WO2024154597A1 - Oil-in-water composition for second agent of coating-type film-forming agent - Google Patents

Abstract

Provided is an oil-in-water composition for a second agent of a coating-type film-forming agent with which it is possible to reduce or prevent problems such as coating unevenness and film shine.　The oil-in-water composition of the present disclosure contains a dispersion medium containing water and a microgel, oil droplets dispersed in the dispersion medium, and a silicone-based surface tension adjustment agent. The surface tension adjustment agent has a surface tension of 30.0 mN/m or less at 25°C in an aqueous solution containing 1 mass% of the surface tension adjustment agent, and the oil-in-water composition of the present disclosure is used as the second agent of a coating-type film-forming agent that contains a first agent containing a crosslinking-reactive component that constitutes the film and a second agent containing a crosslinking component that crosslinks the crosslinking-reactive component.

Description

Oil-in-water type composition for use as second agent in paint-on type film-forming agent

This disclosure relates to an oil-in-water type composition for use as the second agent in a paint-on film-forming agent.

A topical film-forming agent is known that can be applied to the body surface to form a film that can correct wrinkles, scars, etc. while protecting the skin.

Patent Document 1 discloses a formulation for application to the skin, comprising: a) a reactive component including (i) at least one high viscosity vinyl-terminated organopolysiloxane having a viscosity of 100,000 to 500,000 cst or cP at 25°C, at least one low viscosity vinyl-terminated organopolysiloxane having a viscosity of 500 to 50,000 cst or cP at 25°C, and at least one hydride-functionalized polysiloxane; and (ii) a reactive reinforcing component including a reinforcing component; and b) a crosslinking component including a platinum catalyst; wherein the crosslinking component promotes crosslinking of the reactive reinforcing component in situ, resulting in the formation of a film on the skin.

Patent No. 6105468

When a coating-type film-forming agent such as that described in Patent Document 1 is applied to the skin and cross-linked, a film is formed on the skin surface.

　Conventional paint-on film-forming agents tend to repel skin and other skincare products, resulting in uneven application. As a result, as shown in Figure 1, for example, there are cases where shine is accentuated locally in areas where the oil phase components of the second agent are in excess. Such uneven application and shine can lead to an unnatural appearance, and so there has been a demand for improvements to these problems.

The subject of this disclosure is therefore to provide an oil-in-water composition for the second agent of a paint-on film-forming agent that can reduce or prevent defects such as uneven application and shine on the film.

<Aspect 1>
A dispersion medium comprising water and a microgel;
an oil-in-water composition comprising oil droplets dispersed in the dispersion medium; and a silicone-based surface tension modifier,
The oil droplets contain an oil component and a catalyst as a cross-linking component,
The surface tension modifier has a surface tension of 30.0 mN/m or less at 25° C. in an aqueous solution containing the surface tension modifier at 1% by mass,
It is used as the second agent of a coating-type film-forming agent including a first agent containing a crosslinking reactive component that constitutes a film and a second agent containing a crosslinking component that crosslinks the crosslinking reactive component,
Oil-in-water compositions.
<Aspect 2>
The composition according to aspect 1, wherein the microgel is at least one selected from the group consisting of dimethylacrylamide/sodium acryloyldimethyltaurate crosspolymer, ammonium acryloyldimethyltaurate/VP copolymer, ammonium acryloyldimethyltaurate/beheneth-25 methacrylate crosspolymer, and agar.
Aspect 3
The composition according to aspect 1 or 2, wherein the surface tension modifier is at least one selected from the group consisting of polyoxyethylene-methylpolysiloxane copolymer, dimethylpolysiloxane-methyl(polyoxyethylene)siloxane copolymer, and bisPEG-18 methyl ether dimethylsilane.
<Aspect 4>
Aspect 4. The composition of any of aspects 1-3, comprising non-porous particles.
<Aspect 5>
Aspect 5. The composition of any of the preceding aspects, wherein the oil comprises a first unsaturated organopolysiloxane or a first hydride-functionalized polysiloxane.
<Aspect 6>
Aspect 6. The composition of any one of aspects 1 to 5, comprising a polymeric emulsifier.
Aspect 7
The composition according to any one of the preceding aspects, wherein the catalyst is at least one selected from the group consisting of platinum carbonylcyclovinylmethylsiloxane complex, platinum divinyltetramethyldisiloxane complex, platinum cyclovinylmethylsiloxane complex, and platinum octanaldehyde/octanol complex.
<Aspect 8>
A coating-type film-forming agent comprising a first agent and a second agent,
The first agent comprises at least one selected from the group consisting of a second unsaturated organopolysiloxane and a second hydride-functionalized polysiloxane;
The second agent is the oil-in-water composition according to any one of Aspects 1 to 7,
When the first agent contains only the second unsaturated organopolysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent contains the first hydride-functionalized polysiloxane,
When the first agent contains only the second hydride-functionalized polysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent contains the first unsaturated organopolysiloxane;
A paint-type film-forming agent.
<Aspect 9>
9. The forming agent of claim 8, wherein the oil-in-water composition comprises non-porous particles.
Aspect 10
The forming agent according to aspect 8 or 9, wherein the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane are at least one selected from the group consisting of organopolysiloxanes having vinyl groups, vinyl-terminated organopolysiloxanes, and vinylated branched organopolysiloxanes.
<Aspect 11>
11. The forming agent of claim 10, wherein the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane are at least one member selected from the group consisting of vinyl terminated polydimethylsiloxane, vinyl terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl terminated polyphenylmethylsiloxane, vinylphenylmethyl terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane homopolymer, vinyl T-structure polymer, vinyl Q-structure polymer, monovinyl terminated polydimethylsiloxane, vinylmethylsiloxane terpolymer, and vinylmethoxysilane homopolymer.
<Aspect 12>
A forming agent according to any one of aspects 8 to 11, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are non-terminally and/or terminally hydroxylated organopolysiloxanes.
<Aspect 13>
13. The forming agent of claim 12, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are at least one selected from the group consisting of hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl-(dimethylhydrosiloxy)siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane terpolymer.
<Aspect 14>
A kit in which the first agent and the second agent according to any one of aspects 8 to 13 are contained in separate containers, or are contained separately in each compartment of a container having two or more compartments.
<Aspect 15>
A method of using the forming agent according to any one of aspects 8 to 13, comprising the steps of:
The first agent is applied to a body surface to form a first agent layer, and then the second agent is applied onto the first agent layer and crosslinked to form a film.
The second agent is applied to the body surface to form a second agent layer, and then the first agent is applied onto the second agent layer and crosslinked to form a film; or
After preparing a mixture by mixing the first agent and the second agent, the mixture is applied to a body surface and crosslinked to form a film.
how to use.
<Aspect 16>
applying a cosmetic to a body surface before applying the first agent, the second agent, or the mixture to the body surface;
The first agent is applied to a body surface to form a first agent layer, a cosmetic is applied onto the first agent layer, and then the second agent is applied so as to cover the cosmetic.
The second agent is applied to a body surface to form a second agent layer, a cosmetic is applied onto the second agent layer, and then the first agent is applied to cover the cosmetic; or
After forming the film, a cosmetic is applied to the film.
A method of use according to aspect 15.

The present disclosure provides an oil-in-water composition for the second agent of a paint-on film-forming agent that can reduce or prevent defects such as uneven application and shine on the film.

Figure 1 is a photograph showing the state of repelling of the second agent when a conventional paint-type film-forming agent is used. In order to make the repelling phenomenon easier to understand, a red dye is blended into the aqueous phase of the second agent. FIG. 2 is a photograph of a film formed using a paint-on film-forming agent including a second agent (a second agent including a microgel and a specific surface tension modifier) according to one embodiment of the present disclosure. FIG. 3 is a graph showing the gloss level, which is an indicator of the shine of each of the resulting films. FIG. 1A is a photograph of a film of Comparative Example 1 formed by applying a conventional paint-on film-forming agent to artificial skin, and FIG. 1B is a photograph of a film of Example 20 formed by applying a paint-on film-forming agent containing a second agent according to an embodiment of the present disclosure to artificial skin.

The following describes in detail the embodiments of the present disclosure. The present disclosure is not limited to the embodiments below, and can be modified in various ways within the scope of the invention.

The oil-in-water composition of the present disclosure comprises a dispersion medium containing water and a microgel, oil droplets dispersed in the dispersion medium, and a silicone-based surface tension modifier, and the surface tension modifier has a surface tension of 30.0 mN/m or less at 25°C in an aqueous solution containing 1% by mass of the surface tension modifier, and is used as the second agent of a coating-type film-forming agent that comprises a first agent containing a cross-linking reactive component that forms a film, and a second agent containing a cross-linking component that cross-links the cross-linking reactive component.

Although not limited by the theory, it is believed that the principle of action that can reduce or prevent uneven application and shine in the resulting film when the oil-in-water composition disclosed herein is used as the second agent in a paint-on film-forming agent is as follows.

The applied film-forming agent of the present disclosure includes a first agent containing a cross-linking reactive component that constitutes the film, and a second agent containing a cross-linking component that cross-links the cross-linking reactive component. Therefore, when preparing a film using such a first agent and second agent, if uneven application occurs, it is thought that unevenness will also occur in the thickness of the obtained film. As a result, as shown in Figure 1, reflective parts are formed in the obtained film, which is thought to cause problems such as shine. Here, in Figure 1, as a result of the second agent being repelled by the first agent layer, for example, the oil phase component containing a catalyst of the second agent components is scattered, and parts where the cross-linking reaction is likely to proceed are formed locally, which is thought to cause unevenness in the obtained film and the formation of reflective parts.

The inventors therefore first investigated the effect of the viscoelasticity of the second agent using various thickeners in order to improve coating unevenness. As a result, they found that in oil-in-water compositions used as the second agent of paint-on film-forming agents, thickeners that can exert their thickening effect through a moderate packing effect (friction between microgel particles), such as microgels, are more effective than general thickeners that exert their thickening effect through a network structure of polymer chains. However, such thickeners alone were not able to sufficiently improve coating unevenness.

