic or hydrophobic. The hydrophilic dispersion medium 25 is, for example, water, alcohol, or polyhydric alcohol, and may be water, ethanol, propanediol, butanediol, glycerin, polyglycerin, or polyethylene glycol. Examples of the hydrophobic dispersion medium 25 are avocado oil, olive oil, castor oil, camellia oil, and liquid paraffin. The active ingredient 12 and the dispersion medium 25 may be the same type of substance. The dispersion medium 25 may be a mixture of a plurality of types of substances.

The dispersion medium 25 may contain, for example, a liquid substance having a ^{hydrogen bond term δH of 10 MPa 1/2 or more in the Hansen solubility parameter (HSP).} HSP is known as a parameter for evaluating the affinity between materials. The value of HSP (δ) and the dispersion term δD, the polar term δP, and the hydrogen bond term δH have the relationship of the following equation (2).
^{δ 2 = δD 2 + δP 2} + δH 2 (2)

Regenerated cellulose is present in the porous structure 11 of the porous material 10, and many hydrophilic groups are present. Therefore, since the dispersion medium 25 contains a liquid substance having a δH of 10 MPa ^1/2 or more, the porous material 10 easily adheres to the living body. For the value of δH, for example, δ is obtained from the heat of evaporation of the material, δP is obtained from the dipole moment and the molecular volume, and δD is calculated from the refractive index of the material. Sonouede can determine δH from the relationship of the above formula (2) (CM Hansen, " Hansen Solubility Parameters A User's Handbook", CRC Press, Boca Raton, 2 nd edn., See 2007). As the refractive index of the material, for example, a measured value at 25 ° C. using the D line of sodium can be used.

Examples of liquid substances having δH of 10 MPa ^1/2 or more are water, glycerin, ethylene glycol, butanediol, dipropyl glycol, methanol, ethanol, propanol, butanol, octanol, and decanol. In particular, water, glycerin, and ethanol have high affinity with living organisms, and it is desirable to use these liquid substances. The upper limit of the hydrogen bond term δH in HSP of a liquid substance is not limited to a specific value. The hydrogen bond term δH in HSP of a liquid substance is, for example, 43 MPa ^1/2 or less.

The spray agent 20 has a conductivity of 1 mS / cm or less at 25 ° C., for example. In this case, the spray agent 20 adheres to the living body to make it difficult to generate static electricity. In addition, the mist of the spray agent 20 is likely to be generated electrostatically. Further, for example, when the spray agent 20 is electrostatically sprayed, electric discharge is unlikely to occur.

The conductivity of the spray agent 20 at 25 ° C. may be 0.5 mS / cm or less. As a result, the spray agent 20 can be easily sprayed stably. In order to adjust the conductivity of the spray agent 20, the spray agent 20 may contain additives such as a surfactant, a salt, an anionic polymer, and a cationic polymer.

The lower limit of the conductivity of the spray agent 20 at 25 ° C. is not limited to a specific value. The conductivity of the spray agent 20 at 25 ° C. is, for example, 1 nS / cm or more.

The spray agent 20 has a viscosity of 10 Pa · s or less at 25 ° C., for example. In this case, when the spray agent 20 is sprayed, the spray agent 20 is likely to be finely divided, and the spray agent 20 is likely to adhere uniformly to the living body. The viscosity of the spray agent 20 is measured, for example, by a rotary viscometer. In the measurement of the viscosity of the spray agent 20 using the rotary viscometer, the rotation speed of the spindle of the rotary viscometer can be set to ^{, for example, 1s -1.}

The lower limit of the viscosity of the spray agent 20 at 25 ° C. is not limited to a specific value. The viscosity of the spray agent 20 at 25 ° C. is, for example, 0.1 mPa · s or more.

The spray agent 20 may further contain, for example, a cationic substance. In this case, the cation derived from the cationic substance suppresses the hair from being positively charged, and the desired hair style can be easily maintained for a long period of time.

The cationic material is typically dissolved or dispersed in the dispersion medium 25. The cationic material is preferably biocompatible. The example of the cationic substance is the same as the example of the cationic substance which may be contained in the porous structure 11.

The content of the cationic substance in the spray agent 20 is not limited to a specific value. Its content is, for example, 0.001% by weight or more and 50% by weight or less. When the content of the cationic substance in the spray agent 20 is 0.001% by weight or more, the charge on a specific part of the living body such as hair can be reduced. The content of the cationic substance in the spray agent 20 is preferably 0.1% by weight or more. In this case, the charge on a specific part of the living body such as hair can be reduced more reliably.

The spray agent 20 is sprayed toward specific parts of the living body such as hair, scalp, face, arms, and organs, and the porous material 10 can be attached to specific parts.

The spray agent 20 can be sprayed toward the living body, for example, when the living body is wet with water. According to the use of such a spray agent 20, hydrogen bonds are likely to occur between the regenerated cellulose of the porous structure 11 and the living body, and the porous material 10 can be stably attached to the living body for a long period of time.

When the spray agent 20 is used, the temperature of the environment of the living body may be adjusted to 40 ° C. or higher after the spray agent 20 is sprayed toward the living body. By using such a spray agent 20, the fluidity of the dispersion medium 25 or the active ingredient 12 is increased, and a part of the active ingredient 12 is easily released from the porous material 10 into the living body. After that, when the temperature of the environment of the living body is cooled to less than 40 ° C., the adhesion of the porous material 10 to the living body tends to be improved after the porous material 10 is attached to the living body.

When the temperature of the living body environment is adjusted to 40 ° C. or higher after spraying the spraying agent 20, the maximum temperature of the living body environment temperature is not limited to a specific temperature. When the temperature of the living body environment is adjusted to 40 ° C. or higher after spraying the spraying agent 20, the maximum temperature of the living body environment temperature is, for example, 250 ° C. or lower.

The spray agent 20 can be produced, for example, by a method including the following steps (I), (II), and (III).
(I) A porous material 10 having a porous structure 11 containing regenerated cellulose and containing an active ingredient effective for a living body in contact with the porous structure 11 is produced.
(II) The porous material 10 is shredded or refined to give a volume mean diameter of 200 μm or less.
(III) The shredded or finely divided porous material 10 is dispersed in the dispersion medium 25.

