WO2025105223A1 - Film-forming agent for application and kit including said forming agent - Google Patents

Abstract

The purpose of the present invention is to provide a film-forming agent for application which contains an oil-soluble ultraviolet absorber and is capable of forming a film that exhibits excellent ultraviolet protection performance.　A film-forming agent for application according to the present disclosure contains a first agent containing a crosslinkable component as a constituent of a film and a second agent containing a catalyst for crosslinking the crosslinkable component. The first agent and/or the second agent contains an unsaturated organopolysiloxane having a phenyl group and a vinyl group. The first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber. In the unsaturated organopolysiloxane having a phenyl group and a vinyl group, the ratio of the number of moles of the phenyl group to the number of moles of the vinyl group is 0.40 or less.

Description

Coating-type film-forming agent and kit containing said agent

The present disclosure relates to a coating-type film-forming agent and a kit containing the agent.

There are known application-type film-forming agents that can be applied to the body surface to form a film that can correct wrinkles, scars, etc.

Patent document 1 discloses a composition for in situ formation of a layer on the skin surface of a subject, the composition comprising one or more crosslinkable polymers, and an artificial skin comprising a layer formed from the composition.

Special table 2019-503396 publication

It has been found that when an oil-soluble UV absorber is blended with a coating-type film-forming agent such as that described in Patent Document 1, the resulting film may not exhibit suitable UV protection performance.

The subject of this disclosure is therefore to provide a coating-type film-forming agent that contains an oil-soluble UV absorber and is capable of forming a film that exhibits excellent UV protection performance.

<Aspect 1>
A coating-type film-forming agent comprising a first agent containing a crosslinkable reactive component that constitutes a coating, and a second agent containing a catalyst that crosslinks the crosslinkable reactive component,
the first agent and/or the second agent contains an unsaturated organopolysiloxane having a phenyl group and a vinyl group, and the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber,
In the unsaturated organopolysiloxane having a phenyl group and a vinyl group, the molar ratio of the phenyl group to the molar ratio of the vinyl group is 0.40 or less.
A paint-type film-forming agent.
<Aspect 2>
the first agent comprises at least one selected from the group consisting of a first unsaturated organopolysiloxane and a first hydride-functionalized polysiloxane;
When the first agent contains only the first unsaturated organopolysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, the second agent contains the second hydride-functionalized polysiloxane;
When the first agent contains only the first hydride-functionalized polysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, the second agent contains the second unsaturated organopolysiloxane;
2. The forming agent according to claim 1, wherein at least one of the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane comprises the unsaturated organopolysiloxane having a phenyl group and a vinyl group.
<Aspect 3>
The forming agent according to claim 1 or 2, wherein the oil-soluble UV absorber comprises an UV absorber having an IOB of 0.10 or more.
<Aspect 4>
The forming agent according to any one of Aspects 1 to 3, wherein the first agent comprises the unsaturated organopolysiloxane having a phenyl group and a vinyl group, and the oil-soluble ultraviolet absorber.
<Aspect 5>
The forming agent according to any one of aspects 1 to 4, wherein the unsaturated organopolysiloxane having a phenyl group and a vinyl group has a molar ratio of the phenyl group to the molar number of the vinyl group of 0.0040 or more.
Aspect 6
Aspect 6. The forming agent according to any one of aspects 1 to 5, wherein the weight average molecular weight of the unsaturated organopolysiloxane having a phenyl group and a vinyl group is 100,000 or less.
Aspect 7
A forming agent according to any one of Aspects 1 to 6, wherein the first agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group and/or the second agent contains a silicone oil.
<Aspect 8>
A forming agent according to any one of Aspects 1 to 7, wherein the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains inorganic particles.
<Aspect 9>
The forming agent according to any one of aspects 1 to 8, wherein the unsaturated organopolysiloxane having a phenyl group and a vinyl group is at least one selected from the group consisting of vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, and vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer.
Aspect 10
A forming agent according to any one of aspects 2 to 9, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are non-terminally and/or terminally hydrogenated organopolysiloxanes.
<Aspect 11>
11. The forming agent of claim 10, 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 12>
The forming agent according to any one of the preceding aspects, wherein the catalyst is at least one selected from the group consisting of platinum catalysts, rhodium catalysts, and tin catalysts.
<Aspect 13>
The forming agent according to aspect 12, wherein the catalyst is a platinum catalyst, and the platinum 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 14>
A kit, in which the first agent and the second agent in the forming agent according to any one of aspects 1 to 13 are contained in separate containers, or are contained separately in each compartment of a container having two or more compartments.

According to the present disclosure, it is possible to provide a coating-type film-forming agent that contains an oil-soluble UV absorber and is capable of forming a film that exhibits excellent UV protection performance.

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 applied film-forming agent of the present disclosure includes a first agent containing a crosslinkable reactive component that constitutes a film, and a second agent containing a catalyst that crosslinks the crosslinkable reactive component, the first agent and/or the second agent containing an unsaturated organopolysiloxane having a phenyl group and a vinyl group, and the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber, and the unsaturated organopolysiloxane having a phenyl group and a vinyl group has a ratio of the number of moles of phenyl groups to the number of moles of vinyl groups of 0.40 or less.

Although not limited by the theory, the principle of action of the applied film-forming agent disclosed herein is believed to be as follows, which allows the agent to contain an oil-soluble UV absorber and form a film that exhibits excellent UV protection performance.

The paint-type film-forming agent described in Patent Document 1 typically contains unsaturated organopolysiloxanes, which are also considered to be oils. Therefore, it was expected that if an oil-soluble UV absorber was used when an ultraviolet absorber was used, the resulting film would exhibit good ultraviolet protection performance. However, it was found that even if an oil-soluble UV absorber was used, the resulting film may not exhibit good ultraviolet protection performance.

