JP7074535B2 - Water-in-oil solid composition - Google Patents

Description

The present invention relates to a water-in-oil solid composition.

The water-in-oil composition is widely used in a wide range of fields such as cosmetics and pharmaceuticals (Patent Document 1).
Further, there is a water-in-oil solid composition obtained by solidifying a water-in-oil composition, and the water-in-oil solid composition uses a surfactant having a low HLB to add an aqueous component in the oil. It is generally obtained by emulsifying and solidifying it with a wax or oil gelling agent. This water-in-oil solid composition is generally considered to have an emollient effect and a makeup-sustaining effect due to the oil content, a fresh feeling of use in water-based components, and further excellent portability and usability. There is.

As described above, the user desires a water-in-oil solid composition that is expected to have characteristics such as an effect of oil content, a feeling of use, and a solid state.
For example, Patent Document 1 describes a complex comprising an organopolysiloxane derivative having a specific structure, an amphoteric surfactant and / or a semipolar surfactant, an oil component, and water in the oil. Water-based solid emulsified cosmetics have been proposed.

Japanese Unexamined Patent Publication No. 2010-37249

As described above, Patent Document 1 uses a surfactant in consideration of emulsion stability, and follows the conventional concept of a method for preparing a water-in-oil solid composition. However, when a surfactant is not used, problems such as irritation to the skin and heavy elongation are less likely to occur.

Therefore, the main object of this technique is to provide a water-in-oil solid composition having excellent emulsification stability, excellent usability and excellent composition strength.

As a result of diligent studies, the present inventor uses a novel polyurethane gel composition to stably disperse water-based components in oily components and to make a solid composition having excellent composition strength. I found that I could do it, which was completely unexpected.

The polyurethane gel composition used in the present technology is represented by HO-R ³ -OH (in the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond). It is a novel product containing polyurethane and oils that use glycols.

Further, the novel polyurethane gel composition has an unpredictable effect that a water-in-oil solid composition can be obtained without substantially containing a commonly used surfactant. .. That is, this technique newly finds a water-in-oil solid composition different from the conventional concept of preparation using a general surfactant by using a new gel composition.
In this way, by using the novel polyurethane gel composition and the aqueous component, the present inventor can obtain a water-in-oil solid composition having excellent emulsion stability, excellent usability and excellent composition strength. We found that it could be obtained and completed the present invention. The present invention is as follows.

[1]
A water-in-oil solid composition comprising the following component (A) and component (B).
The component (A) is a polyurethane gel composition containing the component (A-1) polyurethane and the component (A-2) oil.
The component (A-1) is
(I) (a) Hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond, linear or branched C2-C6 alkylene). Polyurethane obtained by reaction with glycol represented by (representing a group), or
(Ii) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) Diisocyanate compound, and (b) HO-R ³ -OH (R ₃ in the formula may have an ether bond. It is a polyurethane obtained by reacting with a glycol represented by (representing a C2-C6 alkylene group).
A composition in which the component (B) is an aqueous component.
[2]
The composition according to the above [1], wherein the component (A-1) polyurethane is an oil-soluble polyurethane.
[3]
The composition according to the above [1] or [2], wherein the component (A-1) polyurethane has a weight average molecular weight of 10,000 to 100,000.
[4]
The composition according to any one of the above [1] to [3], wherein the component (A-2) oil is a liquid oil at 25 ° C.
[5]
The composition according to any one of the above [1] to [4], wherein the component (A-2) oil contains an ester oil having 0 or 1 hydroxyl group.
[6]
The component (B) The aqueous component is one or more selected from water, a monohydric alcohol having 1 to 3 carbon atoms, and a polyhydric alcohol, and any one of the above [1] to [5]. The composition according to one.
[7]
The content mass ratio of the component (A) polyurethane gel composition and the component (B) water-based component is component (A) / component (B) = 0.05 to 50, according to the above [1] to [6]. The composition according to any one.
[8]
[1] to [7] above, wherein the content mass ratio of the component (A-1) polyurethane and the component (B) water-based component is component (A-1) / component (B) = 0.015 to 15. The composition according to any one of.
[9]
The composition according to any one of the above [1] to [8], further containing the component (C) water-soluble salt.
[10]
The composition according to any one of the above [1] to [9], further comprising the component (D) surfactant and having a content of 2% by mass or less in the composition.
[11]
A cosmetic containing the composition according to any one of the above [1] to [10].
[12]
A method for producing a water-in-oil solid composition containing a component (A) polyurethane gel composition and a component (B) a water-based component.
The polyurethane gel composition uses glycol represented by HO-R ³ -OH (where R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond). Contains polyurethane and oils,
A method for producing a water-in-oil solid composition.
[13]
The method for producing a water-in-oil solid composition according to the above [12], wherein the polyurethane gel composition is used for making the composition raw material into a water-in-oil type and solidifying it.

According to the present technique, it is possible to provide a water-in-oil solid composition having excellent emulsification stability, excellent usability and excellent composition strength.
The effects described herein are not necessarily limited, and may be any of the effects described herein.

It is a schematic diagram which shows the method of measuring the self-restoring force in this technique.

Next, preferred embodiments of the present technology will be described in detail. However, this technique is not limited to the following preferred embodiments, and can be freely changed within the scope of this technique. In the present specification, the percentage is expressed by mass unless otherwise specified. In addition, in this specification, when the numerical value range is expressed by using ..., the range includes the numerical values at both ends.