The spray agent 20 can be produced, for example, by the following method. First, a cellulose solution is prepared by dissolving cellulose in a solvent. In order to include the cationic substance in the porous structure 11, the cationic substance may be added to prepare a cellulose solution. For example, cellulose having the above-mentioned weight average molecular weight can be used for preparing a cellulose solution. The cellulose used for preparing the cellulose solution may be a cellulose derived from a plant such as pulp or cotton, or a cellulose produced by an organism such as a bacterium, as long as it has a predetermined weight average molecular weight. .. The impurity concentration of cellulose as a raw material is, for example, 20% or less on a weight basis.

As the solvent, a solvent containing an ionic liquid may be used. By using a solvent containing an ionic liquid, cellulose can be dissolved in a relatively short time. An ionic liquid is a salt composed of anions and cations, and can exhibit a liquid state at a temperature of 150 ° C. or lower. As the ionic liquid that dissolves cellulose, an ionic liquid containing an amino acid, an alkyl phosphate or an acetate can be used. By using such an ionic liquid as a solvent, cellulose can be dissolved while suppressing a decrease in molecular weight to some extent. In particular, since amino acids are components existing in the living body, it is possible to prepare a porous material 10 that is safe for the living body by using an ionic liquid containing amino acids.

As the ionic liquid that dissolves cellulose, for example, an ionic liquid represented by the following general formula (s1) can be used. The ionic liquid represented by the general formula (s1) shows an example in which the anion is an amino acid. As can be seen from the general formula (s1), in this example, the anion contains a terminal carboxyl group and a terminal amino group. The cation of the ionic liquid represented by the general formula (s1) may be a quaternary ammonium cation.

In the general formula (s1), R ₁ to R ₆ independently represent a hydrogen atom or a substituent. The substituent may be an alkyl group, a hydroxyalkyl group, or a phenyl group, and may contain a branch in the carbon chain. The substituent may contain a group such as an amino group, a hydroxyl group, and a carboxyl group. n is an integer of 1 or more and 5 or less.

The ionic liquid that dissolves cellulose may be an ionic liquid represented by the following formula (III). In formula (III), R ₁ , R ₂ , R ₃ , and R ₄ independently represent an alkyl group having a hydrogen atom or 1 to 4 carbon atoms.

A second solvent may be further added in the step of preparing the cellulose solution. For example, a second solvent may be further added to a mixture of cellulose having a predetermined weight average molecular weight and an ionic liquid. The second solvent is, for example, a solvent that does not precipitate cellulose. The second solvent can be an aprotic polar solvent.

Next, the obtained cellulose solution is applied to a predetermined substrate to obtain a polymer gel sheet supported by the substrate. Then, the polymer gel sheet on the substrate is immersed in a rinse liquid which is a liquid that does not dissolve cellulose. This step may be said to be a step of cleaning the polymer gel sheet, which removes the solvent containing the ionic liquid from the polymer gel sheet.

As the rinsing liquid, a solvent compatible with the ionic liquid can be used. Examples of such solvents are water, methanol, ethanol, propanol, butanol, octanol, toluene, xylene, acetone, acetonitrile, dimethylacetamide, dimethylformamide, and dimethyl sulfoxide.

Next, for example, the polymer gel sheet is immersed in a solution containing the active ingredient 12, and the active ingredient 12 is contained in the polymer gel sheet. When the polymer gel sheet is immersed in a rinse solution or a solution containing the active ingredient 12, ultrasonic treatment may be performed for 10 seconds or longer. By performing a process of applying vibration having a frequency of, for example, 1 Hz or more, such as ultrasonic waves, pores having a pore diameter of 100 nm or less ^{have a volume of 0.5 cm 3} / g or more and 10 m ² / g or more. A porous structure containing regenerated cellulose having a specific surface area of can be stably produced. The process of applying vibration may be performed when immersed in a rinsing solution.

Then, unnecessary components such as a solvent are removed from the polymer gel sheet. In other words, the polymer gel sheet is dried. As a result, the porous material 10 is obtained. As a method for drying the polymer gel sheet, various drying methods such as natural drying, vacuum drying, heat drying, freeze drying, and supercritical drying can be applied. The polymer gel sheet may be dried by vacuum heating. The conditions for drying the polymer gel sheet are not particularly limited. Appropriate drying times and temperatures can be determined to remove some or all of the solvent and rinse solution of the cellulose solution.

After the polymer gel sheet is dried, a step of adding the active ingredient 12 may be performed. In this case, a step may be performed in which the polymer gel sheet is dried so that a structure corresponding to the porous structure 11 can be formed, and then the active ingredient 12 is contained. For example, after immersing the polymer gel sheet in a rinsing solution to wash the polymer gel sheet, the polymer gel sheet is immersed in a predetermined liquid compound such as tert-butanol and acetic acid, and the polymer gel sheet is dried by freeze-drying or supercritical drying. Thereby, the structure corresponding to the porous structure 11 can be formed prior to the step of containing the active ingredient 12.

After that, a step of shredding or miniaturizing the porous material 10 can be performed so that the porous material 10 has a predetermined volume average diameter. This step may be performed in a state where the porous material 10 is immersed in the dispersion medium 25. Further, the porous material 10 processed so as to have a predetermined volume average diameter may be dispersed in the dispersion medium 25. The method of shredding or refining the porous material 10 is not limited to a specific method. As a method of shredding or refining the porous material 10, the use of a cutting tool such as a razor, a cutter, and scissors, the use of a mesh, the use of a laser, the shredding by punching, and the mill, homogenizer, or deerless dispersion. Miniaturization by machine etc. can be mentioned. In this way, the spray agent 20 is produced.

A spraying device for spraying while storing the spraying agent 20 can be provided. For example, the spraying device 1a shown in FIG. 4 or the spraying device 1b shown in FIG. 5 can be provided.

The spray device 1a includes, for example, a tank 2 and a sprayer 3. The spray agent 20 is stored in the tank 2. The sprayer 3 sprays the spray agent 20 stored in the tank 2.

The tank 2 may be a cartridge type tank configured to be removable. As a result, when the remaining amount of the spray agent 20 in the tank 2 reaches a level at which it is difficult to spray the spray agent 20, it is easy to replenish the spray agent 20. It is also possible to spray different types of spraying agents 20 using one spraying device 1a.