The inventors have unexpectedly discovered that when an unsaturated organopolysiloxane containing a phenyl group and a vinyl group, in which the phenyl group is contained in a specific ratio, is used as the unsaturated organopolysiloxane, and when an oil-soluble ultraviolet absorber is used, the resulting film exhibits excellent ultraviolet protection performance.

Unsaturated organopolysiloxanes containing phenyl and vinyl groups themselves do not have excellent UV protection performance. Nevertheless, the films obtained when using such materials are thought to have excellent UV protection performance due to the compatibility of the unsaturated organopolysiloxane in the film-forming agent with the UV absorber.

Even when an unsaturated organopolysiloxane that does not have a specific proportion of phenyl groups is used, the oil-soluble UV absorber does not bleed out from the film and is therefore believed to be present in the film. However, in such a system, the oil-soluble UV absorber has poor compatibility and is not uniformly dispersed in the film, but exists locally as one body, and it is believed that this is why UV protection performance is not fully demonstrated. On the other hand, when an unsaturated organopolysiloxane that has a specific proportion of phenyl groups is used, the oil-soluble UV absorber becomes more easily mixed due to the influence of the specific proportion of phenyl groups, and as a result, the oil-soluble UV absorber becomes uniformly dispersed in the film, which is believed to improve UV protection performance.

Conventional sunscreen cosmetics have had the problem that, for example, when applied to the skin, the cosmetics peel off due to sweat or rubbing. The applied-type film-forming agent of the present disclosure can be applied to the skin, for example, to cause crosslinking to form a film, and the resulting crosslinked film has superior resistance to peeling due to rubbing, etc., compared to films obtained by applying conventional sunscreen cosmetics to the skin. Therefore, it is believed that the applied-type film-forming agent of the present disclosure, which can exhibit good UV protection performance, can also contribute to solving the problem of peeling that conventional sunscreen cosmetics have.

Furthermore, when removing conventional sunscreen cosmetics from the skin, for example, it is necessary to wash the skin off with a cleanser or the like. On the other hand, the film formed by the applied film-forming agent of the present disclosure has a crosslinked structure, and therefore has superior film strength compared to films that do not have a crosslinked structure. As a result, unlike films formed by conventional sunscreen cosmetics, this film has the advantage that it can be easily peeled off from the skin, for example.

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

In the present disclosure, a "body correction coating" refers to a coating that is intended to provide a coating that, when applied to a subject's skin, has the appearance of natural skin. In this context, "natural skin appearance" means that when applied to the skin, the body correction coating will provide performance similar to or identical to at least one of the appearance, feel, and texture of actual skin, e.g., the treated skin may provide 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, "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 a capillary viscometer or a rotational viscometer).

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

In this disclosure, the term "target area" refers to the area (e.g., skin) to which it is desired to impart UV protection performance.

<<Coating-type film-forming agent>>
The apply-type film-forming agent (which may be simply referred to as a "former") of the present disclosure comprises a first agent containing a crosslinkable reactive component that constitutes a film, and a second agent containing a catalyst that crosslinks this crosslinkable reactive component, wherein the first agent and/or the second agent contains an unsaturated organopolysiloxane having a phenyl group and a vinyl group, and the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber, and further wherein the unsaturated organopolysiloxane having a phenyl group and a vinyl group has a ratio of the number of moles of phenyl groups to the number of moles of vinyl groups of 0.40 or less.

The film obtained by the applied-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. The film obtained by the applied-type film-forming agent of the present disclosure can improve the strength (e.g., toughness) of the film, and as a result, can also improve the body-correcting function. Therefore, the applied-type film-forming agent of the present disclosure can be suitably used as an applied-type body-correcting film-forming agent.

<First Agent>
The paint-type film-forming agent of the present disclosure includes a first agent that includes a crosslinking reactive component that forms a film.

The first agent may contain the above-mentioned unsaturated organopolysiloxane having a phenyl group and a vinyl group, which contains a specific ratio of phenyl groups (sometimes simply referred to as "unsaturated organopolysiloxane having a phenyl group and a vinyl group"). Since the first agent contains a crosslinking reactive component that constitutes the film and can form the final film, if the first agent contains an oil-soluble UV absorber together with the unsaturated organopolysiloxane having a phenyl group and a vinyl group, the UV protection performance of the resulting film can be further improved.

(Unsaturated organopolysiloxane having phenyl and vinyl groups)
In the unsaturated organopolysiloxane having phenyl groups and vinyl groups, the molar number of phenyl groups relative to the molar number of vinyl groups is preferably 0.37 or less, 0.35 or less, 0.33 or less, 0.30 or less, 0.27 or less, 0.25 or less, or 0.23 or less, from the viewpoints of the strength of the resulting coating, compatibility with the oil-soluble ultraviolet absorber, and ultraviolet protection performance, and is also preferably 0.0040 or more, 0.0045 or more, 0.0050 or more, 0.0070 or more, 0.010 or more, more than 0.010, 0.011 or more, 0.012 or more, 0.013 or more, or 0.014 or more. Here, the molar numbers of vinyl groups and phenyl groups in the unsaturated organopolysiloxane can be measured by a relative quantitative method using ¹ H-NMR (nuclear magnetic resonance).

From the viewpoints of compatibility with oil-soluble UV absorbers and UV protection performance, the unsaturated organopolysiloxane having phenyl groups and vinyl groups preferably has a weight average molecular weight of 100,000 or less, 80,000 or less, 60,000 or less, 50,000 or less, or 40,000 or less, more preferably 30,000 or less, 29,000 or less, 28,000 or less, or 27,000 or less, and more preferably 5,000 or more, 6,000 or more, 7,000 or more, or 8,000 or more, and more preferably 9,000 or more, 9,300 or more, or 9,500 or more. Here, the "weight average molecular weight" in this disclosure refers to the weight average molecular weight in terms of polystyrene in gel permeation chromatography measurement.