<1. Water-in-oil solid composition of this technology>
The water-in-oil solid composition of the present technology contains a component (A) polyurethane gel composition and a component (B) water-based component described later.
By using the component (A) polyurethane gel composition, a water-in-oil type and solid composition utilizing the characteristics of the component (B) water-based component can be obtained. Moreover, by using the polyurethane gel composition of the component (A), the raw material of the composition can be made into a water-in-oil type and solidified. This is because the emulsifying ability and gelling ability of the component (A) are exhibited.
Further, the present technique can provide a water-in-oil solid composition having excellent emulsification stability, excellent usability and excellent composition strength.

Component (A) A water-in-oil composition in which water-based components are stably dispersed in oil-based components using a polyurethane gel composition can be obtained. Therefore, the component (A) is an advantage of water-based components in oil. The emollient effect and makeup lasting effect, and the fresh feeling of use due to the water-based ingredients can be obtained.
Further, by using the component (A), the water-based component can be stably dispersed in the oily component without substantially containing the conventional surfactant. This makes it easy to reduce or avoid the disadvantages of conventional surfactants. On the other hand, since it is possible to contain a conventional surfactant to the extent that the effect of the present invention is not impaired, it is also possible to utilize the characteristics of the surfactant.

Then, since the solid composition can be obtained by using the component (A) polyurethane gel composition, the component (A) can obtain excellent portability and usability, which are the advantages of the solid. It is preferable that the solid composition of the present technology is a gel composition because the gel characteristics can be utilized.
Further, the strength of the composition can be increased by containing the component (A) and the water-based component (B). Further, the strength of the composition can be further increased by containing the water-soluble salt of the component (C). When the strength is increased, the amount of the gelling agent generally used can be reduced, so that the present technique can obtain a solid composition having excellent spreadability.
Further, the solid composition of the present technology has a property that the strength of the composition is lowered due to the volatilization of water on the skin. For this reason, there is no discomfort due to the structural viscosity of the cosmetic on the skin, and this technique makes it possible to obtain a solid composition having excellent softness of the back skin.
The component (A) polyurethane gel composition and the component (B) aqueous component will be described in detail below.

<1-1. (A) Polyurethane gel composition>
The component (A) polyurethane gel composition used in the present technique is a polyurethane gel composition containing the component (A-1) polyurethane and the component (A-2) oil. The polyurethane gel composition can be obtained by producing the polyurethane gel composition by using the raw material of the polyurethane component (A-1) in the presence of the oil component (A-2).
The component (A) forms a good water-in-oil mold, and at the same time, the emulsion stability, the feeling of use, and the strength of the composition become better. Further, it is possible to obtain a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Here, the component (A-1) polyurethane is represented by HO-R ³ -OH (in the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond). It is a polyurethane that uses glycol.
Further, the polyurethane component (A-1) preferably contains at least the following polyurethane (i) or (ii).
More preferably, the component (A-1) polyurethane has (i) a hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ has an ether bond. It may be a polyurethane obtained by reaction with a glycol represented by a linear or branched C2-C6 alkylene group), or (ii) (c) with a hydrogenated polybutadiene having a hydroxyl group at the terminal. d) Reaction of the diisocyanate compound with (b) a glycol represented by HO-R ³ -OH (where R ³ in the formula represents a linear or branched C2-C6 alkylene group which may have an ether bond). It is a polyurethane obtained by.
As a result, a good water-in-oil mold is formed, and the emulsion stability, usability, and strength of the water-in-oil solid composition are further improved.

Examples of the glycol represented by (b) HO-R ³ -OH in the component (A-1) include ethylene glycol, propylene glycol, 1,3-butylene glycol, diethylene glycol and the like.

The novel polyurethane gel composition used in this technology was found as a result of the inventor's intensive research and development on the gel material in order to obtain a cosmetic film of an oil-soluble gel with high gloss, elasticity and restoring force. It is a gel composition that has been put out.

The inventors have been conducting research using silicone rubber, polysaccharides, and water-based polyurethane as restorative materials. However, these materials had advantages as well as drawbacks to be solved. Specifically, silicone rubber has the disadvantage of lacking luster and lacking restoring force; polysaccharides have the disadvantage of having weak restoring and restoring force; water-based polyurethane has a limited color range due to its water-based nature, and has sufficient luster. It had the serious drawback of not being;
However, as a result of diligent studies, the inventors have found that in the presence of an oil agent, HO-R ³ -OH (in the formula, R ³ may have an ether bond is a linear or branched C2-C6 alkylene). Polyurethane synthesis was carried out using glycol represented by (representing a group), and a novel gel material was obtained by chance. The novel gel material had a special function of high gloss, elasticity, and restoring force, as shown in Examples described later. This was an unpredictable effect for the inventors.
It is known that polyurethane is obtained by reacting diisocyanate with a polyol. However, there is no example of using polyurethane as an oil-soluble gelling agent, and the polyurethane gel composition of the present technology was found by a new idea of producing in the presence of an oil agent.

The concept of the polyurethane gel composition used in this technique is still under intensive study, but at the present time, the inventors think as follows. (1) The polyurethane in the polyurethane composition forms a plurality of ring-shaped clusters (bunches) by associating the hydrophilic parts in the molecule with each other, and is hydrophilic by contacting the oil agent at the hydrophobic part in the molecule. The inventors believe that it has a basic association thickening mechanism. (2) The polyurethane imparts flexibility and oil solubility because the hydrophobic portion in the molecule is a low crystalline hydrocarbon; the polar groups of the hydrophilic portion in the molecule interact with each other. The inventors think that it imparts gelling power and restoring power. (3) The inventors think that a three-dimensional structure is formed into a transparent gel by finely taking a three-dimensional structure by a hydrophilic group-associating thickening mechanism. The polyurethane is preferably an oil-soluble polyurethane, and the oil-soluble polyurethane is more preferably soluble in cetyl 2-ethylhexanoate at least 1% by mass or more at 30 ° C.