The flow velocity of the spray agent 20 sprayed from the sprayer 3 is not limited to a specific value. The sprayer 3 sprays the spray agent 20 at a flow rate of 0.1 m / s or more, for example. In this case, for example, when the spray agent 20 is sprayed onto the hair, the porous material 10 can be attached not only to the surface of the hair but also to the inside of the hair near the scalp or the scalp.

The sprayer 3 preferably sprays the spray agent 20 at a flow rate of 1 m / s or more. As a result, even a person with a large amount of hair can uniformly adhere the porous material 10. The sprayer 3 sprays the spray agent 20 at a flow rate of 50 m / s or less, for example.

As shown in FIG. 4, the atomizer 3 has a discharge unit 3a. The spray agent 20 stored in the tank 2 passes through the discharge unit 3a and is discharged. The discharge unit 3a has a discharge port for discharging the spray agent 20. The spraying device 1a further includes, for example, a pump 4. When the pump 4 operates, the spray agent 20 stored in the tank 2 is sent to the discharge unit 3a.

As shown in FIG. 4, the spraying device 1a further includes, for example, a heating element 7. The heating element 7 can generate heat at 40 ° C. or higher. As a result, for example, when the heating element 7 is generating heat, the temperature of the spray agent 20 sprayed by the spraying device 1a rises, and the dispersion medium 25 or the active ingredient 12 which is difficult to flow at room temperature is sprayed in a state where it is easy to flow. The agent 20 easily adheres to the living body. After that, the temperature of the spray agent 20 decreases, and the porous material 10 easily adheres to the living body. The heating element 7 is, for example, a resistance heating element.

The heating element 7 is preferably capable of generating heat above 70 ° C. In this case, the spray agent 20 is likely to adhere to the living body in a state where the dispersion medium 25 or the active ingredient 12 is more likely to flow. The heating element 7 is more preferably capable of generating heat above 100 ° C. In this case, the spray agent 20 can be attached to the living body in a state where the dispersion medium 25 or the active ingredient 12 is more easily fluidized, and it is also possible to heat a specific part of the living body such as hair.

The upper limit of the heat generation temperature of the heating element 7 is not limited to a specific value. The upper limit of the heat generation temperature of the heating element 7 is, for example, 250 ° C.

The heating element 7 may be configured to be able to heat, for example, the spray agent 20 stored in the tank 2 or the spray agent 20 flowing between the tank 2 and the discharge unit 3a. As a result, the spray agent 20 can be stably heated by the small heating element 7.

As shown in FIG. 4, the spraying device 1a further includes, for example, a charger 35. The charger 35 charges at least one of the porous material 10 of the spray agent 20 and the dispersion medium 25. For example, the porous material 10 is positively charged by the charger 35, and the positively charged porous material 10 is supplied to the hair, so that the hair can be suppressed from being positively charged. As a result, the hair is less likely to float, and damage to the hair due to static electricity is suppressed. On the other hand, since damaged hair tends to be negatively charged, many porous materials 10 can be attached to the damaged portion of the hair. When the surface of the spray agent 20 is negatively charged by the charger 35, the spray agent 20 flows toward the hair which is easily charged positively, so that the spray agent 20 tends to selectively adhere to the hair instead of the face. ..

The charger 35 includes, for example, a discharge unit 3a and an electrode 3b, and is configured so that a voltage can be applied between the discharge unit 3a and the electrode 3b. The discharge portion 3a is made of a conductive material such as a metal or an alloy. The electrode 3b is also made of a conductive material such as a metal or an alloy. The electrode 3b is arranged so as to face the discharge portion 3a, and the electrode 3b is formed with an opening for passing the spray agent 20 discharged from the discharge portion 3a. When a voltage is applied between the discharge unit 3a and the electrode 3b, the spray agent 20 passing through the discharge unit 3a is discharged from the discharge port of the discharge unit 3a in a positively or negatively charged state. The charged spray agent 20 flies toward the electrode 3b, passes through the opening of the electrode 3b, and is supplied to a predetermined part of the living body such as hair.

As shown in FIG. 4, the spraying device 1a further includes, for example, a controller 5. The controller 5 adjusts at least one item selected from the group consisting of (i), (ii), (iii), (iv), (v), and (vi) below, for example.
(I) Flow velocity of the spray agent 20 sprayed from the sprayer 3 (ii) Temperature of the spray agent 20 sprayed from the sprayer 3 (iii) Spray interval of the spray agent 20 in the sprayer 3 (iv) Spray sprayed by the sprayer 3 Amount of agent 20 (v) Direction of flow of atomizer 20 sprayed by atomizer 3 (vi) Charged state of atomizer 20 sprayed by atomizer 3.

Regarding the item (i), by adjusting the flow velocity of the spray agent 20 sprayed from the sprayer 3, the porous material 10 can be uniformly attached to a wide range of a specific part of the living body such as hair. In addition, for example, the flow velocity of the spray agent 20 can be adjusted according to the amount of hair or the length of the hair, and an appropriate amount of the spray agent can be stably applied to the entire hair. The controller 5 transmits, for example, a control signal to the pump 4 to adjust the output of the pump 4 and adjust the flow velocity of the spray agent 20. The spraying device 1a may include a fan (not shown) that creates a flow of air around the discharge port of the discharge unit 3a. In this case, the controller 5 may transmit a control signal to the fan to adjust the output of the fan and adjust the flow velocity of the spray agent 20.