The unsaturated organopolysiloxane having phenyl groups and vinyl groups can have a viscosity of 100 to 200,000 cst at 25°C. The lower limit of the viscosity can be 200 cst or more, 300 cst or more, 400 cst or more, or 500 cst or more. The upper limit of the viscosity can be 150,000 cst or less, 100,000 cst or less, 80,000 cst or less, or 60,000 cst or less.

The unsaturated organopolysiloxane having a phenyl group and a vinyl group is not particularly limited, and may be, for example, at least one selected from the group consisting of vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, and vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer. Among these, from the viewpoints of compatibility with oil-soluble ultraviolet absorbers and ultraviolet protection performance, it is preferable that the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains a vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer.

In some embodiments, the first agent of the present disclosure contains at least one selected from the group consisting of a first unsaturated organopolysiloxane and a first hydride-functionalized polysiloxane as such a crosslinking reactive component. From the viewpoint of obtaining a good coating, when the first agent contains only the first unsaturated organopolysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, the second agent in the forming agent of the present disclosure contains a second hydride-functionalized polysiloxane, and when the first agent contains only the first hydride-functionalized polysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, it is preferable that the second agent contains a second unsaturated organopolysiloxane. From the viewpoint of obtaining a better coating, it is preferable that the first agent contains both the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane. At least one of the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane contains the above-mentioned unsaturated organopolysiloxane having a phenyl group and a vinyl group.

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, 0.1% by mass or less, or 0.01% 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 is applied to the target site (e.g., skin) by painting, etc., and therefore, 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.

(First Unsaturated Organopolysiloxane)
The first unsaturated organopolysiloxane may be an organopolysiloxane having an unsaturated portion, 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 at least two alkenyl functional groups (e.g., vinyl functional groups) on average and having a viscosity of 1,00 to 2,000,000 cst at 25°C. Here, the "unsaturated portion" in the present disclosure means a portion having a "carbon-carbon double bond" and a "carbon-carbon triple bond", which may be simply referred to as a "double bond" and a "triple bond". The first unsaturated organopolysiloxane may be used alone or in combination of two or more kinds.

Such organopolysiloxanes may contain unsaturation (double or triple bond moieties) in the terminal units of the polymer, in the non-terminal monomer units of the polymer, or in a combination thereof.

In one embodiment, the double bond-containing monomer units in the first unsaturated organopolysiloxane, particularly the other unsaturated organopolysiloxane other than the unsaturated organopolysiloxane having a phenyl group and a vinyl group (sometimes simply referred to as "other unsaturated organopolysiloxane"), may be separated 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 content of unsaturated moieties in the first unsaturated organopolysiloxane, particularly the other 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. The approximate molar amount of unsaturated moieties in such organopolysiloxanes can be calculated based on the average molecular weight of the organopolysiloxane.

In one embodiment, the first unsaturated organopolysiloxane, particularly the other unsaturated organopolysiloxane, can have a viscosity of 500 to 2,000,000 cst at 25° C. The lower limit of the viscosity can be 700 cst or more, 1,000 cst or more, 3,000 cst or more, 5,000 cst or more, 10,000 cst or more, 20,000 cst or more, 40,000 cst or more, 60,000 cst or more, 80,000 cst or more, 100,000 cst or more, 125,000 cst or more, or 150,000 cst or more. The upper limit of the viscosity can be 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, 250,000 cst or less, 200,000 cst or less, 180,000 cst or less, 170,000 cst or less, or 165,000 cst or less.

In one embodiment, the first unsaturated organopolysiloxane, particularly the other unsaturated organopolysiloxane, can have an average molecular weight of 30,000 Da to 500,000 Da. The lower limit of such average molecular weight is preferably 35,000 Da or more, 40,000 Da or more, 50,000 Da or more, 60,000 Da or more, 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. The average molecular weight in this disclosure can be determined by gel permeation chromatography (GPC).

As the first unsaturated organopolysiloxane, for example, at least one unsaturated organopolysiloxane selected from the group consisting of the above-mentioned unsaturated organopolysiloxanes having phenyl groups and vinyl groups, and other unsaturated organopolysiloxanes, can be used.

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

Specific examples of other unsaturated organopolysiloxanes include vinyl-terminated polydimethylsiloxane, 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 kinds. Among them, vinyl-terminated polydimethylsiloxane is preferred, and vinyl dimethicone (divinyl dimethicone) is more preferred. In this disclosure, "end" refers to either one end or both ends. When distinguishing between these, they can be written as, for example, "vinyl one-terminated" and "vinyl both-terminated".

The amount of unsaturated organopolysiloxane in the first agent can be 5.0% by mass or more, 10% by mass or more, 20% by mass or more, 25% 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, 85% by mass or less, 80% by mass or less, 75% by mass or less, 70% by mass or less, 65% by mass or less, 60% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, or 40% by mass or less, based on the entire first agent.

When the first agent contains an unsaturated organopolysiloxane having a phenyl group and a vinyl group as the unsaturated organopolysiloxane, the amount of the unsaturated organopolysiloxane having a phenyl group and a vinyl group can be 40% by mass or more, 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 the unsaturated organopolysiloxane, and can be 100% by mass or less or less than 100% by mass, from the standpoint of compatibility with the oil-soluble ultraviolet absorber and ultraviolet protection performance, etc.

First Hydride-Functionalized Polysiloxane
The first hydride-functionalized polysiloxane is not particularly limited, and may be a polysiloxane having a hydride-functionalized moiety, such as 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, and preferably one or more organopolysiloxanes having an average of at least two Si-H units and 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 some embodiments, the Si-H content of the organopolysiloxane having Si-H units can be 0.10 mmol/g or more, 0.50 mmol/g or more, 1.0 mmol/g or more, 2.0 mmol/g or more, 3.0 mmol/g or more, or 4.0 mmol/g or more, and can be 20 mmol/g or less, 10 mmol/g or less, 9.0 mmol/g or less, 8.0 mmol/g or less, 7.0 mmol/g or less, 6.0 mmol/g or less, or 5.0 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 the 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.