Based on this, the inventor further investigated the effect of the surface tension of the second agent. As a result, it was found that among various surface tension modifiers (such as surfactants), when a specific silicone-based surface tension modifier is blended with a microgel in an oil-in-water composition used as the second agent of a spread-type film-forming agent, uneven application is improved, and as a result, problems such as shine on the film can be reduced or prevented. This is believed to be a unique phenomenon that occurs due to the thickening action caused by the appropriate packing effect of the microgel and the synergistic effect of using it in combination with a specific silicone-based surface tension modifier.

As described above, when the oil-in-water composition of the present disclosure, which contains a microgel and a specific silicone-based surface tension modifier, is used as the second agent of a spread-type film-forming agent, problems such as uneven application and shine on the film can be reduced or prevented. However, the inventors have also found that if you want to improve even the slightest shine, such as that shown in the dashed frame in Figure 2, it is effective to further blend nonporous particles into the second agent.

Generally, porous particles tend to scatter light due to the multiple holes formed in them, so it was thought that the incorporation of porous particles would be effective in preventing shine on the film. However, in the oil-in-water composition of the present disclosure, unexpectedly, the incorporation of porous particles made it easier for uneven application to occur, and as a result, problems such as shine on the film were likely to occur. This is thought to be because when porous particles are incorporated into the oil-in-water composition of the present disclosure, at least one of the microgel and the specific silicone-based surface tension modifier incorporated into the composition to improve uneven application is absorbed by the porous particles, making it impossible to exhibit the desired function. Therefore, it is thought that the incorporation of non-porous particles, rather than porous particles, is effective in the oil-in-water composition of the present disclosure.

The definitions of terms used in this disclosure are as follows:

In this disclosure, a "body correction coating" refers to a coating that is intended to provide a natural skin appearance when applied to the skin of a subject. In this context, "natural skin appearance" means that when applied to the skin, the body correction coating provides similar or identical performance to at least one of the appearance, feel, and texture of actual skin, e.g., the treated skin can provide the physical properties (e.g., elasticity and firmness) of actual (e.g., current) skin.

In this disclosure, "body correction" means to mask, conceal or cover a body or skin imperfection of a subject to visually and/or tactilely improve the body or skin imperfection, but does not include methods of surgery, treatment or diagnosis of a human. Here, "body imperfection" can mean, for example, such part of the subject's body that the subject perceives as a blemish or blemish, or that a person skilled in the art, e.g., a dermatologist, esthetician or plastic surgeon, would consider to be a blemish or blemish. "Body imperfection" includes skin imperfections and loose soft tissues of the body (e.g., loose or sagging skin, looseness of breasts, buttocks, abdomen, chin, neck, etc.), and the like. Also, "skin imperfection" includes those items of the subject's skin that the subject perceives as a blemish or blemish. Examples of skin imperfections include nevus flammeus or nevus flameus (e.g., hemangioma simplex or midline nevus flammeus), melasma, wrinkles, age spots, acne, moles, scars, tattoos, birthmarks, skin deformities, birthmarks, sun damage, aging, uneven skin tone, loose skin, rough skin, hyperpigmentation, enlarged pores, telangiectasias, redness, shine, cellulite, stretch marks, or reduced skin elasticity.

In this disclosure, the term "oil-in-water composition" refers to a composition in which oil droplets are dispersed in a water-containing dispersion medium. Examples of such compositions include a composition in which oil droplets are forcibly dispersed in a water-containing dispersion medium by shaking a liquid in a state in which the water and oil are separated, and an emulsion composition in which an emulsifier is added to disperse oil droplets in a water-containing dispersion medium.

In this disclosure, "viscosity" refers to a measure of the resistance of a fluid to being deformed by either shear or tensile stress. For example, the viscosity of the first and second parts of a paint-on film former affects the thickness, spreadability, and uniformity and/or uniformity of the layer formed on a substrate. Viscosity can be reported as either dynamic viscosity (also known as absolute viscosity, typical units are Pa·s, poise, P, cP) or kinematic viscosity (typical units are cm ² /s, stokes, St, cst), which is the dynamic viscosity divided by the density of the measured fluid. The viscosity ranges of the components disclosed herein are generally provided by the suppliers of each component in units of kinematic viscosity (e.g., cst) measured using a rheometer or a Cannon-Fenske tube viscometer, although the viscosity of a fluid can also be measured using, for example, a rheometer (e.g., a linear shear rheometer or a dynamic shear rheometer) or a viscometer (a viscometric meter, also called, for example, a capillary viscometer or a rotational viscometer).

In this disclosure, the term "microgel" refers to a type of thickener that forms a water-swellable, three-dimensionally crosslinked microgel in an aqueous phase and thickens due to friction between the swollen microgel particles. The microgel may typically contain a solvent.

In this disclosure, "crosslinking" also includes the concept commonly referred to as "curing."

In this disclosure, "body surface" means the skin surface of the body.

Oil-in-water Composition
The oil-in-water composition of the present disclosure (sometimes simply referred to as the "composition") can be used as the second agent of a spread-type film-forming agent that includes a first agent containing a crosslinkable reactive component that constitutes a film, and a second agent containing a crosslinking component that crosslinks the crosslinkable reactive component, and can reduce or prevent defects such as shine in the resulting film.

The effect of reducing shine of the obtained film can be evaluated by a gloss test in the examples described below. A film prepared using the oil-in-water composition of the present disclosure can achieve a gloss at a reflection angle (sometimes called the "light receiving angle") of 45° or 50° of 100 or less, 95 or less, 90 or less, 85 or less, 80 or less, 75 or less, or 70 or less. There is no particular restriction on the lower limit of the gloss, but it can be, for example, 30 or more, 35 or more, 40 or more, 45 or more, or 50 or more.

<Dispersion medium>
The dispersion medium in the oil-in-water composition of the present disclosure comprises water and a microgel.

(water)
The amount of water to be blended is not particularly limited, and from the viewpoints of, for example, the effect of improving coating unevenness, usability, crosslinking reactivity, and the like, the amount of water can be 10 mass % or more, 15 mass % or more, 20 mass % or more, 30 mass % or more, 40 mass % or more, 50 mass % or more, 60 mass % or more, 70 mass % or more, or 80 mass % or more, and can be 90 mass % or less, 80 mass % or less, 70 mass % or less, 60 mass % or less, or 50 mass % or less, relative to the total amount of the composition.

Water that can be used in the oil-in-water composition of the present disclosure is not particularly limited, but may be, for example, water used in cosmetics or quasi-drugs. For example, ion-exchanged water, distilled water, ultrapure water, and tap water can be used.

(Microgel)
The amount of the microgel is not particularly limited, and from the viewpoints of, for example, the effect of improving coating unevenness, usability, crosslinking reactivity, and the like, the amount can be 0.1 mass % or more, 0.3 mass % or more, 0.5 mass % or more, 0.7 mass % or more, or 1.0 mass % or more relative to the total amount of the composition, and can be 10 mass % or less, 8.0 mass % or less, 5.0 mass % or less, or 3.0 mass % or less.

There are no particular limitations on the microgel, and it may be, for example, one that itself forms microgel particles in the aqueous phase, or one that is made by crushing a gel-like material prepared in advance into microgel particles. Microgels may be used alone or in combination of two or more kinds.

The microgel particles are preferably spherical particles from the viewpoints of the effect of improving coating unevenness, usability, crosslinking reactivity, etc. Here, "spherical" in the case of microgel particles includes true spheres, nearly spherical, and spheroids, and even if the surface is uneven, the particle falls under the "spherical" category in this disclosure as long as the overall shape of the particle can be determined to be spherical. Specifically, the "spherical particles" in the case of microgel particles are not limited to true spheres, and can include particles whose minor axis/major axis ratio (ellipticity) is 3.0 or less, 2.5 or less, 2.0 or less, or 1.5 or less. The lower limit of such a ratio can be, for example, 1.0 or more, more than 1.0, or 1.2 or more.

There is no particular limit to the size of the microgel particles, and from the viewpoints of, for example, the effect of improving coating unevenness, usability, crosslinking reactivity, etc., it is preferable that the microgel particles have an equivalent circle diameter of 100 μm or less, 70 μm or less, 50 μm or less, 30 μm or less, 10 μm or less, 5.0 μm or less, or 1.0 μm or less. The lower limit of such particle diameter can be, for example, 0.01 μm or more, 0.05 μm or more, 0.1 μm or more, or 0.5 μm or more. Here, the equivalent circle diameter can mean, for example, the particle diameter when converted into a circular particle having the same area as the projected area of the microgel particle observed with a transmission electron microscope. Such equivalent circle diameter can be defined as the average value of 10 or more particles.

The material constituting the microgel is not particularly limited, and examples thereof include at least one selected from the group consisting of (dimethylacrylamide/sodium acryloyldimethyltaurate) crosspolymer, (ammonium acryloyldimethyltaurate/VP) copolymer, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, and Kanten. Among these, (dimethylacrylamide/sodium acryloyldimethyltaurate) crosspolymer is preferred from the viewpoint of improving coating unevenness.

<Oil Droplets>
The oil phase or oil droplets as the dispersed phase in the oil-in-water composition contain an oil component and a catalyst as a cross-linking component.

(Oil content)
The amount of the oil to be blended is not particularly limited, and from the standpoint of usability, crosslinking reactivity, and the like, for example, it can be 0.01 mass% or more, 0.03 mass% or more, 0.05 mass% or more, 0.07 mass% or more, 0.1 mass% or more, 0.3 mass% or more, 0.5 mass% or more, 0.7 mass% or more, 1.0 mass% or more, 3.0 mass% or more, 5.0 mass% or more, 7.0 mass% or more, 10 mass% or more, 15 mass% or more, or 20 mass% or more, relative to the total amount of the composition, and can be 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, 15 mass% or less, or 10 mass% or less.