Regarding the item (ii), by adjusting the temperature of the sprayed spraying agent 20, for example, it is possible to realize a state in which the living body can be quickly dried without the dispersion medium 25 of the spraying agent 20 suddenly boiling. As a result, the porous material 10 can be quickly and stably attached to the living body. In order to quickly and stably attach the porous material 10 to the living body, it is advantageous to adjust the temperature of the spray agent 20 to a temperature at which the dispersion medium 25 does not suddenly boil. From this point of view, for example, the temperature of the spray agent 20 can be adjusted between a temperature 20 ° C. lower than the boiling point of the dispersion medium 25 and a temperature 5 ° C. lower than the boiling point of the dispersion medium 25. For example, when the dispersion medium 25 is water, the boiling point of the dispersion medium 25 is 100 ° C., so that the temperature of the spray agent 20 can be adjusted in the range of 80 ° C. or higher and 95 ° C. or lower. By controlling the temperature of the spray agent 20 to prevent the dispersion medium 25 from bumping, the large area of the porous material 10 when the ratio (B / A) of the dimension B to the thickness A of the porous material 10 is 2 or more. The part having the above is likely to come into contact with the living body. As a result, the porous material 10 is easily attached to the living body in a state where the portion having a large area of the porous material 10 is in contact with the living body, and the porous material 10 is easily attached to the living body after being attached to the living body. The controller 5 transmits, for example, a control signal to the heating element 7 to adjust the amount of heat generated by the heating element 7 and adjust the temperature of the spray agent 20.

Regarding the items (iii) and (iv), the spray interval of the spray agent 20 in the sprayer 3 or the amount of the spray agent 20 sprayed by the sprayer 3 is adjusted to make the amount of the spray agent 20 required for the living body uniform. Can be supplied to. The controller 5 transmits, for example, a control signal to the pump 4 to adjust the output of the pump 4 and adjust the item (iii) or (iv). For example, when the spraying device 1a is configured as a hair dryer having a function of spraying the spraying agent 20, it is conceivable to spray the spraying agent 20 toward the hair while drying the hair. For example, an appropriate amount of the porous material 10 is attached to the hair by adjusting the spray amount of the spray agent 20 to be small during the period when the hair is extremely wet and by spraying a larger amount of the spray agent 20 during the period when the hair begins to dry. it can. Further, the spraying of the spraying agent 20 and its stop may be repeated at predetermined intervals. This makes it possible to prevent the spray agent 20 from being excessively supplied to a specific portion of the living body. The item (iii) or (iv) may be adjusted according to the exercise state when the spray device 1a is used. For example, when the spray device 1a is moved quickly, the amount of the spray agent 20 to be sprayed is adjusted to a large amount, and when the spray device 1a is moved slowly, the amount of the spray agent 20 to be sprayed is adjusted. Adjusted less. As a result, the porous material 10 can be uniformly attached to the living body. The spraying device 1a may include a gyro sensor or an acceleration sensor (not shown), and the controller 5 may acquire the detection results of these sensors to determine the motion state when the spraying device 1a is used. Good.

Regarding the item (v), by adjusting the flow direction of the spray agent 20 sprayed by the sprayer 3, the spray agent 20 is likely to be supplied to a desired portion of the living body. For example, the spraying device 1a may include an actuator (not shown), and may be configured such that the opening direction of the discharge port of the discharge unit 3a is changed by the actuator. The controller 5 may, for example, transmit a control signal to the actuator to operate the actuator and adjust the item (v). Further, the spray device 1a is provided with a plurality of discharge portions 3a having discharge ports opened in different directions, and is configured to be able to selectively supply the spray agent 20 to any one of the plurality of discharge portions 3a. You may. The controller 5 may, for example, activate a mechanism for selecting the discharge unit 3a to which the spray agent 20 should be supplied, and adjust the item (v). The mechanism for selecting the discharge unit 3a to which the spray agent 20 should be supplied is, for example, a switching valve. For example, when the spraying device 1a is configured as a hair dryer having a function of spraying the spraying agent 20, the controller 5 adjusts the item (v) so that more spraying agent 20 is supplied to the hair tips. You may. This makes it easier to protect the perishable hair tips.

Regarding the item (vi), by adjusting the charged state of the spray agent 20 sprayed by the sprayer 3, the effect on the living body brought about by the spray agent 20 can be adjusted, or the spray agent 20 is specific to the living body. It is easy to selectively adhere to the place. For example, by increasing the positive charge amount of the spray agent 20, the effect of suppressing hair damage can be enhanced. On the other hand, by negatively charging the spray agent 20, the spray agent 20 is more likely to be supplied to the hair which is more likely to be positively charged than the skin which is easily negatively charged. Therefore, the spray agent 20 tends to selectively adhere to the hair instead of the face. In addition, the charged state of the spray agent 20 may be adjusted according to the environmental conditions, the conditions of the living body, or the part of the living body. The controller 5 transmits, for example, a control signal to the charger 35 to adjust the item (vi).

As shown in FIG. 4, the spraying device 1a may further include a sensor 6 for detecting a state of a living body. The controller 5 is selected from, for example, at least one selected from the group consisting of (i), (ii), (iii), (iv), (v), and (vi) based on the detection result of the sensor 6. Adjust one item. Thereby, the spray agent 20 can be supplied according to the state of the living body. The controller 5 acquires a signal indicating the detection result of the sensor 6 and determines the state of the living body.

The sensor 6 detects, for example, the amount of water contained in the living body. The controller 5 adjusts the amount of the spray agent 20 sprayed by the sprayer 3 based on the amount of water detected by the sensor 6. The controller 5 transmits, for example, a control signal to the pump 4 to adjust the output of the pump 4 and adjust the amount of the atomizer 20 sprayed by the atomizer 3. The sensor 6 optically detects, for example, the amount of water to be sensed.

The spraying device 1b is configured in the same manner as the spraying device 1a except for a portion to be described in particular. The components of the spraying device 1b that are the same as or corresponding to the components of the spraying device 1a are designated by the same reference numerals, and detailed description thereof will be omitted. The description of the spraying device 1a also applies to the spraying device 1b, as long as there is no technical conflict.

The spraying device 1b is configured as a hair dryer having a function of spraying the spraying agent 20. The spray device 1b includes a main body portion 41 and a grip portion 42. The main body 41 has a housing 41h that constitutes an outer shell. A blower port 41w is formed at one end of the housing 41h in the longitudinal direction, and a suction port 41s is formed at the other end of the housing 41h in the longitudinal direction. Inside the housing 41h, a fan 71, a motor 72, and a heater 75 are arranged in addition to the tank 2, the atomizer 3, and the pump 4. The fan 71 is arranged between the suction port 41s and the heater 75 in the longitudinal direction of the housing 41h. The fan 71 is connected to the rotor of the motor 72. As the motor 72 operates, the fan 71 rotates, and air flows from the suction port 41s toward the air outlet 41w. The heater 75 is, for example, a resistance heating type electric heater. The heater 75 heats the air flowing from the suction port 41s toward the air outlet 41w. As a result, warm air is blown out from the air outlet 41w.