The component (A) polyurethane gel composition used in the water-in-oil solid composition of the present technology includes the following compositions 1 and 2. Of these, compositions 1 and 2 are preferable. This component (A) and the component (B) described later form a good water-in-oil type, and the emulsion stability, usability and strength of the water-in-oil solid composition become better. ..

Composition 1: Polyurethane gel composition 1 containing component (A-1) (i) polyurethane and component (A-2) oil.
As the component (A-1) polyurethane, (i) (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond). A composition containing a polyurethane obtained by reaction with a glycol represented by (representing a linear or branched C2-C6 alkylene group) and a component (A-2) oil.
Composition 2: Polyurethane gel composition 2 containing component (A-1) (ii) polyurethane and component (A-2) oil agent;
As the component (A-1) polyurethane, (ii) (c) hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO-R ³ -OH (R ³ in the formula has an ether bond). Polyurethane obtained by reaction with glycol represented by (representing a linear or branched C2-C6 alkylene group) which may be used.
In the present art, "end" means "both ends".

The component (a): component (A) polyurethane gel composition (preferably the component (A-1) polyurethane of the component (A-1)) is hydrogenated polybutadiene having an isocyanate group at the terminal. , Not particularly limited. For example, the compound represented by the following general formula (1) is shown, and it is preferable to use the compound from the viewpoint of the effect of the present technique.

(In the formula, R ¹ and R ² independently represent C1 to C6 alkylene groups, n is an integer of 10 to 100, and n ₁ and n ₂ independently represent 0 or 1).

R ¹ and R ² each independently represent the same or different C1 to C6 alkylene groups, and the alkylene may be a straight chain or a branched chain. Examples of the C1 to C6 alkylene group include methylene, ethylene, n-propylene, n-butylene, n-pentylene, n-hexylene and the like. The alkylene group of R ¹ is preferably a C1 to C2 alkylene group. The alkylene group of R2 is preferably a C5 to C6 alkylene group. The alkylene group is preferably linear.
n represents an integer of 10 to 100, and a more preferable range of n is 15 to 55.
n ₁ and n ₂ are independently the same or different, and represent 0 or 1.

The structure of the repeating unit "C ₄ H ₈ " in the hydrogenated polybutadiene moiety of the general formula (1) (the following general formula (6)) is various as shown in the following general formulas (7a) to (7d), for example. There are types. It is preferable to use the compound from the viewpoint of the effect of the present technique.

The hydrogenated polybutadiene moiety in the hydrogenated polybutadiene having an isocyanate group at the terminal used in the present technology may consist of only one of the repeating units as exemplified above, or two or more repeating units. May be included regularly or randomly.
In the present technique, the three-dimensional structure of the repeating unit " _C4 H ₈ " constituting the hydrogenated polybutadiene moiety of the general formula (1) (the above general formula (6)) may be the same or different, and the hydrogenated polybutadiene may be different. All the structures whose parts are represented by the general formula (6) are included in the present technique.
As the hydrogenated polybutadiene having an isocyanate group at the terminal represented by the general formula (1), for example, a compound represented by the following general formula (2) is exemplified, and using the compound is from the viewpoint of the effect of the present technique. Suitable.

(Here, in the equation (2), n represents an integer of 10 to 100)
The compound of the general formula (2) is a hydrogenated polybutadiene having an isocyanate group at the end of the general formula (1) when R ¹ is an ethylene group, R ² is a hexamethylene group, and n ₁ = n ₂ = 1. Equivalent to.

(B): Component (A) Polyurethane gel composition (preferably compositions 1 and 2) component (A-1) Used in polyurethane (b) HO-R ³ -OH (in the formula, R ³ is Examples of glycols represented by linear or branched C2-C6 alkylene groups which may have an ether bond are, for example, ethylene glycol (HOCH ₂ CH ₂ OH), propylene glycol (HOCH ₂ CH (HOCH 2 CH)). OH) CH ₃ ), 1,3-butylene glycol (HOCH ₂ CH ₂ CH (OH) CH ₃ ), diethylene glycol (HOCH ₂ CH ₂ OCH ₂ CH ₂ OH) and the like can be mentioned. It is preferable to use the compound from the viewpoint of the effect of the present technique.
As the (b) HO-R ³ -OH, a compound represented by the following general formula (5) is shown, and the compound is suitable from the viewpoint of the effect of the present technique.

The hydrogenated polybutadiene having a hydroxyl group at the terminal (c) used in the component (A-1) polyurethane of the component (c): component (A) polyurethane gel composition (preferably composition 2) is not particularly limited. For example, the compound represented by the following general formula (3) is shown, and the compound is suitable from the viewpoint of the effect of the present technique.

(In the formula, n represents an integer from 10 to 100)

In the general formula (3), the hydrogenated polybutadiene moiety (general formula (6)) has the same meaning as described above. It is preferable to use the compound from the viewpoint of the effect of the present technique.

Examples of the (d) diisocyanate compound used in the (d): component (A-1) polyurethane (preferably composition 2) include hexamethylene diisocyanate, 1,3-bis (isocyanatomethyl) benzene, and 1 , 3-Bis (isocyanatomethyl) cyclohexane, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate and the like. Of these, hexamethylene diisocyanate represented by the following general formula (4) is preferable.