There are no particular limitations on the amount of the first hydride-functionalized polysiloxane in the first agent, and it can be, for example, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, or 4.5% by mass or more relative to the entire first agent, and can be 50% by mass or less, 40% by mass or less, 30% by mass or less, 20% by mass or less, 15% by mass or less, 10% by mass or less, 8.0% by mass or less, or 5.0% by mass or less.

<Second Agent>
The second agent constituting the paint-on type film-forming agent of the present disclosure contains a catalyst that crosslinks the crosslinking reactive component in the first agent described above. The second agent of the present disclosure may also contain the unsaturated organopolysiloxane having a phenyl group and a vinyl group described above.

(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 complex (sometimes called "platinum divinyldisiloxane") being particularly preferred.

The amount of catalyst in the second agent is not particularly limited and may be adjusted as appropriate according to the required film performance, etc. For example, the amount of catalyst may be 0.001 mass% or more, 0.005 mass% or more, or 0.010 mass% or more, and 5.0 mass% or less, 3.0 mass% or less, 1.0 mass% or less, 0.10 mass% or less, or 0.050 mass% or less, relative to the total amount of the second agent.

The formulation of the second agent of the present disclosure is not particularly limited, and may be, for example, a single-phase system composed of an oil phase in an anhydrous form, 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.

Each of these formulations can be prepared appropriately by conventional methods using a catalyst and, optionally, known materials such as oil, emulsifier, and water, as described below. Silicone oil can be used as the oil, and the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane that can be used in the first agent described above may be used as this silicone oil. In this case, the unsaturated organopolysiloxane and the hydride-functionalized polysiloxane in the second agent can be called the second unsaturated organopolysiloxane and the second hydride-functionalized polysiloxane to distinguish them from the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane in the first agent.

In one embodiment, the second unsaturated organopolysiloxane, particularly the unsaturated organopolysiloxane other than the unsaturated organopolysiloxane having a phenyl group and a vinyl group, can have a viscosity of 50 to 165,000 cst at 25°C. The upper limit of the viscosity is preferably 150,000 cst or less, 100,000 cst or less, 80,000 cst or less, 50,000 cst or less, 30,000 cst or less, or 10,000 cst or less, and more preferably 5,000 cst or less, 2,000 cst or less, or 1,000 cst or less, and most preferably 500 cst or less. The lower limit of the viscosity is preferably 70 cst or more, 100 cst or more, 130 cst or more, or 150 cst or more.

<Oil-soluble UV absorber>
In the coating-type film-forming agent of the present disclosure, at least the first agent and/or the second agent containing an unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber. Here, when the unsaturated organopolysiloxane having a phenyl group and a vinyl group is contained in, for example, only one of the first agent or the second agent, the oil-soluble ultraviolet absorber may not be blended with the agent that does not contain such an unsaturated organopolysiloxane, or may be blended with the agent. In addition, when the unsaturated organopolysiloxane having a phenyl group and a vinyl group is contained in both the first agent and the second agent, the oil-soluble ultraviolet absorber may be contained in at least one of the first agent and the second agent. Therefore, in the present disclosure, "the first agent and the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contain an oil-soluble ultraviolet absorber" means that the oil-soluble ultraviolet absorber is contained in at least one of the first agent and the second agent. The oil-soluble ultraviolet absorber can be used alone or in combination of two or more. In the present disclosure, the term "oil-soluble" refers to the ability to dissolve in the oil in the first agent and/or the second agent in which the ultraviolet absorbent is blended.

Among oil-soluble UV absorbers, UV absorbers with an IOB of 0.10 or more are preferred from the viewpoints of compatibility with unsaturated organopolysiloxanes having phenyl and vinyl groups, and UV protection performance. The IOB value of such UV absorbers can be, for example, 0.10 or more, 0.11 or more, 0.12 or more, or 0.13 or more, and can be 0.50 or less, 0.45 or less, or 0.40 or less. Here, the IOB value is an abbreviation for Inorganic/Organic Balance, which is a value that represents the ratio of the inorganic value to the organic value, and is an index that indicates the degree of polarity of an organic compound. Specifically, the IOB value is expressed as IOB value = inorganic value / organic value. For each "inorganic value" and "organic value", for example, an "organic value" of 20 for one carbon atom in a molecule and an "inorganic value" of 100 for one hydroxyl group are set according to the type of atom or functional group, and the IOB value of an organic compound can be calculated by accumulating the "inorganic value" and "organic value" of all atoms and functional groups in the organic compound (see, for example, Koda Yoshio, "Organic Conceptual Diagram - Basics and Applications", pp. 11-17, Sankyo Publishing, 1984).

Examples of UV absorbers with an IOB of 0.10 or more include organic UV absorbers such as ethylhexyl methoxycinnamate, octocrylene, polysilicone-15, t-butyl methoxydibenzoylmethane, ethylhexyl triazone, bisethylhexyloxyphenol methoxyphenyl triazine, diethylamino hydroxybenzoyl hexyl benzoate, oxybenzone-3, methylene bisbenzotriazolyl tetramethylbutylphenol, homosalate, ethylhexyl salicylate (sometimes called "octyl salicylate"), cresyl methoxycinnamate, drometrizole trisiloxane, and phenylene bis-diphenyl triazine. Among these, at least one selected from the group consisting of octocrylene, t-butyl methoxydibenzoylmethane, homosalate, and ethylhexyl salicylate is preferred from the standpoint of compatibility with unsaturated organopolysiloxanes having phenyl and vinyl groups, and UV protection performance.