A spray port 41m is formed at one end of the housing 41h in the longitudinal direction. The spray agent 20 sprayed by the sprayer 3 is guided to the outside of the spray device 1b through the spray port 41 m. A first passage 45w and a second passage 45m are formed along the longitudinal direction of the housing 41h in the internal space of the housing 41h between one end of the housing 41h in the longitudinal direction and the fan 71. The first passage 45w extends to the air outlet 41w. The second passage 45 m extends to the spray port 41 m. A heater 75 is arranged in the first passage 45w, and a sprayer 3 is arranged in the second passage 45m. The tank 2 and the pump 4 may be arranged in the second passage 45 m. The air sent out by the fan 71 is guided to the outside of the spray device 1b through the first passage 45w. The spray device 1b may be configured so that a part of the air sent out by the fan 71 passes through the second passage 45 m.

For example, a sensor 6 is attached to the outer side surface of the housing 41h, and the sensor 6 can detect the state of the living body to which the air outlet 41w is directed.

The grip portion 42 projects and extends from the side surface of the main body portion 41 in a direction intersecting the longitudinal direction of the housing 41h. The spray device 1b is used in a state where the user grips the grip portion 42 and the air outlet 41w is directed in a desired direction. The grip portion 42 is connected to the main body portion 41 by a hinge 60. When the spray device 1b is not in use, the tip of the grip portion 42 is moved so as to approach the housing 41h, and the grip portion 42 is folded so as to extend in the longitudinal direction of the housing 41h. A power switch 55 is attached to the outer side surface of the grip portion 42. The power switch 55 is, for example, a slide type switch. A controller 5 is arranged inside the grip portion 42, and the atomizer 3, the pump 4, the sensor 6, the motor 72, the heater 75, the power switch 55, and the controller 5 are connected by wiring. The controller 5 has an electric circuit for supplying power to each component and controlling the operation. These circuits may be integrated on one substrate or dispersed on a plurality of substrates.

A power cord 80 is attached to the tip of the grip portion 42, and the wiring of the power cord 80 is connected to the controller 5.

When the power switch 55 is turned on, electric power is supplied to the controller 5 through the power cord 80, and further electric power is supplied to the atomizer 3, the pump 4, the sensor 6, the motor 72, or the heater 75 as needed. When power is supplied to the sprayer 3 or the pump 4, the spraying agent 20 is sprayed from the sprayer 3, and the sprayed spraying agent 20 is guided to the outside of the spraying device 1b through the second passage 45 m and the spray port 41 m. .. When electric power is supplied to the motor 72, the fan 71 operates and the air sent out by the fan 71 is blown out from the air outlet 41w through the first passage 45w. In this case, the spray agent 20 sprayed from the sprayer 3 can be supplied to the user's hair along with the flow of air blown from the air outlet 41w. When electric power is supplied to the heater 75, the air flowing through the first passage 45w is heated, and warm air is blown out from the air outlet 41w.

The spraying agents of the present disclosure will be described in more detail by way of examples. The spraying agent of the present disclosure is not limited to the following examples.

<Example 1>
A regenerated cellulose membrane forming a porous structure of a porous material was prepared by the following procedure. First, cellulose derived from bleached pulp made from wood and having a purity of 80% or more was prepared. A cellulose solution was prepared by dissolving cellulose derived from bleached pulp in an ionic liquid. As the ionic liquid, 1-ethyl-3-methylimidazolium diethylphosphate was used. A liquid film was formed on the substrate by applying a gap coating to apply a cellulose solution to the surface of the substrate. At this time, the thickness of the regenerated cellulose film was adjusted by adjusting the size of the gap.

Then, a washing step including ultrasonic treatment for 10 seconds under the conditions of 28 kHz and 0.5 W / cm ² was carried out to remove the ionic liquid in the liquid film, and a polymer gel sheet was obtained. The polymeric gel sheet was immersed in tert-butanol for 1 hour and then frozen in the freezer. The polymer gel sheet was freeze-dried under the condition of 1 MPa using a freeze-dryer FDU-2200 manufactured by Tokyo Rika Kikai Co., Ltd. In this way, a regenerated cellulose membrane was obtained.

Then, the regenerated cellulose membrane was immersed in camellia oil and shredded using an ultrasonic homogenizer SONIFIER 450 manufactured by BRANSON under the conditions of output: 30 W to 50 W and duty cycle: 0.5 pulse / sec. Then, the liquid containing camellia oil is vacuum-filtered with a 20 μm to 25 μm mesh filter paper, and the spray agent according to Example 1 containing a porous material containing camellia oil as an active ingredient and camellia oil as a dispersion medium is applied. Obtained. The content of regenerated cellulose in the spray agent according to Example 1 was 0.4% by weight. The content of camellia oil in the porous material was 91% by weight. The viscosity of the spray agent according to Example 1 at 25 ° C. was measured using a rotary viscometer. As a result, the viscosity was 5 Pa · s. In that measurement, the rotational speed of the spindle of the rotary viscometer was set to ^{1s -1.}

The weight average molecular weight of the regenerated cellulose forming the regenerated cellulose film was measured according to the Gel Permeation Chromatography (GPC) -Multi Angle Light Scattering (MALS) method. In this measurement, a liquid feeding unit LC-20AD manufactured by Shimadzu Corporation was used, and a differential refractometer Optilab rEX manufactured by Wyatt Technology Corporation and a multi-angle light scattering detector DAWN HELEOS were used as detectors. As a column, TSKgel α-M manufactured by Tosoh Corporation was used, and as a solvent, dimethylacetamide to which lithium chloride was added at a concentration of 0.1 M was used. This measurement was performed under the conditions of column temperature: 23 ° C. and flow velocity: 0.8 mL / min. As a result of the measurement, the weight average molecular weight of the regenerated cellulose forming the regenerated cellulose membrane was about 200,000.