In the component (A) polyurethane gel composition (preferably composition 1), (i): (a) hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R3-OH (in the formula, R3 is ether). When a polyurethane is produced by double-adding a glycol represented by (representing a linear or branched C2-C6 alkylene group) which may have a bond, the molar ratio (a): (b) = 1: 4 It is preferably carried out at a ratio of ~ 4: 1, more preferably at a molar ratio (a) :( b) = 2: 3 to 3: 2, still more preferably 4: 5 to 4: 3, and even more preferably 9. : 10 to 10: 9. In this case, the weight average molecular weight (Mw) of (a) is preferably 1000 to 3000. Within this range, a good water-in-oil mold is formed, and a good emulsion stability, a good feeling in use, and a good strength of the composition can be obtained in the water-in-oil solid composition.

In the component (A) polyurethane gel composition (preferably composition 2), (ii): (c) hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) a diisocyanate compound, and (b) HO-R ³ -OH (b) In the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond), and when polyurethane is produced by reaction with a glycol represented by a glycol, the molar ratio (c): (b). ) = 1: 4 to 4: 1, more preferably a molar ratio (c): (b) = 2: 3 to 3: 2, and even more preferably 4: 5 to 4: 3. Even more preferably, it is 9:10 to 10: 9. Within this range, a good water-in-oil mold is formed, and a good emulsion stability, a good feeling in use, and a good strength of the composition can be obtained in the water-in-oil solid composition.

The weight average molecular weight (Mw) of the polyurethane obtained in (i) or (ii) is preferably 10,000 to 100,000, more preferably 20,000 to 80,000, and even more preferably 30,000 to 70,000. Within this range, a good water-in-oil mold is formed, and in the water-in-oil solid composition, good emulsification stability, good usability and good composition strength can be obtained.

The content of the component (A-1) polyurethane in the component (A) polyurethane gel composition is preferably 1 to 35% by mass, more preferably 5 to 30% by mass, still more preferably 10 to 30% by mass. be.
The content of the component (A-2) oil in the component (A) polyurethane gel composition is preferably 65 to 99% by mass, more preferably 70 to 95% by mass, and further preferably 70 to 90% by mass. be.
Within this range, a good water-in-oil mold is formed, and in the water-in-oil solid composition, good emulsification stability, good usability and good composition strength can be obtained.

Ingredient (A) The ingredient (A-2) oil used in the polyurethane gel composition is not particularly limited as long as it is usually used in cosmetics. The properties are not particularly limited, but it is preferably an oil agent that is liquid at 25 ° C. Further, it is preferable to use it as a solvent when producing the polyurethane gel composition of the present technology.
Component (A) The component (A-2) oil used in the polyurethane gel composition may be, for example, a hydrocarbon oil or an ester oil (particularly, the number of hydroxyl groups is 0) regardless of the origin of animal oil, vegetable oil, synthetic oil and the like. Alternatively, one ester oil), fatty acids, silicone oils, fluorine-based oils and the like can be mentioned.

Of these, the lower the polarity, the higher the strength of the polyurethane gel composition tends to be. Therefore, from hydrocarbon oils, ester oils having 0 or 1 hydroxyl groups, and silicone oils containing phenyl groups. It is exemplified that one or more selected ones are used, and it is preferable to include these one or two or more in the component (A-2) oil.
One or more selected from these hydrocarbon oils, ester oils and silicone oils may be contained in the component (A-2) oil preferably in an amount of 90% by mass or more, more preferably 95% by mass or more. Suitable.
Further, it is preferable to use the component (A-2) oil as a solvent in the production. By using the oil agent in the production, the characteristics of the produced polyurethane gel composition are improved. Further, the hardness of the composition can be adjusted by appropriately using an oil agent in the produced polyurethane gel composition.

Ingredients (A) Ingredients used in polyurethane gel compositions (A-2) More specifically, hydrocarbons such as liquid paraffin, squalane, polybutene and polyisobutylene; olive oil, castor oil, mink oil, etc. Fats and oils such as macadamian nut oil; jojoba oil, cetyl isooctanoate (cetyl 2-ethylhexanate), isopropyl myristate, isopropyl palmitate, octyldodecyl myristate, glyceryl trioctanoate, polyglyceryl diisostearate, diglyceryl isostearate, Esters such as diisostearyl malate, glyceryl tribehenate, pentaerythrit rosinate, neopentylglycol dioctanoate; silicones such as methylphenylpolysiloxane and diphenylpolysiloxane, and these may be one or two. More than seeds can be used.

The component (A) polyurethane gel composition used in the present technique has the advantages of not only transparency and gloss but also extremely high elasticity and restoring force.
As a result of measuring the load value with a needle, 30 parts of this polyurethane gel composition and 70 parts of liquid paraffin (kinematic viscosity at 40 ° C. by the ASTM D445 measurement method is 8 mm2 / s) were heated and melted at 85 ° C. to 30 ° C. The gel obtained by cooling showed excellent characteristics with a load value of 0.2 to 10 N when a 2 cmφ spherical adapter was inserted with a 10 mm needle at 2 cm / min. This hardness property indicates that the component (A) polyurethane gel composition used in the present technique has a gel restoring force.
Regarding transparency, the component (A) polyurethane gel composition used in this technique has a transmittance of 90% or more at a wavelength of 700 nm. This high permeability indicates that the component (A) polyurethane gel composition used in the present technique has extremely high transparency.