The oil is not particularly limited, and examples thereof include liquid oils, solid oils, waxes, hydrocarbon oils, silicone oils, and polar oils. The oils can be used alone or in combination of two or more. Among them, silicone oil is preferred from the viewpoint of affinity with the first agent layer formed by the first agent described below. The proportion of silicone oil in the oil is not particularly limited, and can be, for example, 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more relative to the total amount of oil. There is no particular limit to the upper limit of such a proportion, but it can be, for example, 100% by mass or less, less than 100% by mass, 98% by mass or less, or 95% by mass or less.

The composition of the present disclosure may contain a first unsaturated organopolysiloxane, which is a type of silicone oil, as an oil component. The first unsaturated organopolysiloxane may function as a constituent material of the coating, and may also function as a dispersant for the catalyst.

The first unsaturated organopolysiloxane is not particularly limited, and may be, for example, one or more organopolysiloxanes having at least two carbon-carbon double bonds or at least one carbon-carbon triple bond in the molecule. Such unsaturated organopolysiloxanes are preferably one or more organopolysiloxanes having an average of at least two alkenyl functional groups and a viscosity of 10,000 to 2,000,000 cst at 25°C. Here, in this disclosure, the "carbon-carbon double bond" and the "carbon-carbon triple bond" may be simply referred to as "double bond" and "triple bond". The first unsaturated organopolysiloxane may be used alone or in combination of two or more kinds.

Such organopolysiloxanes may contain unsaturated portions (double bonds or triple bonds) in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in a combination of these, and it is particularly preferred that they are contained in the non-terminal monomer units of the polymer.

In some embodiments, the double bond-containing monomer units in the organopolysiloxane may be spaced apart, on average, by 40 monomer units or more, 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units or more.

In one embodiment, the amount of double- or triple-bond-containing monomer units in the organopolysiloxane having a double bond or triple bond can be, for example, 0.01% by weight or more or 0.03% by weight or more, and 2% by weight or less or 0.6% by weight or less.

In some embodiments, the vinyl equivalent of the organopolysiloxane having double or triple bonds can be, for example, 0.005 or more, or 0.01 or more, and 0.5 or less, or 0.25 or less per kilogram. The approximate molar amount of unsaturated double or triple bonds in the organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane. Here, the average molecular weight or molecular mass of each component disclosed herein is generally provided by the supplier of each component and can be expressed in units of Daltons (Da) or its equivalent in g/mol.

In one embodiment, the content of unsaturated portions of the unsaturated organopolysiloxane can be 0.001 mmol/g or more, 0.005 mmol/g or more, 0.010 mmol/g or more, 0.050 mmol/g or more, or 0.10 mmol/g or more, and can be 5.0 mmol/g or less, 3.0 mmol/g or less, 1.0 mmol/g or less, 0.50 mmol/g or less, 0.40 mmol/g or less, 0.30 mmol/g or less, 0.25 mmol/g or less, 0.20 mmol/g or less, or 0.15 mmol/g or less.

In one embodiment, the first unsaturated organopolysiloxane can have a viscosity of 10,000 to 2,000,000 cst at 25° C. The lower limit of the viscosity is preferably 20,000 cst or more, 40,000 cst or more, 60,000 cst or more, 80,000 cst or more, or 100,000 cst or more, and more preferably 125,000 cst or more or 150,000 cst or more. The upper limit of the viscosity is preferably 1,000,000 cst or less, 500,000 cst or less, 450,000 cst or less, 400,000 cst or less, 350,000 cst or less, 300,000 cst or less, or 250,000 cst or less, more preferably 200,000 cst or less or 180,000 cst or less, and even more preferably 165,000 cst or less.

In one embodiment, the first unsaturated organopolysiloxane can have an average molecular weight of 60,000 Da to 500,000 Da. The lower limit of the average molecular weight is preferably 72,000 Da or more, 84,000 Da or more, 96,000 Da or more, or 100,000 Da or more, and more preferably 140,000 Da or more or 150,000 Da or more. The upper limit of the average molecular weight is preferably 200,000 Da or less, 190,000 Da or less, 180,000 Da or less, or 170,000 Da or less, more preferably 160,000 Da or less, and even more preferably 155,000 Da or less.

As the first unsaturated organopolysiloxane, for example, at least one unsaturated organopolysiloxane selected from the group consisting of organopolysiloxanes having vinyl groups, vinyl-terminated organopolysiloxanes, and vinylated branched organopolysiloxanes can be used.

Specific examples thereof include vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane homopolymer, vinyl T-structure polymer, vinyl Q-structure polymer, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymer, and vinylmethoxysilane homopolymer. The first unsaturated organopolysiloxane can be used alone or in combination of two or more. Among these, vinyl-terminated polydimethylsiloxane is preferred, and vinyl dimethicone (divinyl dimethicone) is more preferred. In this disclosure, "terminal" refers to either one terminal or both terminals. When distinguishing between these, it can be written as "vinyl one terminal" or "vinyl both terminals", for example.

b. First hydride-functionalized polysiloxane The composition of the present disclosure may include a first hydride-functionalized polysiloxane, which is a type of silicone oil, as an oil component. The first hydride-functionalized polysiloxane may function as a constituent material of the coating.

The first hydride-functionalized polysiloxane is not particularly limited, and may be, for example, a compound represented by the following formula 1. The first hydride-functionalized polysiloxane may be used alone or in combination of two or more kinds:

In formula 1, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are each independently selected from hydrogen, C _1-20 alkyl, C _2-20 alkenyl, C _5-10 aryl, hydroxyl, or C _1-20 alkoxy, and m and n are each independently an integer from 10 to 6,000, provided that at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b is hydrogen.

In some embodiments, at least one of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b is hydrogen, and the remainder are C _1-20 alkyl.

In some embodiments, at least two of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are hydrogen (e.g., two Si—H units per functionalized hydridopolysiloxane molecule).

In other embodiments, at least three of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are hydrogen (e.g., three Si—H units per functionalized hydridopolysiloxane molecule).

In some embodiments, at least two of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are hydrogen (e.g., two Si—H units per functionalized hydridopolysiloxane molecule), and the remainder are C _1-20 alkyl.

In other embodiments, at least three of R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b , R ^9b and R ^10b are hydrogen (e.g., three Si—H units per functionalized hydridopolysiloxane molecule), and the remainder are C _1-20 alkyl.

In some embodiments, at least two of R ^4b , R ^5b , R ^9b and R ^10b are hydrogen (eg, two Si—H units per functionalized hydridopolysiloxane molecule), and the remainder are C _1-20 alkyl.

In other embodiments, at least three of R ^4b , R ^5b , R ^9b and R ^10b are hydrogen (eg, three Si—H units per functionalized hydridopolysiloxane molecule), and the remainder are C _1-20 alkyl.

In some embodiments, the sum of m and n is an integer between 10 and 1,300, between 10 and 1,100, between 10 and 600, between 15 and 500, between 15 and 400, between 20 and 300, between 20 and 200, between 25 and 100, between 25 and 75, between 30 and 50, or between 40 and 45.

In some embodiments, the first hydride-functionalized polysiloxane can be a non-terminally and/or terminally hydrogenated organopolysiloxane, which is composed of one or more organopolysiloxanes having at least two Si-H units in the molecule, preferably one or more organopolysiloxanes having an average of at least two Si-H units and having a viscosity of 2 to 100,000 cst at 25°C.

In an embodiment, the organopolysiloxane having Si—H units may contain such Si—H units in a terminal unit of the polymer, in a non-terminal monomer unit of the polymer, or in a combination thereof. Of these, it is preferred that the Si—H units are contained in a non-terminal monomer unit of the polymer. In this case, the first hydride-functionalized polysiloxane may be alkyl-terminated. For example, in formula 1, one or both of R ^2b and R ^7b may be a C _1-20 alkyl.

In one embodiment, in formula 1, one, two, three, four, five or six of R ^1b , R ^2b , R ^3b , R ^6b , R ^7b and R ^8b may be C _1-20 alkyl.

In one embodiment, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b and R ^10b are each C _1-20 alkyl, for example C ₁ alkyl (for example methyl), and R ^9b may be hydrogen.

In one embodiment, R ^1b , R ^2b , R ^3b , R ^4b , R ^5b , R ^6b , R ^7b , R ^8b and R ^9b are each C _1-20 alkyl, for example C ₁ alkyl (for example methyl), and R ^10b may be hydrogen.

In some embodiments, the Si-H containing monomer units in the organopolysiloxane may be spaced apart, on average, by 1 monomer unit or more, 2 monomer units or more, 5 monomer units or more, 10 monomer units or more, 20 monomer units or more, 40 monomer units or more, 200 monomer units or more, 400 monomer units or more, 1,000 monomer units or more, or 2,000 monomer units or more.

In one embodiment, the amount of Si-H-containing monomer units in the organopolysiloxane having Si-H units can be 0.003% by weight or more, 0.01% by weight or more, 0.1% by weight or more, 1% by weight or more, 3% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 26% by weight or more, and can be 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, 30% by weight or less, or 27% by weight or less.

In some embodiments, the Si-H content of the organopolysiloxane having Si-H units can be 0.1 mmol/g or more, 0.5 mmol/g or more, 1 mmol/g or more, 2 mmol/g or more, 3 mmol/g or more, or 4 mmol/g or more, and can be 20 mmol/g or less, 10 mmol/g or less, 9 mmol/g or less, 8 mmol/g or less, 7 mmol/g or less, 6 mmol/g or less, or 5 mmol/g or less. The approximate molar amount of Si-H units in the organopolysiloxane can be calculated based on the average molecular weight of the organopolysiloxane.

In one embodiment, the first hydride-functionalized polysiloxane can have a viscosity of 2 to 500,000 cst at 25° C. The lower limit of the viscosity is preferably 3 cst or more, 4 cst or more, 5 cst or more, 10 cst or more, 12 cst or more, 15 cst or more, 20 cst or more, 25 cst or more, or 30 cst or more, and more preferably 40 cst or more. The upper limit of the viscosity is preferably 200,000 cst or less, 100,000 cst or less, 50,000 cst or less, 20,000 cst or less, 10,000 cst or less, 5,000 cst or less, 2,000 cst or less, or 1,000 cst or less, and more preferably 500 cst or less. The viscosity of the hydride-functionalized polysiloxane is particularly preferably in the range of 45 to 100 cst or 45 to 50 cst at 25°C.