Using a particle size distribution meter MT3300 manufactured by Nikkiso Co., Ltd., the particle size distribution of the porous material in the spray agent according to Example 1 was measured. As a result, the porous material had a volume mean diameter of about 12 μm. When there were two or more peaks in the measurement of particle size distribution, peak separation was performed to confirm the particle size of each. As a result, assuming that the peak at the smallest particle size comes from the thickness of the porous material and the peak at the larger particle size comes from the dimensions of the porous material in the direction perpendicular to the thickness of the porous material, it is porous. The volume average diameter of the material was determined. The thickness (A) of the porous material confirmed from the peak separation of the particle size distribution is about 2 μm, and the dimensions of the porous material in the direction perpendicular to the thickness direction of the porous material with respect to the thickness (A) of the porous material ( The ratio (B / A) of B) was about 5.

Using the specific surface area / pore distribution measuring device BELSORP-mini2 manufactured by Microtrac Bell, the porous structure of the porous material was measured using the regenerated cellulose membrane before containing camellia oil. This measurement was carried out according to the gas adsorption method using nitrogen. As a result, in the porous structure of the porous material, the average pore diameter is about 19 nm, the volume of the pore having a pore diameter of 100 nm or less is 2.1 cm ³ / g, and the fine pore having a pore diameter of 100 nm or less. The specific surface area of the pores was 264 m ² / g or more.

The tensile elastic modulus of the regenerated cellulose film was evaluated according to JIS K7127: 1999 using a tensile tester EZ-L manufactured by Shimadzu Corporation. As a result, the tensile elastic modulus of the regenerated cellulose film forming the porous structure of the porous material in the spray agent according to Example 1 was 0.11 GPa.

The conductivity of the spray agent according to Example 1 at 25 ° C. was measured using an electric conductivity meter conforming to JIS K0130: 2008. As a result, the conductivity was 0.1 μS / cm or less.

<Example 2>
The spray agent according to Example 2 was prepared in the same manner as in Example 1 except for the following points. In the preparation of the cellulose solution, α-cellulose (obtained from Sigma-Aldrich) having a purity of 90% or more was used instead of cellulose derived from bleached pulp made from wood and having a purity of 80% or more. In addition, chitosan, which weighs three times the weight of α-cellulose, was dissolved in the ionic liquid together with α-cellulose. As the ionic liquid, 1-ethyl-3-methylimidazolium acetate was used. The content of camellia oil as an active ingredient in the porous material of the spray agent according to Example 2 was 89% by weight. The porous structure was composed of regenerated cellulose and chitosan, a cationic polymer. The ratio of the content of chitosan to the content of regenerated cellulose in the porous structure was 3 times by weight. The concentration of the material forming the porous structure in the spray agent according to Example 2 was 0.14% by weight. In the same manner as in Example 1, the particle size distribution of the porous material in the spray agent according to Example 2 was measured. As a result, the porous material in the spray agent according to Example 2 had a volume average diameter of about 13 μm. The thickness (A) of the porous material confirmed from the peak separation of the particle size distribution is about 6 μm, and the dimensions of the porous material in the direction perpendicular to the thickness direction of the porous material with respect to the thickness (A) of the porous material ( The ratio (B / A) of B) was about 3. In the porous structure of the porous material in the spray agent according to Example 2, the volume of pores having a pore diameter of 100 nm or less is 1.9 cm ³ / g, and the specific surface area of the pores is 231 m ² / g or more. Met.

<Example 3>
The spray agent according to Example 1 and tert-butanol were mixed in the same volume to obtain the spray agent according to Example 3. The hydrogen bond term δH in the Hansen solubility parameter of tert-butanol is 14.7 MPa ^1/2 .

<Comparative example 1>
Camellia oil was prepared as a spray agent according to Comparative Example 1.

<Comparative example 2>
A non-woven fabric (manufactured by Asahi Kasei Corporation, product name: Eltus) mainly made of polyethylene terephthalate (PET) is immersed in camellia oil, and an ultrasonic homogenizer SONIFIER 450 manufactured by BRANSON is used to output: 30 W to 50 W and a duty cycle. : The non-woven fabric was shredded under the condition of 0.5 pulse / sec. In this way, a spray agent according to Comparative Example 2 having a porous structure containing PET and the like and containing a porous material containing camellia oil as an active ingredient and camellia oil as a dispersion medium was obtained. .. The content of camellia oil in the porous material was about 54%. The thickness (A) of the porous material was about 170 μm, and the minimum dimension (B) of the porous material in the direction perpendicular to the thickness direction of the porous material was about 500 μm. The thickness (A) was measured with a micrometer and the minimum dimension (B) was determined by microscopic observation.

The porous structure of the non-woven fabric before containing camellia oil was measured using a specific surface area / pore distribution measuring device BELSORP-mini2 manufactured by Microtrac Bell. This measurement was carried out according to the gas adsorption method using nitrogen. As a result, in the porous structure of the non-woven fabric, the volume of the pores having a pore diameter of 100 nm or less is 0.016 cm ³ / g, and the specific surface area of the pores having a pore diameter of 100 nm or less is 8.1 m ² / g. That was all.

<Comparative example 3>
A mesh mainly made of polypropylene (PP) was finely cut. After that, the cut mesh is immersed in camellia oil, and Comparative Example 3 has a porous structure containing PP and the like, and contains a porous material containing camellia oil as an active ingredient and camellia oil as a dispersion medium. The spray agent according to the above was obtained. The content of camellia oil in the porous material of the spray agent according to Comparative Example 3 was 14% by weight. The thickness (A) of the porous material was 832 μm, and the minimum dimension (B) of the porous material in the direction perpendicular to the thickness direction of the porous material was about 1 mm. The thickness (A) was measured with a micrometer and the minimum dimension (B) was determined by microscopic observation.

The porous structure of the mesh before containing camellia oil was measured using a specific surface area / pore distribution measuring device BELSORP-mini2 manufactured by Microtrac Bell. This measurement was carried out according to the gas adsorption method using nitrogen. As a result, in the porous structure of the mesh, the volume of the pores having a pore diameter of 100 nm or less is 0.008 cm ³ / g, and the specific surface area of the pores having a pore diameter of 100 nm or less is 1.1 m ² / g. That was all. The tensile elastic modulus of the porous material was evaluated according to JIS K7127: 1999 using a tensile tester EZ-L manufactured by Shimadzu Corporation. As a result, the tensile elastic modulus of the porous material in the spray agent according to Comparative Example 3 was 1.3 GPa.