In the method for producing the component (A) polyurethane gel composition of the present technique, it is preferable to produce polyurethane in the presence of the above-mentioned (A-2) oil agent. Further, it is more preferable to use the specific polyol in the component (A-1) as a polyurethane raw material and to produce polyurethane in the presence of the oil agent (A-2). The polyurethane gel composition of the component (A) of the present technology can be produced by using a known polyurethane production method.

For example, the polyurethane gel composition 1 used in the present technology has, in the component (A-2) oil, hydrogenated polybutadiene having an isocyanate group at the (a) terminal of A and (b) HO-R ³ -OH (in the formula). , R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond) and is obtained by carrying out a hydrogenation reaction.
For example, the polyurethane gel composition 2 of the present technology has (c) hydrogenated polybutadiene having a hydroxyl group at the terminal, and (b) HO-R ³ -OH (in the formula, R ³ may have an ether bond. It can be produced by charging a glycol represented by (representing a C2-C6 alkylene group of a chain or a branch) and a component (A-2) oil agent, mixing them uniformly, and adding (d) a diisocyanate compound to react. can.

In addition to the above components (A-1) and (A-2), the polyurethane gel composition of the present technology may appropriately contain arbitrary ingredients that can be used in the pharmaceutical field or the cosmetic field as long as the effects of the present technology are not impaired. It may be contained. Optional ingredients include, for example, volatile ingredients, surfactants, oily ingredients, powders, water-soluble polymers, UV absorbers, moisturizers, anti-fading agents, antioxidants, defoamers, beauty ingredients, preservatives, etc. Other ingredients usually used in cosmetics can be appropriately used to impart various effects such as fragrances.

<1-2. (B) Water-based component>
The component (B) used in the water-in-oil solid composition of the present technology is a water-based component. The water-based component contains at least water, and those containing water and a water-soluble alcohol are preferable. As a result, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved. The component (B) may be produced by a known production method, or a commercially available product may be purchased.

The water-soluble alcohol is preferably a polyhydric alcohol and / or a monohydric alcohol.
As the polyhydric alcohol, one or more selected from dihydric alcohols such as propylene glycol and 1,3-butylene glycol; and liquid polyhydric alcohols such as polyethylene glycol, glycerin and dipropylene glycol can be selected. .. The polyhydric alcohol preferably has a molecular weight of up to about 20,000.
The monohydric alcohol is preferably a lower alcohol having 1 to 3 carbon atoms, and examples of the lower alcohol include methanol, ethanol, isopropanol and the like, and one or more of these can be selected.

The water-based component of the component (B) preferably contains one or more selected from water, a monohydric alcohol having 1 to 3 carbon atoms, and a polyhydric alcohol.
The aqueous component (B) preferably contains one or more selected from water, ethanol, 1,3-butylene glycol, dipropylene glycol, and glycerin.
As a result, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.

The water-based component of the component (B) preferably contains at least 30% by mass or more of water. The component (B) contains 50% by mass or more of water, more preferably 60% by mass or more of water, and even more preferably 70% by mass or more of water. As the range, it is preferable that the component (B) contains water in an amount of more preferably 70 to 98% by mass, still more preferably 70 to 90% by mass. Within this range, a good water-in-oil mold is formed, and good emulsion stability, good usability and good composition strength can be obtained.

In addition, the water-based component may contain a plant extract or the like as an optional component as long as the effect of the present technique is not impaired. Examples of the plant extract include aloe vera, hamamelis, cucumber, lemon, lavender, rose and the like, and one or more of them can be used as needed.

<1-3. Content and amount of the above (A) and the above (B) in the water-in-oil solid composition of the present technology>
In the water-in-oil solid composition of the present technology, the content mass ratio of the component (A) polyurethane gel composition and the component (B) water-based component is preferably component (A) / component (B) = 0.05. It is -50, more preferably 0.1-35, still more preferably 0.3-5. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.
In the water-in-oil solid composition in the present technology, the content mass ratio of the component (A-1) polyurethane and the component (B) aqueous component is preferably component (A-1) / component (B) = 0. It is 015 to 15, more preferably 0.1 to 10, and even more preferably 0.1 to 2. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.

The content of the component (A) polyurethane gel composition in the water-in-oil solid composition in the present technology is not particularly limited, but is preferably 0.5% by mass or more as the lower limit value thereof, and as the upper limit value thereof. It is preferably 50% by mass or less, more preferably 2 to 40% by mass, and even more preferably 5 to 25% by mass. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.

The content of the component (A-1) polyurethane in the water-in-oil solid composition in the present technology is not particularly limited, but the lower limit thereof is preferably 0.05% by mass or more, more preferably 0.5% by mass. % Or more, more preferably 2% by mass or more, and the upper limit thereof is preferably 20% by mass or less, more preferably 15% by mass or less, still more preferably 8% by mass or less, and the range is more preferably 0. It is .6 to 12% by mass, more preferably 3 to 7% by mass.
The content of the component (A-2) oil in the water-in-oil solid composition in the present technique is not particularly limited, but the lower limit thereof is preferably 20% by mass or more, more preferably 30% by mass or more. The upper limit is preferably 90% by mass or less, more preferably 80% by mass or less, and the range is more preferably 25 to 85% by mass, and even more preferably 40 to 70% by mass.

The content of the component (B) water-based component in the water-in-oil solid composition in the present technology is not particularly limited, but the lower limit thereof is preferably 0.5% by mass or more, more preferably 9% by mass or more. It is more preferably 30% by mass or more, the upper limit thereof is preferably 60% by mass or less, more preferably 55% by mass or less, and the range is more preferably 30 to 50% by mass. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.