In one embodiment, the hydride-functionalized polysiloxane can have an average molecular weight of 400 to 500,000 Da. The lower limit of such average molecular weight is preferably 500 Da or more, 800 Da or more, 900 Da or more, 1,000 Da or more, 1,200 Da or more, 1,400 Da or more, 1,600 Da or more, 1,800 Da or more, 2,000 Da or more, or 2,200 Da or more, and more preferably 2,300 Da or more. The upper limit of the average molecular weight is preferably 250,000 Da or less, 140,000 Da or less, 100,000 Da or less, 72,000 Da or less, 62,700 Da or less, 60,000 Da or less, 50,000 Da or less, 49,500 Da or less, 36,000 Da or less, 28,000 Da or less, 25,000 Da or less, 20,000 Da or less, 15,000 Da or less, 10,000 Da or less, 5,000 Da or less, or 4,000 Da or less, and more preferably 2,500 Da or less.

The first hydride-functionalized polysiloxane may be, but is not limited to, at least one selected from the group consisting of hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl-(dimethylhydrosiloxy)siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane terpolymer. Among these, hydride-terminated polydimethylsiloxane is preferred, and hydrogen dimethicone is more preferred.

c. Other silicone oils The other silicone oils other than the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane are not particularly limited, and for example, chain silicones such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, and methylhydrogenpolysiloxane; cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane, etc. can be used. The other silicone oils can be used alone or in combination of two or more kinds.

(catalyst)
The catalyst is not particularly limited, and may be, for example, any substance capable of causing, promoting, or initiating a physical and/or chemical crosslinking reaction of the unsaturated organopolysiloxane and hydride-functionalized polysiloxane, which are crosslinking reactive components constituting the coating. The catalyst may or may not undergo permanent physical and/or chemical changes during or at the end of the process.

The catalyst may be, but is not limited to, a metal catalyst capable of initiating and/or promoting crosslinking at or below body temperature, such as Group VIII metal catalysts, for example, platinum catalysts, rhodium catalysts, palladium catalysts, cobalt catalysts, nickel catalysts, ruthenium catalysts, osmium catalysts, and iridium catalysts, and Group IVA metal catalysts, for example, germanium catalysts and tin catalysts. Of these, platinum catalysts, rhodium catalysts, and tin catalysts are preferred. The catalysts may be used alone or in combination of two or more.

Platinum catalysts include, for example, platinum carbonylcyclovinylmethylsiloxane complexes, platinum divinyltetramethyldisiloxane complexes, platinum cyclovinylmethylsiloxane complexes, platinum octanaldehyde/octanol complexes, and other Pt(0) catalysts, such as Karstedt's catalyst, platinum-alcohol complexes, platinum-alkoxide complexes, platinum-ether complexes, platinum-aldehyde complexes, platinum-ketone complexes, platinum-halogen complexes, platinum-sulfur complexes, platinum-nitrogen complexes, platinum-phosphorus complexes, platinum-carbon double bond complexes, platinum-carbon triple bond complexes, platinum-imido complexes, platinum-amide complexes, platinum-ester complexes, platinum-phosphate ester complexes, platinum-thiol ester complexes, platinum lone pair complexes, platinum-aromatic complexes, platinum π-electron complexes, and combinations thereof. Among these, at least one selected from the group consisting of platinum carbonylcyclovinylmethylsiloxane complex, platinum divinyltetramethyldisiloxane complex, platinum cyclovinylmethylsiloxane complex, and platinum octanaldehyde/octanol complex is preferred.

Rhodium catalysts include, for example, tris(dibutylsulfide)rhodium trichloride and rhodium trichloride hydrate.

Examples of tin catalysts include tin(II) octanoate, tin(II) neodecanoate, dibutyltin diisooctylmaleate, di-n-butyl bis(2,4-pentanedionate)tin, di-n-butylbutoxychlorotin, dibutyltin dilaurate, dimethyltin dineodecanoate, dimethylhydroxy(oleate)tin, and tin(II) oleate.

Among these catalysts, platinum catalysts are more preferred, with platinum divinyltetramethyldisiloxane complexes being particularly preferred.

The amount of catalyst in the oil-in-water composition may be adjusted appropriately according to the required film performance, and is not particularly limited. For example, the amount of catalyst may be 0.001% by mass or more, 0.005% by mass or more, or 0.010% by mass or more, and 1.0% by mass or less, 0.10% by mass or less, or 0.050% by mass or less, based on the total amount of the composition.

(emulsifier)
In some embodiments, the oil-in-water composition of the present disclosure can contain an emulsifier.The emulsifier in the present disclosure refers to an agent having emulsifying function (surface activity), and can also include agents generally called surfactants.In addition, the oil-in-water composition containing an emulsifier can be called an oil-in-water emulsion composition.

There is no particular limit to the amount of emulsifier used, and from the standpoint of emulsion stability, for example, it can be 0.01 mass% or more, 0.05 mass% or more, 0.1 mass% or more, or 0.2 mass% or more relative to the total amount of the composition. There is no particular limit to the upper limit of the amount of emulsifier used, but from the standpoint of film durability, for example, it is preferable that the amount of emulsifier used is 5.0 mass% or less, 4.0 mass% or less, 3.0 mass% or less, 2.0 mass% or less, or 1.0 mass% or less.

As the emulsifier, for example, anionic, cationic, amphoteric, or nonionic emulsifiers can be used. The emulsifiers can be used alone or in combination of two or more kinds.

Specific examples of the emulsifier include at least one selected from the group consisting of hydrocarbon surfactants, silicone surfactants, polymeric emulsifiers, and amphiphilic powders.

Examples of hydrocarbon surfactants include polyoxyethylene alkyl ethers, polyoxyethylene steryl ethers, polyoxyethylene fatty acid esters, polyoxyethylene polyhydric alcohol fatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, glycol fatty acid esters, glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and polyglycerin fatty acid esters.

Examples of silicone surfactants include polyether-modified silicones and alkyl-co-modified polyether-modified silicones. If a silicone surfactant exhibits a surface tension of 30.0 mN/m or less at 25°C in an aqueous solution containing 1% by mass of the surfactant, the silicone surfactant can be considered a silicone surface tension adjuster, as described below.

Among emulsifiers, polymer emulsifiers are preferred from the viewpoints of uniform dispersion (emulsifying ability) of the catalyst in the composition and storage stability of the catalyst. Polymer emulsifiers typically have a larger molecular weight and are intended to be emulsifiers (surfactants) with lower emulsifying ability than general emulsifiers (surfactants). Polymer emulsifiers may be used in combination with the emulsifiers mentioned above.

The weight average molecular weight of the polymer emulsifier may be 500 or more, 700 or more, 1,000 or more, 1,500 or more, or 2,000 or more from the viewpoint of emulsifying properties, etc. The upper limit of the weight average molecular weight of the polymer emulsifier is not particularly limited, and may be, for example, 1,000,000 or less, 100,000 or less, 10,000 or less, or 5,000 or less. The weight average molecular weight of the emulsifier is a polystyrene-equivalent value obtained by dissolving the emulsifier in N,N-dimethylformamide (DMF) to prepare a 0.5% solution, and using this to measure by GPC (gel permeation chromatography) under the following conditions:
Column: Two α-M columns (Showa Denko KK) were connected in series.
Eluent: 60 mmol/L H ₃ PO ₄ and 50 mmol/L LiBr in DMF Flow rate: 1.0 mL/min Column temperature: 40° C.
Detector: RI
Calibration curve: Prepared using polystyrene.

The polymer emulsifier is not particularly limited, and examples thereof include at least one selected from the group consisting of (acrylates/alkyl acrylate (C10-30)) crosspolymer, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, (hydroxyethyl acrylate/sodium acryloyldimethyltaurate) copolymer, PEG-modified crosspolymer/copolymer siloxane, polyether-modified crosspolymer/copolymer siloxane, stearoxyhydroxypropylmethylcellulose, and polyoxyethylene. Among these, from the viewpoint of emulsion stability, etc., (acrylates/alkyl acrylate (C10-30)) crosspolymer is preferred.

The amount of polymer emulsifier may be 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.2% by mass or more relative to the total amount of the composition, from the viewpoint of uniform dispersion (emulsification) of the catalyst in the composition, and may be 30% by mass or less, 25% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 5% by mass or less, 3% by mass or less, or 1% by mass or less.

The weight average molecular weight of a typical emulsifier (surfactant) other than a polymer emulsifier can be less than 500, 450 or less, or 400 or less, and can be 100 or more, 150 or more, or 200 or more.

The HLB of common emulsifiers (surfactants) other than polymer emulsifiers can be 2.0 or more, 3.0 or more, or 4.0 or more, and can be 10.0 or less, 9.0 or less, or 8.0 or less.

<Silicone-based surface tension adjuster>
The oil-in-water composition of the present disclosure contains a silicone-based surface tension modifier (sometimes simply referred to as a "surface tension modifier"). Such a surface tension modifier exhibits a surface tension of 30.0 mN/m or less at 25°C in an aqueous solution containing 1% by mass of the surface tension modifier. The surface tension modifier may be used alone or in combination of two or more kinds. The surface tension is the average value of values obtained by measuring three times at 25°C using a Wilhelmy plate.

From the viewpoint of improving coating unevenness, the surface tension of the surface tension adjuster is preferably 29.0 mN/m or less, 28.5 mN/m or less, 28.0 mN/m or less, 27.5 mN/m or less, or 27.0 mN/m or less. The lower limit of such surface tension can be, for example, 20.0 mN/m or more, 21.0 mN/m or more, 22.0 mN/m or more, 23.0 mN/m or more, 24.0 mN/m or more, or 25.0 mN/m or more.

From the viewpoint of improving coating unevenness, the amount of the surface tension modifier is preferably 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, 0.07% by mass or more, or 0.1% by mass or more, based on the total amount of the composition. The upper limit of the amount can be, for example, 10% by mass or less, 7.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, or 1.0% by mass or less.