There are no particular limitations on the amount of oil-soluble UV absorber blended, and it can be blended appropriately depending on the required UV protection performance. The amount of oil-soluble UV absorber blended can be, for example, 1.0% by mass or more, 3.0% by mass or more, 5.0% by mass or more, 7.0% by mass or more, 10% by mass or more, 13% by mass or more, 15% by mass or more, 17% by mass or more, or 20% by mass or more relative to the entire first or second agent, and can be 40% by mass or less, 37% by mass or less, 35% by mass or less, 33% by mass or less, 30% by mass or less, or 25% by mass or less.

<Optional ingredients>
In the paint-type film-forming agent of the present disclosure, various components can be appropriately blended with the first agent and/or the second agent within a range that does not adversely affect the effects of the present disclosure. These optional components can also be blended with the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group. The optional components can be used alone or in combination of two or more.

The optional components are not particularly limited, but examples include feel modifiers, adhesion modifiers, spreadability promoters, diluents, adhesion modifiers, oils, emulsifiers (surfactants), inorganic particles, organic particles, water, humectants, preservatives, coloring materials (e.g., pigments, dyes, colorants), pearling agents, matting agents, beads, cloth, rubber materials (e.g., rubber sheets made of silicone rubber, etc.), components that thicken the water or oil phase (thickeners), protective colloids, skin permeation promoters, optical modifiers, scattering agents, adsorbents, magnetic materials, gas transport modifiers, liquid transport modifiers, pH modifiers, sensitization modifiers, and aesthetic modifiers.

Other examples of the skin care products include cosmetic agents such as moisturizers, skin protectants, skin soothing agents, skin whitening agents, skin brighteners, skin softeners, 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; and other cosmetic agents such as pain relievers, analgesics, anti-pruritic agents, anti-acne agents (e.g., beta-hydroxy acids, salicylic acid, benzoyl peroxide), anti-inflammatory agents, anti Included may be therapeutic agents such as histamines, corticosteroids, NSAIDs (nonsteroidal anti-inflammatory drugs), antiseptics, antibiotics, antibacterials, antifungals, antivirals, antiallergy agents, anti-irritants, 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; and may include, for example, antioxidants, vitamins, vitamin _D3 analogs, retinoids, minerals, mineral oils, petrolatum, fatty acids, plant extracts, polypeptides, antibodies, proteins, sugars, humectants, and emollients.

Here, some of the main optional ingredients are described in detail below.

(Oil content)
Examples of the oil include liquid oils and fats, solid oils and fats, waxes, hydrocarbon oils, ester oils, silicone oils, and polar oils other than the above-mentioned oil-soluble UV absorbers. The oil may be a non-volatile oil or a volatile oil. The oil may be used alone or in combination of two or more. Here, "volatile" refers to an oil that exhibits a volatile content of more than 5% when left at atmospheric pressure and 105°C for 3 hours. Such a volatile content can be specified as 10% or more, 20% or more, 40% or more, 50% or more, 60% or more, 80% or more, or 100%. Alternatively, the boiling point at 1 atmosphere (101.325 kPa) can be used as an indicator of volatility. This boiling point can be 250°C or less, 240°C or less, or 230°C or less, and can be 80°C or more, 100°C or more, 120°C or more, 150°C or more, or 160°C or more. In addition, in the present disclosure, "non-volatile" refers to a material that exhibits a volatile content of 5% or less when left at 105°C for 3 hours.

For example, silicone oils other than the above-mentioned unsaturated organopolysiloxanes and hydride-functionalized polysiloxanes can be used as the silicone oil. Examples of such silicone oils that can be used include linear silicones such as dimethylpolysiloxane (dimethicone), methylphenylpolysiloxane, and methylhydrogenpolysiloxane; and cyclic silicones such as diphenylsiloxyphenyltrimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane. Silicone oils are easily compatible with unsaturated organopolysiloxanes having phenyl and vinyl groups, and can therefore be suitably blended with the first agent and/or the second agent that contains unsaturated organopolysiloxanes having phenyl and vinyl groups.

The amount of oil (e.g., silicone oil) to be blended is not particularly limited, and can be blended appropriately depending on, for example, the type of formulation used, the required film strength, etc. The amount of oil (e.g., silicone oil) to be blended can be, for example, 5.0% by mass or more, 7.0% by mass or more, 10% by mass or more, 15% by mass or more, 20% by mass or more, 23% by mass or more, 25% by mass or more, 27% by mass or more, or 30% by mass or more relative to the entire first or second agent, and can be 60% by mass or less, 57% by mass or less, 55% by mass or less, 50% by mass or less, 45% by mass or less, 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less.

(Inorganic particles)
At least one of the first agent and the second agent in the coating-type film-forming agent of the present disclosure may contain inorganic particles. In particular, when inorganic particles are blended with the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group and the oil-soluble ultraviolet absorber, the ultraviolet protection performance can be further improved. The inorganic particles can be used alone or in combination of two or more kinds.

From the viewpoint of further improving the UV protection performance, the inorganic particles are preferably inorganic oxide particles. As for the inorganic particles, only hydrophobically treated particles (hydrophobic inorganic particles) or only untreated particles (e.g., hydrophilic inorganic particles) may be used, or hydrophobically treated particles (hydrophobic inorganic particles) and untreated particles (e.g., hydrophilic inorganic particles) may be used in combination.

Examples of inorganic oxides constituting the inorganic oxide particles include zinc oxide, titanium oxide, aluminum oxide, and silicon oxide (e.g., fumed silica and anhydrous silica). Among these, from the viewpoint of further improving the UV protection performance, at least one selected from the group consisting of silicon oxide, titanium oxide, and zinc oxide is preferred, and silicon oxide is more preferred.

The hydrophobic inorganic particles can typically be inorganic particles that have been hydrophobized with a surface treatment agent. There are no particular limitations on the hydrophobization treatment, and examples of the treatment include at least one selected from the group consisting of silylation treatment, dimethylsilylation treatment, and trimethylsilylation treatment.