The content of the component (B) water in the water-in-oil solid composition in the present technology is not particularly limited, but the lower limit thereof is preferably 0.5% by mass or more, more preferably 5% by mass or more, and further. It is preferably 20% by mass or more, and the upper limit thereof is preferably 50% by mass or less, more preferably 40% by mass or less, still more preferably 30% by mass or less, and the range is more preferably 14.5 to 38. It is 5.5% by mass, more preferably 25 to 35% by mass. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.
The content of the water-soluble alcohol component (B) in the water-in-oil solid composition in the present technique is not particularly limited, but is preferably 0.05% by mass or more, more preferably 0. It is 1% by mass or more, more preferably 1% by mass or more, the upper limit thereof is preferably 30% by mass or less, more preferably 25% by mass or less, and the range is more preferably 4 to 15% by mass. .. Within this range, a good water-in-oil mold is formed, and the emulsion stability, usability and composition strength are improved.

<1-4. Ingredient (C) water-soluble salt and ingredient (D) surfactant>
As described above, the water-in-oil solid composition of the present technology contains at least the component (A) and the component (B). More preferably, the water-in-oil solid composition of the present technology preferably contains the component (C) water-soluble salt and / or the component (D) surfactant described later, if necessary. Further, the water-in-oil solid composition of the present technology may appropriately contain any component as long as the effect of the present technology is not impaired.

<(C) Water-soluble salt>
The water-in-oil solid composition of the present technology preferably further contains the component (C) water-soluble salt, that is, contains the above-mentioned components (A) and (B), and the component (C). It is preferable to do so. By using a water-soluble salt in the present technique, the emulsion stability can be improved and the composition strength can be further improved.

The water-soluble salt used in the water-in-oil solid composition of the present technology is not particularly limited as long as it is water-soluble, and may be either an inorganic salt or an organic salt. Moreover, examples of a water-soluble salt include a metal salt, an ammonium salt, an organic acid salt, an inorganic acid salt, an amino acid salt and the like. One or more can be selected from these groups. The water-soluble means a substance that can be dissolved by stirring or the like with water at room temperature (25 ° C.).

The metal salt is not particularly limited, but is an alkali metal salt (for example, sodium salt, potassium salt, lithium salt, etc.), alkaline earth metal salt (for example, calcium salt, magnesium salt, etc.), zinc salt, copper salt, iron, etc. Salts, aluminum salts and the like can be mentioned, and one or more can be selected from these groups.
The inorganic acid salt is not particularly limited, and examples thereof include nitrates, sulfates, halogen salts, phosphates, and the like, and one or more of these groups can be selected.
Further, as the halogen, more specifically, for example, chlorine, bromine, fluorine and the like can be mentioned, and one kind or two or more kinds can be selected from these groups.
In the present technology, alkali metal halides and alkaline earth halides are preferable from the viewpoint of water solubility and pharmaceutical affairs, and alkali metal halides (for example, sodium chloride, etc.) are preferable from the viewpoint of water solubility. (Potassium chloride, etc.) is preferable.

Examples of the organic acid salt include, but are not limited to, Na pyrrolidone carboxylate, lactate, acetate, citrate, malate, succinate, carbonate, isocitrate, fumarate and the like. , One or more can be selected from these groups.
The amino acid salt is not particularly limited, and examples thereof include alanine salt, arginine salt, glutamine salt, glutamic acid salt, glycine salt, histidine salt, phenylalanine salt, tyrosine salt, and polymer salts thereof. Two or more types can be selected.
Of these, inorganic salts and / or organic acid salts are preferable as the water-soluble salts of the present technology.

The content mass ratio of the component (B) water-based component: component (C) water-soluble salt in the water-in-oil solid composition in the present technique is not particularly limited, but component (B) / component (C) = 2 to It is preferably 200, more preferably 5 to 150, and even more preferably 10 to 100. Within this range, a good water-in-oil type can be formed, and a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin can be obtained.

In the water-in-oil solid composition in the present technology, the content mass ratio of the component (A-1) polyurethane: component (C) water-soluble salt is not particularly limited, but the component (A-1) /. The component (C) is preferably 1 to 100, more preferably 5 to 80, and even more preferably 5 to 50. Within this range, a good water-in-oil type can be formed, and a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin can be obtained.

The content of the component (C) in the water-in-oil solid composition in the present technology is not particularly limited, but is preferably 5% by mass or less, more preferably 3% by mass or less as the upper limit value, and preferably as the lower limit value. Is 0.001% by mass or more, more preferably 0.1% by mass or more, and the range is more preferably 0.05 to 3% by mass, still more preferably 0.3 to 1% by mass. Within this range, a good water-in-oil mold is formed, and good emulsion stability, good usability and good composition strength can be obtained.

<(D) Surfactant>
The water-in-oil solid composition of the present technology can further contain the component (D) surfactant. That is, the water-in-oil solid composition of the present technology can contain the above-mentioned components (A) and (B), as well as the component (D). Further, it is preferable that the amount of the surfactant in the water-in-oil solid composition in the present technique is 2% by mass or less.
This technique has an advantage that it can be made surfactant-free because it has emulsion stability even if it does not substantially contain a surfactant. With this technology, by reducing the amount or content of the surfactant used, the effect of reducing irritation to the skin can be expected.
On the other hand, since this technology can contain up to 2% by mass of the surfactant, a water-in-oil solid composition that utilizes the characteristics of the surfactant while having the good effects of this technology can be obtained. Be done.