There are no particular limitations on the surface tension modifier, so long as it is a silicone-based agent (an agent containing a silicone component such as a silicone chain) with a predetermined surface tension, and it may be, for example, a silicone-based surfactant with emulsifying ability (surface activity ability) as described above, or an agent without emulsifying ability. When the surface tension modifier is a silicone-based surfactant with emulsifying ability, the surface tension modifier may be contained in the interface between the oil droplets and the dispersion medium, but when it is an agent without emulsifying ability, the surface tension modifier may be contained in the dispersion medium. In this way, the surface tension modifier may be contained in the dispersion medium and/or the oil droplets described above.

Specific examples of surface tension adjusters are preferably at least one selected from the group consisting of polyoxyethylene-methylpolysiloxane copolymer, dimethylpolysiloxane-methyl(polyoxyethylene)siloxane copolymer, and bisPEG-18 methyl ether dimethylsilane, from the viewpoint of improving coating unevenness. Among these, silicone surfactants such as polyoxyethylene-methylpolysiloxane copolymer and dimethylpolysiloxane-methyl(polyoxyethylene)siloxane copolymer are more preferred, polyoxyethylene-methylpolysiloxane copolymer is even more preferred, and PEG-10 methyl ether dimethicone and PEG-11 methyl ether dimethicone are particularly preferred.

<Non-porous particles>
In some embodiments, the oil-in-water composition of the present disclosure comprises non-porous particles. When a composition comprising non-porous particles is used as the second agent, the shine of the resulting film can be further reduced or prevented. In particular, when the first agent of the coating-type film-forming agent is applied to the body surface to form a first agent layer, and then the second agent is applied, it is preferable to use an oil-in-water composition comprising non-porous particles as the second agent. In this case, the non-porous particles contained in the second agent are easily arranged near the surface of the film, so that the shine of the film can be further reduced or prevented. The non-porous particles can be used alone or in combination of two or more kinds. Here, "non-porous" means substantially non-porous, and is not limited to the case where there are no holes at all. The non-porous particles of the present disclosure may refer to particles having a BET specific surface area measured by the BET method (gas adsorption method) of 100 m ² /g or less, 80 m ² /g or less, 50 m ² /g or less, 30 m ² /g or less, or 25 m ² /g or less. There is no particular restriction on the lower limit of the BET specific surface area, and it may be, for example, 0 m ² /g or more, more than 0 m ² /g, 1 m ² /g or more, or 2 m ² /g or more.

The amount of non-porous particles is preferably 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, 5.0% by mass or more, 6.0% by mass or more, 7.0% by mass or more, 8.0% by mass or more, or 9.0% by mass or more, based on the total amount of the composition, from the viewpoint of suppressing shine. The upper limit of such amount is preferably 20% by mass or less, 15% by mass or less, 13% by mass or less, 12% by mass or less, 11% by mass or less, or 10% by mass or less, from the viewpoint of preventing defects such as uneven application, for example.

There are no particular limitations on the size of the nonporous particles, and from the viewpoint of suppressing shine, for example, it is preferable for the nonporous particles to have an equivalent circle diameter of 1.0 μm or more, 1.5 μm or more, 2.0 μm or more, 2.5 μm or more, 3.0 μm or more, or 3.5 μm or more, 10 μm or less, 9.0 μm or less, 8.0 μm or less, 7.0 μm or less, 6.0 μm or less, or 5.0 μm or less. Here, the equivalent circle diameter can mean, for example, the particle diameter when converted into a circular particle having the same area as the projected area of the nonporous particle observed under a transmission electron microscope. Such equivalent circle diameter can be defined as the average value of 10 or more particles.

The nonporous particles may be, for example, solid nonporous particles or hollow nonporous particles. From the viewpoint of suppressing shine, solid nonporous particles are preferred. From the viewpoint of suppressing shine, the nonporous particles are preferably spherical particles, and preferably particles exhibiting a refractive index of 1.4 to 1.6. Here, the term "spherical" in nonporous particles includes true spheres, nearly spherical shapes, and spheroids, and even if the surface is uneven, the particle falls under the category of "spherical" in this disclosure as long as the overall shape of the particle can be determined to be spherical. Specifically, the term "spherical particles" in nonporous particles is not limited to true spheres, and may include particles whose minor axis/major axis ratio (ellipticity) is 1.5 or less, 1.2 or less, or 1.1 or less. The lower limit of such a ratio may be, for example, 1.0 or more, more than 1.0, or 1.2 or more.

The material of the non-porous particles is not particularly limited, and may be an inorganic material or a resin material. Specific examples of such materials include inorganic oxides (e.g., zinc oxide, titanium oxide, aluminum oxide, and silicon oxide), boron nitride, magnesium carbonate, magnesium hydroxide, barium sulfate, kaolin, perlite, talc, mica, silicone resin, polyamide resin, and (meth)acrylic resin. Among these, from the viewpoint of suppressing shine, inorganic materials are preferred, inorganic oxides are more preferred, and silicon oxide (silica) is particularly preferred.

The nonporous particles may be particles that have been hydrophobized with a surface treatment agent, or may not be hydrophobized. If hydrophobization is performed, there are no particular limitations on the treatment, and examples include dimethylsilylation treatment and trimethylsilylation treatment.

When porous particles are blended into the oil-in-water composition of the present disclosure, uneven application may occur, and as a result, problems such as shininess of the film may occur.Therefore, when porous particles are blended into the oil-in-water composition, from the viewpoint of suppressing problems such as uneven application and shininess, the porous particles are preferably blended at a ratio of 10% by mass or less, 8.0% by mass or less, 5.0% by mass or less, 3.0% by mass or less, 1.0% by mass or less, 0.5% by mass or less, or 0.1% by mass or less with respect to the total amount of the composition, and it is more preferable that the porous particles are not blended into the oil-in-water composition.Note that the porous particles refer to particles having a larger number of holes on the surface than the non-porous particles of the present disclosure, and may refer to particles having a BET specific surface area measured by the BET method (gas adsorption method) of 300 m ² /g or more, 500 m ² /g or more, or 700 m ² /g or more.

<<Coating-type film-forming agent>>
The oil-in-water composition of the present disclosure can be suitably used as the second agent of a coating-type film-forming agent (sometimes simply referred to as a "forming agent") that includes a first agent and a second agent. Such a forming agent can form a film, for example, by coating the first agent on a body surface to form a first agent layer, and then coating the second agent on the first agent layer to crosslink the first agent layer. The film obtained by the coating-type film-forming agent of the present disclosure may be a body correcting film having a body correcting function, or may be a film without a body correcting function.

In some embodiments, the application performance of the first agent of the spread-type film-forming agent can be evaluated by viscosity using a Brookfield viscometer (Shibaura Systems Co., Ltd., Vismetron (trademark)). The viscosity of the first agent in the spread-type film-forming agent of the present disclosure (e.g., the viscosity immediately after preparation) measured under conditions of 25°C and 60 rpm (rotor No. 3 or No. 4) is, for example, 100 mPa·s or more, 500 mPa·s or more, 1,000 mPa·s or more, 2,000 mPa·s or more, 5,000 mPa·s or more, 7,500 mPa·s or more, 10,000 mPa·s or more, or 15,000 mPa·s or more. The viscosity can be 1,000,000 mPa·s or more, and can be 1,000,000 mPa·s or less, 750,000 mPa·s or less, 500,000 mPa·s or less, 250,000 mPa·s or less, 200,000 mPa·s or less, 175,000 mPa·s or less, 150,000 mPa·s or less, 125,000 mPa·s or less, 100,000 mPa·s or less, or 80,000 mPa·s or less. In particular, from the viewpoint of smooth application performance and suppression of dripping from the skin, the first agent of the paint-on film-forming agent preferably has a viscosity of 20,000 mPa·s or less, 15,000 mPa·s or less, or 10,000 mPa·s or less immediately after preparation, and preferably has a viscosity of 3,000 mPa·s or more, 5,000 mPa·s or more, or 7,000 mPa·s or more.

In some embodiments, the application performance of the second agent of the paint-on film-forming agent can be evaluated by viscosity using a Brookfield viscometer (Shibaura Systems Co., Ltd., Vismetron (trademark)). The viscosity of the second agent in the paint-on film-forming agent of the present disclosure (e.g., the viscosity immediately after preparation) measured under conditions of 25°C and 10 revolutions per minute (rotor No. 7) can be, for example, 10,000 mPa·s or more, 20,000 mPa·s or more, 30,000 mPa·s or more, 40,000 mPa·s or more, or 50,000 mPa·s or more, and can be 1,000,000 mPa·s or more. The viscosity can be set to 750,000 mPa.s or less, 500,000 mPa.s or less, 250,000 mPa.s or less, 200,000 mPa.s or less, 175,000 mPa.s or less, 150,000 mPa.s or less, 125,000 mPa.s or less, 120,000 mPa.s or less, 115,000 mPa.s or less, or 110,000 mPa.s or less. In particular, from the viewpoint of improving coating unevenness and suppressing shine, the second agent of the paint-on film-forming agent preferably has a viscosity of 20,000 mPa·s or more, 30,000 mPa·s or more, 40,000 mPa·s or more, or 50,000 mPa·s or more immediately after preparation, and preferably has a viscosity of 200,000 mPa·s or less, 175,000 mPa·s or less, 150,000 mPa·s or less, 125,000 mPa·s or less, 120,000 mPa·s or less, 115,000 mPa·s or less, or 110,000 mPa·s or less.

<First Agent>
The first agent constituting the paint-on type film-forming agent of the present disclosure contains at least one selected from the group consisting of the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane. However, when the first agent contains only the second unsaturated organopolysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent composed of the above-mentioned oil-in-water composition contains the above-mentioned first hydride-functionalized polysiloxane, and when the first agent contains only the second hydride-functionalized polysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent contains the first unsaturated organopolysiloxane.