<Mounting test A>
(Test A-1)
A sprayer with a tank, a pump, and a sprayer and with air pressure was prepared. The spray agent according to Example 1 was placed in a tank, and 100 μL of the spray agent was sprayed toward the hair of the subject at a flow rate of about 0.4 m / s. The porous material contained in the spray agent was applied to the hair for 10 hours or more without any discomfort. When five observers observed the subject's hair after wearing it, none of the observers noticed that the porous material was attached to the hair. Pressure was applied to the hair by hand 4 hours after the spraying of the spraying agent. As a result, the hair became moist and the hair became more cohesive, and I was able to feel the beauty effect. I felt that the inside of the hair, which was close to the skin, was a little moist. The test results are shown in Table 1. In the wearing feeling column of Table 1, "A" means that there was no discomfort, and "X" means that the feeling of roughness was felt. In the visibility column of Table 1, "A" means that 5 observers could not see, and "X" means that 5 observers could see. In the column of cosmetology effect after 4 hours in Table 1, "A" means that the cosmetology effect was felt very much, "B" means that the cosmetology effect was felt a little, and "X" means that the cosmetology effect was felt. It means it wasn't.

(Test A-2)
Using a hair dryer, 100 μL of the spray agent according to Example 1 was sprayed toward the hair of the subject so as to ride on warm air adjusted to a flow rate of about 5 m / s and a temperature of 40 ° C. or higher. The porous material contained in the spray agent was applied to the hair for 10 hours or more without any discomfort. When five observers observed the subject's hair after wearing it, none of the observers noticed that the porous material was attached to the hair. Pressure was applied to the hair by hand 4 hours after the spraying of the spraying agent. As a result, the hair became moist and the hair became more cohesive, and I was able to feel the beauty effect. The beauty effect was fully realized even on the inside of the hair, which is close to the skin. The results are shown in Table 1.

(Test A-3)
Test A-3 was carried out in the same manner as in Test A-1 except that the spray agent according to Comparative Example 1 was used instead of the spray agent according to Example 1. Four hours after the spraying of the spraying agent, pressure was applied to the hair by hand, but no cosmetic effect was obtained. The results are shown in Table 1.

(Test A-4)
Test A-4 was carried out in the same manner as in Test A-1 except that the spray agent according to Comparative Example 2 was used instead of the spray agent according to Example 1. The hair to which the porous material of the spray agent according to Comparative Example 2 was attached felt rough. In addition, the porous material was highly visible, and all five observers noticed that the porous material was attached. Four hours after the spraying of the spray agent, pressure was applied to the hair with a handgrip, but the beauty effect of the handgrip was not obtained. The results are shown in Table 1.

(Test A-5)
Test A-5 was carried out in the same manner as in Test A-1 except that the spray agent according to Comparative Example 3 was used instead of the spray agent according to Example 1. The hair to which the porous material of the spray agent according to Comparative Example 3 was attached felt very rough. In addition, the porous material was highly visible, and all five observers noticed that the porous material was attached. Four hours after the spraying of the spray agent, pressure was applied to the hair with a handgrip, but the beauty effect of the handgrip was not obtained. The results are shown in Table 1.

<Mounting test B>
(Test B-1)
Two commercially available hair bundles were overlapped and clipped to prepare a test hair bundle. The hair forming the hair bundle was human hair. A spraying device was placed toward one of the two hair bundles, and 100 μL of the spray agent according to Example 1 was sprayed toward the test hair bundle at a flow rate of about 0.4 m / s. After that, the weight Wt of the spray agent attached to the entire test hair bundle and the weight Wb of the spray agent attached to the hair bundle arranged far from the spray device among the two hair bundles forming the test hair bundle are added. Decided. These weights were determined by measuring the weight of the hair tress before and after spraying the spray. The ratio of the weight Wb to the weight Wt is shown in FIG.

(Test B-2)
Test B-2 was carried out in the same manner as in Test B-1 except that the flow velocity in spraying the spray was adjusted to about 0.8 m / s, and the weight Wt of the spray and the weight Wb of the spray were determined. .. The ratio of the weight Wb to the weight Wt is shown in FIG.

(Test B-3)
100 μL of the spray agent according to Example 1 was manually applied to one of the two hair bundles without spraying. After that, the weight Wt of the spray agent attached to the entire test hair bundle and the spray agent attached to the hair bundle arranged far from the side to which the spray agent was applied among the two hair bundles forming the test hair bundle. The weight Wb was determined. These weights were determined by measuring the weight of the hair tress before and after spraying the spray. The ratio of the weight Wb to the weight Wt is shown in FIG.

As shown in FIG. 6, it was suggested that the spraying agent easily adheres uniformly to the living body such as hair by spraying the spraying agent according to Example 1. From the viewpoint of evenly adhering the spray agent to the living body such as hair, it was suggested that it is advantageous to have a large flow velocity in spraying the spray agent.

<Evaluation of styling sustainability>
(Evaluation 1)
Two commercially available hair bundles were overlapped and sandwiched with clips to prepare a hair bundle for evaluation. The hair forming the hair bundle was human hair. After washing the evaluation hair bundle and drying it with a hair dryer, the shape was adjusted with a curling iron, and the widest width of the evaluation hair bundle was measured to determine the initial value Vi of the width of the evaluation hair bundle. Then, using a spraying device, 100 μL of the spray agent according to Example 1 was sprayed toward the evaluation hair bundle at a flow rate of about 0.4 m / s, and the porous material of the spray agent was attached to the evaluation hair bundle. did. Then, the environment of the evaluation hair bundle was maintained at 20 ° C. and a relative humidity of 50% RH for 4 hours. Then, the widest width of the evaluation hair bundle was measured, and the value Vr of the width of the evaluation hair bundle was determined. After that, the handgrip was applied to the evaluation hair bundle 5 times, and the work of grasping the hair and applying pressure was repeated 10 times. Then, the widest width of the evaluation hair bundle was measured, and the value Vp of the width of the evaluation hair bundle was determined. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