The component (D) surfactant used in the present technique is not particularly limited as long as it is usually used for cosmetics, and any one can be used. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants, etc., and one or more of these may be combined as necessary. Can be contained.
Examples of anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants will be described later, but commercially available surfactants can be used as the surfactants used in this technique. ..

Of the component (D) surfactants, nonionic surfactants are suitable. This makes it possible to obtain a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin.
The nonionic surfactant is not particularly limited, and one or more can be selected from the examples described below. Of these, those having an HLB of 2 to 12 are preferable, and those having an HLB of 3 to 9 are more preferable, from the viewpoint of emulsion stability.
The HLB (hydrophilic-lipophilic balance) value used in this technique is a value obtained by the Griffin method.

Examples of the nonionic surfactant include glycerin fatty acid ester and its alkylene glycol adduct, polyglycerin fatty acid ester and its alkylene glycol adduct, propylene glycol fatty acid ester and its alkylene glycol adduct, sorbitan fatty acid ester and its alkylene glycol. Examples thereof include adducts, sorbitol fatty acid esters and alkylene glycol adducts thereof, polyalkylene glycol fatty acid esters, polyoxyalkylene modified silicones, polyoxyalkylene alkyl co-modified silicones and the like.

Examples of the anionic surfactant include higher alkyl sulfate esters such as fatty acid soap, sodium lauryl sulfate and potassium lauryl sulfate, alkyl ether sulfates such as POE (polyoxyethylene, the same applies hereinafter) sodium lauryl sulfate, and lauroyl sarcosine. N-acylsulfosinate such as sodium, phosphate ester salt such as POE oleyl ether phosphate, POE stearyl ether sodium phosphate, sodium di-2-ethylhexyl sulfosuccinate, monolauroyl monoethanolamide polyoxyethylene sulfosuccinate sodium , Sodium sulfosuccinate such as lauryl polypropylene glycol sodium sulfosuccinate, N-acylglutamate such as monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, monosodium N-myristoyl-L-monosodium glutamate, N-stearoyl-N- N-acylmethyl taurine salt such as sodium methyl taurine, higher fatty acid ester sulfate ester salt such as cured coconut oil fatty acid sodium glycerin sulfate, POE alkyl ether carboxylate, POE alkyl allyl ether carboxylate, α-olefin sulfonate, Examples thereof include higher fatty acid ester sulfonate, secondary alcohol sulfate ester salt, and higher fatty acid alkylolol amide sulfate ester salt.

Examples of the cationic surfactant include alkylamine salts, polyamine and alkanolamine fatty acid derivatives, alkyl quaternary ammonium salts, cyclic quaternary ammonium salts and the like.

Examples of the amphoteric surfactant include amino acid type and betaine type carboxylic acid type, sulfuric acid ester type, sulfonic acid type and phosphoric acid ester type, and examples thereof include N, N-dimethyl-N-alkyl-N. -Carboxymethylammonium betaine, N, N-dialkylaminoalkylenecarboxylic acid, N, N, N-trialkyl-N-sulfoalkyleneammonium betaine, N, N-dialkyl-N, N-bis (polyoxyethylene sulfate) Examples thereof include ammonium betaine, 2-alkyl-1-hydroxyethyl-1-carboxymethylimidazolinium betaine, and lecithin.

The content of the component (D) surfactant in the water-in-oil solid composition in the present technology is 2% by mass or less, and the softness of the back skin is maintained to some extent while utilizing the characteristics of the surfactant. It is preferable from the viewpoint of being able to do it. It is more preferably 1% by mass or less, further preferably 0.5% by mass or less, and even more preferably substantially free (for example, 0% by mass).
In the water-in-oil solid composition of the present technology, the content mass ratio of the component (A-1) polyurethane: component (D) surfactant is component (A-1) / component (D) = 0.1 or more. It is preferably 1 or more, more preferably 2 or more. In the case of component (D) / component (A-1), it is preferably 0.5 or less, more preferably 0.3 or less, and further preferably 0.1 or less.
This makes it possible to obtain a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

<2. Method for manufacturing water-in-oil solid composition>
The method for producing the water-in-oil solid composition of the present technology is not particularly limited, but may be carried out according to a known method for producing a water-in-oil solid composition. For example, by mixing the component (A) polyurethane gel composition and the component (B) water-based component (and any optional component as appropriate), a water-in-oil solid composition of the present technology can be obtained. At this time, in order to better mix each component (raw material of the composition), the mixture may be heated at about 60 to 120 ° C.
The water-in-oil solid composition of the present technology can be easily obtained by mixing the component (A) and the component (B) without using a special treatment device. Further, when producing the water-in-oil solid composition of the present technology, the polyurethane gel composition can be used to make the composition raw material into a water-in-oil type and solidify it. Further, the obtained water-in-oil solid composition has excellent effects as described above, and also has very good manufacturing workability and manufacturing efficiency.
When producing the water-in-oil solid composition of the present technology, the component (A) and the component (B) are further mixed with the component (C) water-soluble salt and / or the (D) surfactant as appropriate. You may.