The dosage form of the first agent is not particularly limited, and may be, for example, a single-phase system composed of an oil phase, a non-emulsified oil-in-water or water-in-oil two-phase system, or a two-phase system composed of an oil-in-water emulsion composition or a water-in-oil emulsion composition. Here, a single-phase system composed of an oil phase is typically an anhydrous form. In this disclosure, "anhydrous" not only means that the composition does not contain water, but also means that the water content is low, i.e., 10% by mass or less, 5% by mass or less, 2% by mass or less, 1% by mass or less, or 0.1% by mass or less. In addition, a non-emulsified two-phase system may include a water-in-oil composition in which water droplets are forcibly dispersed in a dispersion medium containing oil by shaking a liquid in a state in which the water and oil are separated, or an oil-in-water composition in which oil droplets are forcibly dispersed in a dispersion medium containing water.

Each of these formulations can be prepared appropriately by conventional methods using a crosslinking reactive component and, optionally, known materials such as oils, emulsifiers, and water, as described below.

The first agent can be applied to the body surface by painting or the like, so from the viewpoint of application performance, it preferably has a glass transition temperature below body temperature. For example, the glass transition temperature can be 37°C or lower, 25°C or lower, 10°C or lower, or 0°C or lower. There is no particular restriction on the lower limit of the glass transition temperature, but it can be, for example, -30°C or higher, -20°C or higher, or -10°C or higher. Here, "glass transition temperature" refers to the temperature at which a transition from a solid state to a liquid state occurs, and can be measured, for example, using a differential scanning calorimeter (DSC) in accordance with ASTM D3418-03.

(Second Unsaturated Organopolysiloxane)
As the second unsaturated organopolysiloxane, the same material as the above-mentioned first unsaturated organopolysiloxane can be used.

The amount of the second unsaturated organopolysiloxane in the first agent can be adjusted appropriately according to the required film performance, etc., and is not particularly limited. For example, the amount of the second unsaturated organopolysiloxane can be 5% by mass or more, 10% by mass or more, 20% by mass or more, 30% by mass or more, 35% by mass or more, or 40% by mass or more, and can be 90% by mass or less, 80% by mass or less, 70% by mass or less, 60% by mass or less, 50% by mass or less, or 45% by mass or less, based on the entire first agent.

Second Hydride-Functionalized Polysiloxane
The second hydride-functionalized polysiloxane can be the same material as the first hydride-functionalized polysiloxane described above.

The amount of the second hydride-functionalized polysiloxane in the first agent can be adjusted appropriately according to the required film performance, etc., and is not particularly limited. For example, the amount of the second hydride-functionalized polysiloxane can be 1 mass% or more, 3 mass% or more, or 5 mass% or more, and 75 mass% or less, 60 mass% or less, 50 mass% or less, 40 mass% or less, 30 mass% or less, 20 mass% or less, or 10 mass% or less, based on the entire first agent.

(Other polymers)
The first agent may optionally contain other polymers other than the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane. The other polymers may be used alone or in combination of two or more.

In one embodiment, the other polymer can have a viscosity of 0.7 cst to 50,000 cst at 25° C. The lower limit of such viscosity can be 1 cst or more, 6 cst or more, 10 cst or more, 20 cst or more, 50 cst or more, 100 cst or more, 200 cst or more, 300 cst or more, 400 cst or more, 750 cst or more, 1,000 cst or more, 1,500 cst or more, 2,000 cst or more, 2,500 cst or more, 3,000 cst or more, 3,500 cst or more, or 4,000 cst or more. The upper limit of the viscosity can be 45,000 cst or less, 40,000 cst or less, 35,000 cst or less, 30,000 cst or less, 25,000 cst or less, 20,000 cst or less, 15,000 cst or less, 12,000 cst or less, 10,000 cst or less, 5,000 cst or less, 4,000 cst or less, 2,000 cst or less, 1,500 cst or less, or 1,000 cst or less.

In some embodiments, the other polymer can have an average molecular weight of 180 Da to 80,000 Da. The lower limit of the average molecular weight can be 500 Da or more, 800 Da or more, 1,500 Da or more, 3,000 Da or more, 6,000 Da or more, 9,400 Da or more, 10,000 Da or more, 15,000 Da or more, 20,000 Da or more, 30,000 Da or more, 40,000 Da or more, 50,000 Da or more, 55,000 Da or more, 60,000 Da or more, or 62,000 Da or more. The upper limit of the average molecular weight can be 75,000 Da or less, 70,000 Da or less, 65,000 Da or less, or 63,000 Da or less.

The other polymer may preferably be one or more organopolysiloxanes having, on average, at least one alkenyl functional group and a viscosity of 0.7 to 50,000 cst at 25°C.

Specific examples of other polymers include vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, At least one selected from vinyl siloxane copolymer, vinyl-terminated vinyl rubber, vinyl methyl siloxane homopolymer, vinyl T-structure polymer, vinyl Q-structure polymer, unsaturated organic polymer (e.g., unsaturated fatty alcohol, unsaturated fatty acid, unsaturated fatty ester, unsaturated fatty amide, unsaturated fatty urethane, unsaturated fatty urea, ceramide, crocetin, lecithin, and sphingosine), monovinyl-terminated polydimethyl siloxane, vinyl methyl siloxane terpolymer, vinyl methoxy silane homopolymer, vinyl-terminated polyalkyl siloxane polymer, and vinyl-terminated polyalkoxy siloxane polymer can be used. Among these, vinyl-terminated polydimethyl siloxane is preferred, and divinyl dimethicone and 1,3-divinyl tetramethyl disiloxane are more preferred.

The amount of the other polymer in the first agent is not particularly limited and may be adjusted as appropriate depending on the required film performance, etc. For example, the amount of the other polymer may be 0.01% by mass or more, 0.1% by mass or more, 0.3% by mass or more, or 0.5% by mass or more relative to the entire first agent, and may be 20% by mass or less, 15% by mass or less, or 10% by mass or less.

<Functional Group Ratios in the Second Unsaturated Organopolysiloxane, the Second Hydride-Functionalized Polysiloxane, and the Other Polymers>
In one embodiment, the molar ratio of Si—H functional groups from the second hydride-functionalized polysiloxane to alkenyl functional groups from the second unsaturated organopolysiloxane is preferably from 60:1 to 1:5, more preferably from 45:1 to 15:1.

In one embodiment, the molar ratio of Si-H functional groups from the second hydride-functionalized polysiloxane to alkenyl functional groups from the other polymer is preferably from 60:1 to 1:5, more preferably from 45:1 to 15:1.

In one embodiment, the molar ratio of the alkenyl functional groups derived from the second unsaturated organopolysiloxane to the alkenyl functional groups derived from the other polymer is preferably from 100:1 to 1:100, and more preferably from 10:1 to 1:10.

<Second Agent>
The spreadable film-forming agent of the present disclosure uses the oil-in-water composition of the present disclosure described above as the second agent.

The second agent can also contain other polymers that can be blended into the first agent, as described above.

When the first unsaturated organopolysiloxane and other polymers are used in the second agent, the functional group ratios thereof can be the same as the functional group ratios in the second unsaturated organopolysiloxane and other polymers described above.

<Optional ingredients>
In the paint-type film-forming agent of the present disclosure, various components can be appropriately blended into the first agent and/or the second agent within a range that does not adversely affect the effects of the present disclosure.

The optional components are not particularly limited, but examples include feel modifiers, adhesion modifiers, spreadability promoters, diluents, adhesion modifiers, emulsifiers (surfactants), emollients, solvents, film-forming agents, humectants, preservatives, fibers, pigments, dyes, components that thicken the aqueous or oil phase (thickeners), protective colloids, fillers, skin permeation enhancers, optical modifiers, scattering agents, dispersants, adsorbents, magnetic materials, gas transport modifiers, liquid transport modifiers, pH modifiers, sensitization modifiers, and aesthetic modifiers. The optional components can be used alone or in combination of two or more. In particular, when a dispersant such as sodium hexametaphosphate is blended with non-porous particles in the second agent, shine can be further suppressed.

In some embodiments, the compositions of the present disclosure may further comprise one or more drugs in addition to the first agent and/or the second agent. Such drugs may include, for example, cosmetic agents, therapeutic agents, stimuli-responsive agents, and drug delivery agents.

Suitable cosmetic agents include, for example, moisturizers, UV absorbers, skin protectants, skin soothing agents, skin whitening agents, skin brighteners, skin emollients, skin smoothing agents, skin bleaching agents, skin exfoliants, skin tightening agents, beauty agents, vitamins, antioxidants, cell signaling agents, cell regulating agents, cell interacting agents, skin tanning agents, anti-aging agents, anti-wrinkle agents, spot reducers, alpha-hydroxy acids, beta-hydroxy acids, and ceramides.

Suitable therapeutic agents include, for example, pain relievers, analgesics, antipruritic agents, antiacne agents (e.g., beta-hydroxy acids, salicylic acid, benzoyl peroxide), anti-inflammatory agents, antihistamines, corticosteroids, NSAIDs (nonsteroidal anti-inflammatory drugs), antiseptics, antibiotics, antibacterial agents, antifungal agents, antiviral agents, antiallergy agents, antiirritants, insect repellents, phototherapy agents, blood clotting agents, antineoplastic agents, immune system enhancers, immune system suppressants, coal tar, anthralin, fluocinonide, methotrexate, cyclosporine, pimecrolimus, tacrolimus, azathioprine, fluorouracil, ceramides, counterirritants, and skin cooling compounds.

Suitable agents can include, for example, antioxidants, vitamins, vitamin _D3 analogs, retinoids, minerals, mineral oil, petrolatum, fatty acids, plant extracts, polypeptides, antibodies, proteins, sugars, humectants, and emollients.

How to use the coating agent
The spreadable film-forming agent of the present disclosure can be used, for example, for cosmetic or medical purposes. Here, the method of using the spreadable film-forming agent of the present disclosure does not include methods for surgery, treatment, or diagnosis of humans.