The amount of inorganic particles (e.g., inorganic oxide particles or hydrophobized inorganic oxide particles) can be, for example, 0.1% by mass or more, 0.5% by mass or more, 1.0% by mass or more, 2.0% by mass or more, 3.0% by mass or more, 4.0% by mass or more, 4.5% by mass or more, or 5.0% by mass or more relative to the entire first or second agent, and can be 20% by mass or less, 15% by mass or less, 10% by mass or less, 7.0% by mass or less, or 5.0% by mass or less, from the viewpoint of further improving the UV protection performance.

(emulsifier)
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. Here, the emulsifier in the present disclosure refers to an agent having an emulsifying function (surface activity), and can also include agents generally called surfactants.

Specific examples of the emulsifier include at least one selected from the group consisting of hydrocarbon surfactants, silicone surfactants, 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 silicone and alkyl-co-modified polyether-modified silicone.

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% 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 first or second agent. There is no particular limit to the upper limit of the amount of emulsifier used, and it can be, for example, 5.0% by mass or less, 4.0% by mass or less, 3.0% by mass or less, 2.0% by mass or less, 1.0% by mass or less, or 0.5% by mass or less.

(water)
The water is not particularly limited, and for example, water used in cosmetics or quasi-drugs can be used, such as ion-exchanged water, distilled water, ultrapure water, and tap water.

There are no particular limitations on the amount of water to be added, and it can be adjusted as appropriate depending on, for example, the type of formulation used.

How to use the coating agent
The method of using the applied-type film-forming agent of the present disclosure is not particularly limited, and may include, for example, any of the following steps. Note that, according to this method, for example, makeup can be applied to the face, and therefore the method can also be called a makeup method. In addition, the method of using the applied-type film-forming agent of the present disclosure does not include methods for surgery, treatment, or diagnosis of humans:
Applying the first agent to the target site to form a first agent layer, and then applying the second agent onto the first agent layer to form a coating, or
The second agent is applied to the target area to form a second agent layer, and then the first agent is applied onto the second agent layer to form a film; or, the first agent and the second agent are mixed to prepare a mixture, and then the mixture is applied to the target area to form a film.

From the viewpoint of obtaining a uniform coating with few unevenness, the preferred method of use is to apply the first agent to the target area to form a first agent layer, and then apply the second agent onto this first agent layer and crosslink it to form a coating. Here, the materials described above can be used for the first agent and the second agent in the same way.

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 of applying a second agent to the formed coating to form a second agent layer, and then applying a first agent onto the second agent layer to further form a coating; or an operation of mixing the first agent and the second agent to prepare a mixture, and then applying the mixture to the formed coating to further form a coating.

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

There are no particular limitations on the cosmetics, and examples of the cosmetics that can be used include skin care cosmetics such as serums, lotions, and emulsions, sunscreen cosmetics (sun protection cosmetics), base cosmetics, or 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 does not have enough 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, for example, when a film made from the applied film-forming agent of the present disclosure is applied to the skin, it is possible to protect the skin from harmful ultraviolet rays, and 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 beauty effect. Note that a "beauty method" refers to applying the applied film-forming agent of the present disclosure to a target site to form a film and improve the condition of the target site (for example, skin), 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 target area, the cosmetic application layer, or the first or second agent layer, and for example, methods such as spreading with fingers, spray application, transfer, etc. can be used.

In addition, for example, when the first agent and/or the second agent are separated into water and oil, it is preferable to shake these agents to forcibly make them into a two-phase system (oil-in-water type or water-in-oil type) from the viewpoint of the crosslinking reactivity between the first agent and the second agent, and the dispersibility of the oil-soluble UV absorber in the coating.

<Target area>
The applied film-forming agent of the present disclosure can be applied to any part of the body, for example, the surface of the skin. The applied film-forming agent of the present disclosure can be appropriately applied to, for example, the head (e.g., scalp, etc.), face (e.g., lips, eyes, nose, cheeks, forehead, etc.), neck, ears, hands, arms, legs, feet, chest, abdomen, back, buttocks, nails, body hair (e.g., hair, eyelashes, eyebrows, beard, etc.), etc.

<<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 above-mentioned first and second agents constituting the agent. In addition to the first and second agents, the kit may have optional components such as a component for facilitating application of the first agent, etc. to a target site, the various cosmetics described above, or the kit may be used in combination with optional components.

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 the formed film from the target area, 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 instructions for use printed on, for example, the packaging container that contains the kit, or the 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.

In one embodiment, the kit can be used in combination with a remover for removing the formed film from the target site. Here, "use in combination" includes using the kit and remover as an integrated unit, i.e., including the remover in the kit, or using the kit and remover separately. For example, it is preferable to use a kit including a coat-type film-forming agent in combination with a separate remover, since it is possible to provide an optimal coat-type film-forming agent and remover for each individual.

Remover
The film formed on the target site by the applied film-forming agent of the present disclosure can be suitably removed from the target site by using the specific remover shown below. When the specific remover of the present disclosure is used, the strength of the film is not reduced, so the film can be peeled off from the target site in one go without breaking. For example, when a conventional sunscreen cosmetic is applied to the skin and then removed from the skin, it is necessary to wash it off with a detergent or the like. On the other hand, the film formed by the applied film-forming agent of the present disclosure does not require such a procedure, and the film exhibiting ultraviolet protection performance can be peeled off from the target site (e.g., skin) more easily.

In some embodiments, a suitable remover used to remove a film formed by the applied film-forming agent of the present disclosure contains at least one selected from the group consisting of a hydrocarbon oil having a weight-average molecular weight of 300 or more and 800 or less, and a polar oil having a weight-average molecular weight of 260 or more and 400 or less. From the viewpoint of effectively removing the film, it is preferable to use such a hydrocarbon oil and a polar oil in combination.