(Evaluation 2)
Evaluation 2 was carried out in the same manner as in Evaluation 1 except that the spray agent according to Example 2 was used instead of the spray agent according to Example 1. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

(Evaluation 3)
Evaluation 2 was carried out in the same manner as in Evaluation 1 except that the spray agent according to Example 3 was used instead of the spray agent according to Example 1. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

(Evaluation 4)
Evaluation 1 except that 100 μL of the spray agent according to Example 1 was sprayed on the evaluation hair bundle so as to ride on warm air adjusted to a flow rate of about 5 m / s and a temperature of 40 ° C. or higher using a hair dryer. Evaluation 4 was carried out in the same manner as above. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

(Evaluation 5)
Evaluation 5 was carried out in the same manner as in Evaluation 1 except that the spraying agent was not sprayed. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

(Evaluation 6)
Evaluation 6 was carried out in the same manner as in Evaluation 1 except that camellia oil was used instead of the spray agent according to Example 1. The values of the ratio of the value Vr to the initial value Vi (Vr / Vi) and the ratio of the value Vp to the initial value Vi (Vp / Vi) are shown in FIGS. 7 and 8, respectively.

Hair bundles tend to spread in high humidity environments. Therefore, from the viewpoint of styling sustainability, it is advantageous that the value of Vr / Vi or Vp / Vi is small. According to FIG. 7, in the evaluations 1, 2, 3, and 4, the value of Vr / Vi was small, and it was suggested that the styling was easily maintained by using the spray agent according to Examples 1, 2, and 3. .. Further, according to FIG. 8, it can be seen that the values of Vp / Vi are smaller in the evaluations 1, 2, 3, and 4, and the styling effect is enhanced by applying pressure to the hair by hand.

The fact that the porous structure of the porous material of the spray agent according to Example 2 contained chitosan, which is a cationic polymer, resulted in a smaller value of Vr / Vi or Vp / Vi in Evaluation 2. It is believed that it contributed. The fact that the spray agent according to Example 3 ^{contained tert-butanol having δH of 10 MPa 1/2} or more contributed to the further reduction of the value of Vr / Vi or Vp / Vi in Evaluation 3. it is conceivable that.

The spraying agent of the present disclosure can be used for beauty such as hair care and skin care.

1a, 1b Atomizer 2 Tank 3 Atomizer 5 Controller 6 Sensor 7 Heating element 10 Porous material 11 Porous structure 12 Active ingredient 20 Atomizer 25 Dispersion medium 35 Charger

Claims (20)

A porous material having a porous structure containing regenerated cellulose and containing an active ingredient effective for a living body in contact with the porous structure,
Containing a dispersion medium for dispersing the porous material,
The porous material has a volume mean diameter of 200 μm or less and has a volume average diameter of 200 μm or less.
The volume of the pores having a pore diameter of 100 nm or less in the porous structure is 0.5 cm ³ / g or more, and the specific surface area of the pores in the porous structure is 10 m ² / g or more.
The content of the active ingredient in the porous material is 30% or more on a weight basis.
Spray agent. The spray agent according to claim 1, wherein the regenerated cellulose has a weight average molecular weight of 100,000 or more. The spray agent according to claim 1 or 2, wherein the ratio of the dimensions of the porous material to the thickness of the porous material in the direction perpendicular to the thickness direction of the porous material is 2 or more. The spray agent according to any one of claims 1 to 3, wherein the porous structure has an elastic modulus of 1 GPa or less. The spray agent according to any one of claims 1 to 4, wherein the porous structure further contains a cationic substance. The spray agent according to any one of claims 1 to 5, which has a conductivity of 1 mS / cm or less at 25 ° C. The spray agent according to any one of claims 1 to 6, which has a viscosity of 10 Pa · s or less at 25 ° C. The spray agent according to any one of claims 1 to 7, further containing a cationic substance. The spray agent according to any one of claims 1 to 8, wherein the dispersion medium contains a liquid substance having a hydrogen bond term δH of 10 MPa ^{1/2 or more in the Hansen solubility parameter.} A tank for storing the spray agent according to any one of claims 1 to 9, and a tank for storing the spray agent.
A sprayer for spraying the spray agent,
Sprayer. The spraying device according to claim 10, wherein the sprayer sprays the spraying agent at a flow rate of 0.1 m / s or more. The spraying device according to claim 10 or 11, further comprising a heating element capable of generating heat at 40 ° C. or higher. The spray device according to any one of claims 10 to 12, further comprising a charger for charging at least one of the porous material of the spray agent and the dispersion medium. The flow velocity of the spray agent sprayed from the atomizer, the temperature of the atomizer sprayed from the atomizer, the spray interval of the atomizer in the atomizer, the amount of the atomizer sprayed by the atomizer, the spray by the atomizer. 13. The spray according to claim 13, further comprising a controller that adjusts at least one item selected from the group consisting of the flow direction of the spray agent to be sprayed and the charged state of the spray agent sprayed by the sprayer. apparatus. Equipped with a sensor that detects the state of the living body
The spray device according to claim 14, wherein the controller adjusts the item based on the detection result of the sensor. The sensor detects the amount of water contained in the living body and
The spraying device according to claim 15, wherein the controller adjusts the amount of the spraying agent sprayed by the sprayer based on the amount of water detected by the sensor. A method for using a spraying agent, which comprises spraying the spraying agent according to any one of claims 1 to 9 toward the living body when the living body is wet with water. A method for using a spraying agent, which comprises spraying the spraying agent according to any one of claims 1 to 9 toward the living body and then adjusting the temperature of the environment of the living body to 40 ° C. or higher. To prepare a porous material having a porous structure containing regenerated cellulose and containing an active ingredient effective for a living body in contact with the porous structure.
By shredding or refining the porous material to give a volume mean diameter of 200 μm or less,
Including dispersing the shredded or finely divided porous material in a dispersion medium.
The volume of the pores having a pore diameter of 100 nm or less in the porous structure is 0.5 cm ³ / g or more, and the specific surface area of the pores in the porous structure is 10 m ² / g or more.
The content of the active ingredient in the porous material is 30% or more on a weight basis.
A method for producing a spray agent. The method for producing a spray agent according to claim 19, wherein the porous structure has an elastic modulus of 1 GPa or less.

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