The method of using the coating-type film-forming agent of the present disclosure is not particularly limited, and examples of the method include a method in which the first agent is applied to the body surface to form a first agent layer, and then the second agent is applied on the first agent layer and crosslinked to form a film; a method in which the second agent is applied to the body surface to form a second agent layer, and then the first agent is applied on the second agent layer and crosslinked to form a film; or a method in which the first agent and the second agent are mixed to prepare a mixture, and then the mixture is applied to the body surface and crosslinked to form a film. From the viewpoint of obtaining a uniform film with few unevenness, a preferred method of use is a method in which the first agent is applied to the body surface to form a first agent layer, and then the second agent is applied on the first agent layer and crosslinked to form a film. Here, the materials described above can be used for the first agent and the second agent in the same manner.

This method may be performed once, or may be performed multiple times (e.g., two or more times, or three or more times) on the formed coating. When performed multiple times, the method may include, for example, any of the following operations:
Applying a first agent to the formed coating to form a first agent layer, and then applying a second agent onto the first agent layer to further form a coating; or
An operation in which a second agent is applied to the formed coating to form a second agent layer, and then a first agent is applied onto the second agent layer to further form a coating; or an operation in which the first agent and the second agent are mixed to prepare a mixture, and then the mixture is applied to the formed coating to further form a coating.

In some embodiments, a cosmetic may be applied to the body surface before applying the first agent, the second agent, or a mixture containing the first agent and the second agent to the body surface; a first agent may be applied to the body surface to form a first agent layer, a cosmetic may be applied onto the first agent layer, and then the second agent may be applied to cover the cosmetic; a second agent may be applied to the body surface to form a second agent layer, a cosmetic may be applied onto the second agent layer, and then the first agent may be applied to cover the cosmetic; or a film may be formed, and then the cosmetic may be applied to the film.

There are no particular limitations on the cosmetics that can be used, and examples of such cosmetics include skin care cosmetics such as serums, lotions, and emulsions, sunscreen cosmetics (sun protection cosmetics), base cosmetics, and make-up cosmetics such as foundations, glosses, lipsticks, eye shadows, and nail polishes, or cosmetics that combine the functions of two or more of these cosmetics.

Furthermore, in some embodiments, the method of using the applied film-forming agent of the present disclosure can also be used as a cosmetic method. For example, when skin is exposed to dryness, moisture is unknowingly lost, and the stratum corneum on the skin surface may not be able to maintain its moisture content. When the skin lacks moisture, it is no longer able to effectively produce the moisturizing components (Natural Moisturizing Factors (NMFs)) that it produces itself. As a result, the barrier function and moisturizing function of the skin surface are reduced, making the skin more susceptible to damage, which is thought to cause a loss of moisture and lead to rough skin, etc.

On the other hand, when a film made from the applied film-forming agent of the present disclosure is applied to the skin, the occlusion effect of the film (the effect of preventing moisture from escaping from the skin) allows the skin to be well moisturized. As a result, for example, the skin's own production function of moisturizing ingredients is improved, and turnover problems in the stratum corneum are also improved, making skin problems such as roughness less likely to occur, and improving the cosmetic effect. Note that the term "cosmetic method" refers to applying the applied film-forming agent of the present disclosure to the skin to form a film and beautify the skin's condition, or a method for beautifying the skin's condition, and is different from a method of surgery, treatment, or diagnosis of humans.

There are no particular limitations on the method for applying the first or second agent to the skin, the cosmetic application layer, or the first or second agent layer, and for example, methods such as spreading with fingers, spray application, and transfer can be used.

Also, for example, when the first and/or second agents are separated into water and oil, it is preferable to shake these agents to forcibly turn them into a two-phase system (oil-in-water type or water-in-oil type) from the viewpoint of improving coating unevenness, etc.

<Application area>
The applied film-forming agent of the present disclosure can be applied to any part of the skin surface of any part of the body, that is, any part of the body surface. For example, it can be appropriately applied to the skin surface of the head, face (lips, eyes, nose, cheeks, forehead, etc.), neck, ears, hands, arms, legs, feet, chest, abdomen, back, buttocks, etc. Here, the skin also includes nails that have hardened due to changes in the keratin of the epidermis of the skin.

<Kit with a coating-type film-forming agent>
The paint-type film-forming agent of the present disclosure can be provided as a kit having the first and second agents that constitute the agent. In addition to the first and second agents, the kit may also have optional agents such as agents for facilitating application of the first agent or the like to the body surface, or the various cosmetics described above, or may be used in combination with these agents.

Such optional components include, for example, an instruction manual, a spatula-shaped applicator, a brush, a cotton swab, a cutter, scissors, the various cosmetics mentioned above, a remover for removing film from the body surface, a mirror, etc. Here, "instructions for use" can include not only general instructions for use that are attached in the form of a document within the kit, but also, for example, instructions for use printed on a packaging container that contains the kit, or on a packaging container such as a tube for injecting the first agent, etc.

In some embodiments, the kit may include, for example, the first and second agents packaged in separate containers or in separate compartments of a container having two or more compartments to prevent contact between the first and second agents. The packaged agents may be configured to be applied one at a time or to be mixed together before or during use.

Membrane
<thickness>
The thickness of the film prepared using the coating-type film-forming agent of the present disclosure described above is not particularly limited, and can be appropriately adjusted in consideration of, for example, breathability, invisibility, compressibility, occlusion to the skin, etc. The thickness of the film can be, for example, 0.5 μm or more, 1 μm or more, 10 μm or more, 30 μm or more, 40 μm or more, 50 μm or more, 70 μm or more, or 100 μm or more. There is no particular limit to the upper limit of the thickness, but it can be, for example, 1 mm or less, 800 μm or less, 500 μm or less, 300 μm or less, 150 μm or less, 100 μm or less, 90 μm or less, 80 μm or less, 70 μm or less, 60 μm or less, or 50 μm or less. Here, the thickness can be defined as the average value calculated by measuring the thickness of any part of the film five times using a high-precision digital micrometer (MDH-25MB, manufactured by Mitutoyo Corporation). The thickness of the coating refers to the thickness of the coating prepared using the coating-type coating-forming agent after it has been thoroughly dried (for example, after it has been dried in an atmosphere at room temperature for 6 hours or more).

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these. Unless otherwise specified, the blend amounts are indicated in mass %. The evaluation methods described in the examples are not limited to the oil-in-water compositions or formers described in the examples, and can be similarly carried out on the oil-in-water compositions or formers described above.

"Evaluation test"
The following tests were carried out using the test samples obtained by the manufacturing methods described below, and the results are summarized in Tables 1 to 5 and FIGS.

<surface tension>
A test sample for surface tension evaluation was prepared by adding the test material as a surface tension regulator to ion-exchanged water at a blending ratio of 1 mass %. The surface tension of the test sample was measured three times by the Wilhelmy method using a dynamic contact angle measuring device (DCAT21, manufactured by Data Physics) in an atmosphere of 25 ° C. The surface tension values listed in the table are the average values obtained by measuring three times.

<viscosity>
The viscosity of the test sample was measured using a Brookfield viscometer (Vismetron (trademark), manufactured by Shibaura Semtec Co., Ltd.) at 25° C., rotor No. 7, and 10 rpm. The viscosity values shown in the table are the average values obtained by measuring three times.

<Uneven coating evaluation test: Repelling resistance>
The first agent of the paint-on film-forming agent was applied to the backs of the hands of 20 expert panelists to form a first agent layer, and then each test sample was applied to this first agent layer. The unevenness of the application was evaluated according to the following criteria:
(Evaluation criteria)
S: 19 or more out of 20 expert panelists evaluated that the test sample was evenly applied to the back of the hand with no repellency.
A: 17 to 18 expert panelists out of 20 evaluated that the test sample was evenly applied to the back of the hand and did not repel.
B: 14 to 16 expert panelists out of 20 evaluated that the test sample was evenly applied to the back of the hand and did not repel.
C: 10 to 13 expert panelists out of 20 evaluated that the test sample was evenly applied to the back of the hand and did not repel.
D: Nine or fewer expert panelists out of 20 judged that the test sample was evenly applied to the back of the hand with no repellency.

<Shine evaluation test: Shine resistance>
The shine of the film formed in the coating unevenness evaluation test after 30 minutes was evaluated according to the following criteria:
(Evaluation criteria)
S: 19 or more out of 20 expert panelists evaluated that the film was not shiny.
A: 17 to 18 of 20 expert panelists evaluated that the film was not shiny.
B: 14 to 16 of 20 expert panelists evaluated that the film was not shiny.
C: 10 to 13 expert panelists out of 20 evaluated that the film was not shiny.
D: Nine or less out of 20 expert panelists evaluated that the film was not shiny.

<Glossiness>
A first agent of a coating-type film-forming agent was applied to black artificial leather (Saplare (trademark), Idemitsu Fine Techno Co., Ltd.) to form a first agent layer, and then a test sample was applied as a second agent to this first agent layer to form a film having a thickness of about 100 μm after drying at room temperature for 6 hours, thereby preparing a test sample for evaluating gloss. The obtained test sample was set in a goniophotometer (Gonio SPECTROPHOTOMETER GSP-1B, Murakami Color Research Laboratory Co., Ltd.) and the gloss was measured in the reflection angle range of -25° to 75°.

Test Example 1: Effect of Surface Tension Adjuster
In Test Example 1, the effect of different surface tension modifiers in the second agent applied to the first agent layer of the paint-on film-forming agent on coating unevenness was examined. The results are shown in Table 1. Note that the test samples of Reference Examples 1 to 8 contain only a surface tension modifier and water, and do not contain any catalyst or other components, and are therefore listed as Reference Examples.

<First agent: Single-phase system composed of oil phase>
The first agent was prepared by uniformly mixing 30 parts by weight of 165,000 cst divinyl dimethicone as the second unsaturated organopolysiloxane, 7 parts by weight of 45 cst hydrogen dimethicone as the second hydride-functionalized polysiloxane, 6 parts by weight of silylated silica as a filler, and 57 parts by weight of a mixture of dimethicone and trisiloxane as an oil.

<Second Agent>
A second agent such as an oil-in-water composition was produced by the following method using the formulation shown in Table 1. Here, the numbers shown below correspond to the numbers indicating the components on the left side of the formulation in Table 1.