(Hydrocarbon oil)
From the viewpoint of suitably removing the film, the weight average molecular weight of the hydrocarbon oil is preferably 320 or more, or 350 or more, and more preferably 380 or more, and is preferably 750 or less, or 700 or less, and more preferably 690 or less. The hydrocarbon oils can be used alone or in combination of two or more kinds.

The type of hydrocarbon oil is not particularly limited, and examples include liquid paraffin (mineral oil), olefin oligomers and their hydrogenated products (e.g., hydrogenated polydecene), and squalane.

The amount of hydrocarbon oil is not particularly limited, and from the viewpoint of effectively removing the film, it can be, for example, 1.0 mass% or more, 5.0 mass% or more, 10 mass% or more, 20 mass% or more, or 30 mass% or more relative to the total amount of the composition constituting the remover. There is no particular upper limit to the amount, and it can be, for example, 100 mass% or less, less than 100 mass%, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.

(polar oil)
From the viewpoint of suitable removal of the film, the weight average molecular weight of the polar oil is preferably 265 or more or 270 or more, and preferably 390 or less, 380 or less, or 370 or less. From the viewpoint of suitable removal of the film, the IOB value of the polar oil is preferably 0.12 or more or 0.13 or more, and preferably 1.48 or less, 1.47 or less, or 1.46 or less. The polar oils may be used alone or in combination of two or more kinds.

There are no particular limitations on the type of polar oil, and examples include ester oils. Specific examples include isopropyl myristate (IOB value = 0.18), ethylhexyl ethylhexanoate (IOB value = 0.20), alkyl benzoate (C12-15) (IOB value = 0.18), diethylhexyl succinate (IOB value = 0.32), neopentyl glycol diheptanoate (IOB value = 0.33), tri(caprylic acid/capric acid)glyceryl (IOB value = 0.28), PPG-3 dipivalate (IOB value = 1.46), and octyl palmitate (IOB value = 0.13).

There is no particular limit to the amount of polar oil blended, and from the viewpoint of effectively removing the film, for example, it can be 1.0 mass% or more, 5.0 mass% or more, 10 mass% or more, 15 mass% or more, or 20 mass% or more relative to the total amount of the composition constituting the remover. There is no particular limit to the upper limit of the blended amount, and it can be, for example, 100 mass% or less, less than 100 mass%, 80 mass% or less, 70 mass% or less, 60 mass% or less, or 50 mass% or less.

(optional ingredient)
The remover of the present disclosure can be appropriately blended with various components within a range that does not adversely affect the film removal effect. Examples of various components include surfactants (emulsifiers), moisturizers, thickeners, water-soluble polymers, oil-soluble polymers, film-forming agents, higher fatty acids, sequestering agents, lower alcohols, higher alcohols, polyhydric alcohols, denatured alcohols, various extracts, sugars, amino acids, organic amines, polymer emulsions, chelating agents, UV absorbers, pH adjusters, skin nutrients, vitamins, water-soluble drugs applicable to medicines, quasi-drugs, cosmetics, etc., buffers, color-fading inhibitors, antioxidants, preservatives, dispersants, propellants, fillers, pigments, dyes, colorings, fragrances, water, and other oils other than those mentioned above. Optional components can be used alone or in combination of two or more.

The remover of the present disclosure may contain oils other than the above-mentioned hydrocarbon oils and polar oils. However, silicone oils may reduce the strength of the film, and as a result, may reduce the film removal performance. Therefore, from the viewpoint of effectively removing the film, the amount of silicone oil is preferably 10 mass % or less, 5.0 mass % or less, 1.0 mass % or less, 0.5 mass % or less, or 0.1 mass % or less relative to the total amount of the composition constituting the remover, and it is more preferable that silicone oil is not included in the composition constituting the remover.

How to use the remover
There is no particular limitation on the method of using the remover. In general, the remover can be applied to a part or the whole of the film formed on the target site, and then optionally rubbed. Then, the film can be removed by pulling the film that has peeled off from the target site with a finger or the like.

Membrane
<Thickness>
The thickness of the film formed 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, UV protection performance, breathability, invisibility, occlusion to the target site (e.g., skin), aesthetics, 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, or 40 μm or more. There is no particular limit to the upper limit of the thickness, but it can be, for example, 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).

<Ultraviolet protection performance>
The coating film formed using the coating-type coating agent of the present disclosure can exhibit excellent ultraviolet protection performance (ultraviolet light absorption ability). Such performance can be evaluated by the improvement rate of ultraviolet protection performance calculated using the absorbance integrated value described below. The coating film of the present disclosure can exhibit an improvement rate of more than 130%, 135% or more, 140% or more, 143% or more, 145% or more, 147% or more, or 150% or more. The upper limit of such improvement rate can be, for example, 250% or less, 230% or less, or 200% or less.

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 shown in mass %. The evaluation methods described in the examples are not limited to the forming agents and films formed by the forming agents described in the examples, but can be similarly applied to the above-mentioned forming agents and films formed by the forming agents.

Evaluation Test
The following tests were carried out using the test samples obtained by the manufacturing methods described below, and the results are shown in Table 2.

<Film-forming property test>
The first and second agents of the test sample were applied to the back of the hand in that order, and after 5 minutes, the applied area was touched with a finger to confirm whether a film that would not peel off when touched with a finger had been formed. In the table, the case where such a film was formed is indicated as "passed," and the case where such a film was not formed is indicated as "failed."