(Comparative Example 1)
The materials No. 1 to No. 4 and No. 9 to No. 11 were uniformly mixed to prepare an aqueous phase part, and then the materials No. 5 to No. 8 were added to this aqueous phase part and mixed uniformly to prepare the second agent of the oil-in-water composition of Comparative Example 1.

(Reference Examples 1 to 8)
Test samples of Reference Examples 1 to 8 were prepared by mixing each surface tension modifier with water.

<result>
From the results in Table 1, it was confirmed that the second agent of Comparative Example 1, which does not contain a surface tension modifier, is easily repelled by the first agent layer. On the other hand, when comparing Reference Examples 1 to 8, it was found that the repelling property was improved by using a silicone-based surface tension modifier having a surface tension of 30.0 mN/m or less.

Test Example 2: Effect of thickener
In Test Example 2, the effect of different thickeners in the second agent of a paint-on film-forming agent on coating unevenness was examined. The results are shown in Table 2. Note that the composition of the formulation shown in Table 2 does not contain a surface tension modifier.

<First Agent>
The first agent of Test Example 1 was used in the same manner.

<Second Agent>
(Comparative Examples 2 to 10)
The second parts of the oil-in-water compositions of Comparative Examples 2 to 10 were prepared in the same manner as Comparative Example 1, except that the formulation was changed to that shown in Table 2. The thickener was added when the aqueous phase part was prepared.

<result>
The results of Comparative Examples 4 and 6 in Table 2 show that the use of a microgel type thickener tends to improve repellency resistance.

Test Example 3: Effect of combined use of specific surface tension adjuster and thickener
In Test Example 3, the effect of the combination of a silicone-based surface tension regulator having a specified surface tension and a microgel-type thickener in the second agent of a paint-on film-forming agent on uneven application was investigated. The results are shown in Tables 3 and 4.

<First Agent>
The first agent of Test Example 1 was used in the same manner.

<Second Agent>
(Examples 1 to 9 and Comparative Examples 11 to 13)
Except for changing the formulations to those shown in Tables 3 and 4, the second parts of the oil-in-water compositions of Examples 1 to 9 and Comparative Examples 11 to 13 were prepared in the same manner as in Comparative Example 1. The surface tension modifier and thickener were added when the aqueous phase part was prepared.

<result>
As is clear from the results in Tables 3 and 4, it was confirmed that the use of a silicone-based surface tension modifier having a surface tension of 30.0 mN/m or less in combination with a microgel-type thickener significantly improves repellency resistance.

Test Example 4: Effect of combined use of specific surface tension adjusters, thickeners, and particles
In Test Example 4, the effect of using a silicone-based surface tension regulator having a specific surface tension and a microgel-type thickener and particles in the second agent of a coating-type film-forming agent on coating unevenness and shininess was examined.The results are shown in Tables 5 and 6.Note that the reference comparative example in Table 5 is actually an example because this composition also contains a specific surface tension regulator and thickener, but it is an example used to compare a composition containing porous particles with a composition containing non-porous particles, so it is referred to as a reference comparative example.

<First Agent>
The first agent of Test Example 1 was used in the same manner.

<Second Agent>
(Examples 10 to 21 and Reference Comparative Examples 1 to 4)
Except for changing the formulations to those shown in Tables 5 and 6, the second agents of the oil-in-water compositions of Examples 10 to 21 and Reference Comparative Examples 1 to 4 were prepared in the same manner as in Comparative Example 1. The surface tension modifier, thickener, and particles were added during the preparation of the aqueous phase part.

<result>
As is clear from the results in Tables 5 and 6, it was confirmed that when nonporous particles are further blended into an oil-in-water emulsion composition used as the second agent in a spread-type film-forming agent, in addition to a silicone-based surface tension modifier having a surface tension of 30.0 mN/m or less and a microgel-type thickener, the shine resistance is further improved.

In addition, the results of Reference Comparative Examples 1 to 4 in Table 5 show that the incorporation of porous particles into an oil-in-water emulsion composition reduces repellency resistance.

The results of Examples 17 and 20 also show that the addition of a dispersant further improves shine resistance.

Test Example 5: Glossiness of the coating
In Test Example 5, the first agent of Test Example 1 was used as the first agent of the paint-on film-forming agent, and the oil-in-water compositions of Comparative Example 1 and Example 20 were used as the second agent of the paint-on film-forming agent, and the gloss evaluation was carried out as described above. The results are shown in Figures 3 and 4.

<result>
As is clear from Figures 3 and 4, it was confirmed that the gloss, i.e., shine, was lower when the oil-in-water composition of Example 20 was used as the second agent compared to Comparative Example 1. From Figure 3, it was found that Example 20 containing nonporous particles can reduce the gloss by about 30% compared to Comparative Example 1. The gloss of Comparative Example 1 and Example 20 at a reflection angle of 45° was 111.6 and 79.5, respectively, and the gloss of Comparative Example 1 and Example 20 at a reflection angle of 50° was 109.3 and 82.1, respectively.

Claims (16)

A dispersion medium comprising water and a microgel;
an oil-in-water composition comprising oil droplets dispersed in the dispersion medium; and a silicone-based surface tension modifier,
The oil droplets contain an oil component and a catalyst as a cross-linking component,
The surface tension modifier has a surface tension of 30.0 mN/m or less at 25° C. in an aqueous solution containing the surface tension modifier at 1% by mass,
It is used as the second agent of a coating-type film-forming agent including a first agent containing a crosslinking reactive component that constitutes a film and a second agent containing a crosslinking component that crosslinks the crosslinking reactive component,
Oil-in-water compositions. The composition according to claim 1, wherein the microgel is at least one selected from the group consisting of (dimethylacrylamide/sodium acryloyldimethyltaurate) crosspolymer, (ammonium acryloyldimethyltaurate/VP) copolymer, (ammonium acryloyldimethyltaurate/beheneth-25 methacrylate) crosspolymer, and agar. The composition according to claim 1 or 2, wherein the surface tension modifier is at least one selected from the group consisting of polyoxyethylene-methylpolysiloxane copolymer, dimethylpolysiloxane-methyl(polyoxyethylene)siloxane copolymer, and bisPEG-18 methyl ether dimethylsilane. The composition of claim 1 or 2, comprising non-porous particles. The composition of claim 1 or 2, wherein the oil comprises a first unsaturated organopolysiloxane or a first hydride-functionalized polysiloxane. The composition according to claim 1 or 2, which contains a polymeric emulsifier. The composition according to claim 1 or 2, wherein the catalyst is at least one selected from the group consisting of platinum carbonylcyclovinylmethylsiloxane complex, platinum divinyltetramethyldisiloxane complex, platinum cyclovinylmethylsiloxane complex, and platinum octanaldehyde/octanol complex. A coating-type film-forming agent comprising a first agent and a second agent,
The first agent comprises at least one selected from the group consisting of a second unsaturated organopolysiloxane and a second hydride-functionalized polysiloxane;
The second agent is the oil-in-water composition according to claim 1,
When the first agent contains only the second unsaturated organopolysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent contains the first hydride-functionalized polysiloxane,
When the first agent contains only the second hydride-functionalized polysiloxane among the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane, the second agent contains the first unsaturated organopolysiloxane;
A paint-type film-forming agent. The forming agent of claim 8, wherein the oil-in-water composition comprises non-porous particles. The forming agent according to claim 8 or 9, wherein the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane are at least one selected from the group consisting of organopolysiloxanes having vinyl groups, vinyl-terminated organopolysiloxanes, and vinylated branched organopolysiloxanes. The forming agent according to claim 10, wherein the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane are at least one selected from the group consisting of vinyl-terminated polydimethylsiloxane, vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer, vinyl-terminated trifluoropropylmethylsiloxane-dimethylsiloxane copolymer, vinyl-terminated diethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane-dimethylsiloxane copolymer, trimethylsiloxy-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, silanol-terminated vinylmethylsiloxane-dimethylsiloxane copolymer, vinylmethylsiloxane homopolymer, vinyl T-structure polymer, vinyl Q-structure polymer, monovinyl-terminated polydimethylsiloxane, vinylmethylsiloxane terpolymer, and vinylmethoxysilane homopolymer. The forming agent according to claim 8 or 9, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are non-terminally and/or terminally hydroxylated organopolysiloxanes. The forming agent according to claim 12, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are at least one member selected from the group consisting of hydride-terminated polydimethylsiloxane, hydride-terminated polyphenyl-(dimethylhydrosiloxy)siloxane, hydride-terminated methylhydrosiloxane-phenylmethylsiloxane copolymer, trimethylsiloxy-terminated methylhydrosiloxane-dimethylsiloxane copolymer, polymethylhydrosiloxane, trimethylsiloxy-terminated polyethylhydrosiloxane, triethylsiloxane, methylhydrosiloxane-phenyloctylmethylsiloxane copolymer, and methylhydrosiloxane-phenyloctylmethylsiloxane terpolymer. A kit in which the first agent and the second agent according to claim 8 or 9 are contained in separate containers, or are contained separately in each compartment of a container having two or more compartments. A method for using the forming agent according to claim 8 or 9, comprising the steps of:
The first agent is applied to a body surface to form a first agent layer, and then the second agent is applied onto the first agent layer and crosslinked to form a film.
The second agent is applied to the body surface to form a second agent layer, and then the first agent is applied onto the second agent layer and crosslinked to form a film; or
After preparing a mixture by mixing the first agent and the second agent, the mixture is applied to a body surface and crosslinked to form a film.
how to use. applying a cosmetic to a body surface before applying the first agent, the second agent, or the mixture to the body surface;
The first agent is applied to a body surface to form a first agent layer, a cosmetic is applied onto the first agent layer, and then the second agent is applied so as to cover the cosmetic.
The second agent is applied to a body surface to form a second agent layer, a cosmetic is applied onto the second agent layer, and then the first agent is applied to cover the cosmetic; or
After forming the film, a cosmetic is applied to the film.
16. The method of use according to claim 15.