<UV protection test>
The first agent of the test sample was dropped in an amount of 1 mg/ ^cm2 onto a measurement plate (S plate) (5 x 5 cm V-groove PMMA plate, SPFMASTER-PA01), and the first agent layer was formed by spreading it almost evenly with a finger. Then, the second agent of the test sample was dropped on the first agent layer in an amount of 1 mg/ ^cm2 , and the second agent was spread almost evenly with a finger to form a film. The absorbance of the formed film was measured using a Hitachi Ltd. U-3500 self-recording spectrophotometer. Here, an uncoated plate was used as a control. The absorbance (Abs) was calculated according to the following formula 2, and the measured values at 280 nm to 400 nm were integrated to obtain the integrated absorbance value:
Abs=-log(T/To)...Formula 2
T: transmittance of sample, To: transmittance of uncoated plate

From the obtained integrated absorbance values of the samples, the improvement rate of the UV protection performance based on the control sample was calculated using the following formula 3. It can be said that the higher the improvement rate, the better the UV protection performance. The sample of Comparative Example 4 was used as the control sample. The sample of Comparative Example 1 did not contain an ultraviolet absorber, and the samples of Comparative Examples 2 and 3 could not form a film, so the UV protection test was not performed:
Improvement rate (%) of UV protection performance = [integrated absorbance value of sample] / [integrated absorbance value of control sample] × 100 ... formula 3

Test Example
Each test sample in this test example was prepared according to the following method. In this test example, the influence of an oil-soluble UV absorber on an unsaturated organopolysiloxane having a phenyl group and a vinyl group was examined. The results are shown in Table 2. In Table 2, "Mw" refers to the weight average molecular weight, and "moles of phenyl groups/moles of vinyl groups" refers to the moles of phenyl groups relative to the moles of vinyl groups in the unsaturated organopolysiloxane having a phenyl group.

Comparative Example 1
(First Agent)
A first agent was prepared by uniformly mixing 24.3 parts by weight of vinyl dimethicone having a viscosity of 165,000 cst as the first unsaturated organopolysiloxane, 4.7 parts by weight of hydrogen dimethicone as the first hydride-functionalized polysiloxane, and 71.0 parts by weight of volatile dimethicone.

(Second Agent)
The ingredients in Table 1 were mixed uniformly to prepare a second agent.

Examples 1 to 9 and Comparative Examples 2 to 8
A first agent was prepared in the same manner as in Comparative Example 1, except that the components and their amounts in the first agent were changed to those shown in Table 2. The second agent used was the same as in Comparative Example 1.

<result>
As is clear from the results in Table 2, for example, it was found that Examples 1 to 9, which were configured using an unsaturated organopolysiloxane containing phenyl groups in a specific proportion, had improved UV protection performance compared to Comparative Examples 5 to 7, which were configured using an unsaturated organopolysiloxane that did not contain phenyl groups in a specific proportion, and Comparative Example 8, which was configured using an unsaturated organopolysiloxane that did not contain phenyl groups in a specific proportion.

Claims (14)

A coating-type film-forming agent comprising a first agent containing a crosslinkable reactive component that constitutes a coating, and a second agent containing a catalyst that crosslinks the crosslinkable reactive component,
the first agent and/or the second agent contains an unsaturated organopolysiloxane having a phenyl group and a vinyl group, and the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains an oil-soluble ultraviolet absorber,
In the unsaturated organopolysiloxane having a phenyl group and a vinyl group, the molar ratio of the phenyl group to the molar ratio of the vinyl group is 0.40 or less.
A paint-type film-forming agent. the first agent comprises at least one selected from the group consisting of a first unsaturated organopolysiloxane and a first hydride-functionalized polysiloxane;
When the first agent contains only the first unsaturated organopolysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, the second agent contains the second hydride-functionalized polysiloxane;
When the first agent contains only the first hydride-functionalized polysiloxane among the first unsaturated organopolysiloxane and the first hydride-functionalized polysiloxane, the second agent contains the second unsaturated organopolysiloxane;
2. The forming agent according to claim 1, wherein at least one of the first unsaturated organopolysiloxane and the second unsaturated organopolysiloxane comprises the unsaturated organopolysiloxane having a phenyl group and a vinyl group. The forming agent according to claim 1 or 2, wherein the oil-soluble UV absorber includes an UV absorber having an IOB of 0.10 or more. The forming agent according to claim 1 or 2, wherein the first agent contains the unsaturated organopolysiloxane having a phenyl group and a vinyl group and the oil-soluble ultraviolet absorber. The forming agent according to claim 1 or 2, wherein the unsaturated organopolysiloxane having phenyl groups and vinyl groups has a molar ratio of the phenyl groups to the molar ratio of the vinyl groups of 0.0040 or more. The forming agent according to claim 1 or 2, wherein the weight average molecular weight of the unsaturated organopolysiloxane having a phenyl group and a vinyl group is 100,000 or less. The forming agent according to claim 1 or 2, wherein the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains silicone oil. The forming agent according to claim 1 or 2, wherein the first agent and/or the second agent containing the unsaturated organopolysiloxane having a phenyl group and a vinyl group contains inorganic particles. The forming agent according to claim 1 or 2, wherein the unsaturated organopolysiloxane having a phenyl group and a vinyl group is at least one selected from the group consisting of vinyl-terminated diphenylsiloxane-dimethylsiloxane copolymer, vinyl-terminated polyphenylmethylsiloxane, and vinylphenylmethyl-terminated vinylphenylsiloxane-phenylmethylsiloxane copolymer. The forming agent according to claim 2, wherein the first hydride-functionalized polysiloxane and the second hydride-functionalized polysiloxane are non-terminally and/or terminally hydrogenated organopolysiloxanes. The forming agent according to claim 10, 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. The forming agent according to claim 1 or 2, wherein the catalyst is at least one selected from the group consisting of platinum catalysts, rhodium catalysts, and tin catalysts. The forming agent according to claim 12, wherein the catalyst is a platinum catalyst, and the platinum 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 kit in which the first agent and the second agent in the forming agent according to claim 1 or 2 are contained in separate containers, or are contained separately in each compartment of a container having two or more compartments.