<3. Cosmetics, etc.>
The water-in-oil solid composition of the present technology can be used as cosmetics, external skin preparations, pharmaceuticals and the like. As described above, the cosmetics and the like of the present technology have an advantage that they may be surfactant-free.
Using the water-in-oil solid composition of the present technology, it is possible to produce products such as cosmetics, external skin preparations, and pharmaceuticals. Further, it is possible to manufacture a molded processed product using a mold such as a gold plate by using the water-in-oil solid composition of the present technology. When the water-in-oil solid composition of the present technology is used, it may be added to the above-mentioned component (A) polyurethane gel composition and component (B) water-based component (further, component (C) and / or component (D) as appropriate). Or, in the water-in-oil solid composition of the present technology obtained from these, a volatile component, a surfactant, an oil component, a powder, an aqueous component, a water-soluble polymer, an ultraviolet absorber, a moisturizing agent, and an anti-fading agent. , Antioxidants, antifoaming agents, beauty ingredients, preservatives, fragrances and the like, other ingredients usually used to impart various effects can be appropriately used.

The amount or content of the water-in-oil solid composition of the present technology is not particularly limited, and the water-in-oil solid composition may be appropriately contained in cosmetics or skin external preparations. Further, the solvent used when preparing cosmetics and the like is not particularly limited, but for example, the above-mentioned oil agent can be used.

Specific examples of the cosmetics and external preparations for skin include basic cosmetics such as milky lotions, creams, lotions, beauty liquids, packs, all-in-one gels, sunscreens, and cleaning agents, makeup bases, BB creams, and foundations. It is in any form such as make-up cosmetics such as cheeks and lipsticks, hair nourishing agents, hair tonics, shampoos, hair cosmetics such as rinses, dispersions, ointments, liquids, aerosols, patches, paps, liniments, etc. You may. Among these, make-up cosmetics such as make-up base, BB cream, foundation, blusher, and lipstick are preferable because the effect of the water-in-oil composition of the present technology is remarkably exhibited.

The aqueous component is not particularly limited, and any component that is liquid at room temperature and is usually used for cosmetics can be used. For example, polyhydric alcohols such as water, ethanol, propylene glycol, 1,3-butylene glycol and dipropylene glycol, glycerols such as glycerin, diglycerin and polyglycerin, aloe vera, hamamelis, cucumber, lemon, lavender, rose and the like. Examples of the plant extract of the above, and one or more of these aqueous components can be used as needed. The content of the aqueous component used in the present invention varies depending on usability, usability, and dosage form, and is not particularly limited, but 10 to 90% by mass, particularly 20 to 75% by mass, of all the components have a cosmetic effect and use. It is preferable in terms of sex and usability.

Examples of the moisturizer include urea, hyaluronic acid, chondroitin sulfate, pyrrolidone carboxylate and the like. Among the gelling agents, the aqueous ones include Arabic gum, tragacant gum, galactan, carob gum, guar gum, karaya gum, carrageenan, pectin, agar, quince seed (malmero), starch (rice, corn, potato, wheat), and Plant-based polymers such as alga colloid, tranth gum, and locust bean gum, microbial polymers such as xanthan gum, dextran, succinoglucan, and purulan, animal-based polymers such as collagen, casein, albumin, and gelatin, carboxymethyl starch, and methyl. Steel polymers such as hydroxypropyl starch, cellulose polymers such as methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, hydroxymethyl cellulose, hydroxypropyl cellulose, sodium cellulose sulfate, sodium carboxymethyl cellulose, alginic acid such as sodium alginate and propylene glycol alginate Vinyl polymers such as polymer, sodium polyacrylate, carboxyvinyl polymer, alkyl modified carboxyvinyl polymer, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, ethylene oxide propylene oxide copolymer, bentonite, aluminum silicate. Examples thereof include inorganic gelling agents such as magnesium, laponite, hectrite, and silicic anhydride, and thickeners.

If the colorant is a colorant usually used for cosmetics, the colorant has a spherical shape, a plate shape, a spindle shape, a needle shape, etc. The particle structure and the like are not particularly limited, and inorganic pigments, organic pigments, brilliant pigments, metals and the like can be used. Specific powders include white inorganic pigments such as titanium oxide, zinc oxide, cerium oxide, and barium sulfate, colored inorganic pigments such as iron oxide, carbon black, chromium oxide, chromium hydroxide, dark blue, ultramarine, and red iron oxide, and mica. Titanium, bismuth oxychloride, organic pigment-treated mica titanium, titanium dioxide-coated mica, titanium dioxide-coated synthetic gold mica, titanium dioxide-coated oxychloride bismuth, titanium oxide mica, navy blue-treated mica titanium, carmine-treated mica titanium, fish scale foil, dioxide Glittering pigments such as titanium-coated glass powder, polyethylene terephthalate / aluminum / epoxy laminated powder, polyethylene terephthalate / polyolefin laminated film powder, polyethylene terephthalate / polymethylmethacrylate laminated film powder, and other resin laminated powders, Red No. 201, Red No. 202, Organic pigment powders such as Red 205, Red 226, Red 228, Orange 203, Orange 204, Blue 404, Yellow 401, Red 3, Red 104, Red 106, Orange 205, Organic pigment powder such as zirconium, barium or aluminum lake such as yellow 4, yellow 5, green 3, and blue 1, or metal powder such as aluminum powder, gold powder, and silver powder, and fine particle titanium oxide-coated mica titanium. , Fine particle zinc oxide-coated mica titanium, barium sulfate-coated mica titanium, titanium oxide-containing silicon dioxide, zinc oxide-containing silicon dioxide, and other composite powders can be exemplified, and one or more of them may be used as necessary. can do. These use one or more of fluorine-based compounds, silicone-based compounds, metal soaps, lecithin, hydrogenated lecithin, collagen, hydrocarbons, higher fatty acids, higher alcohols, esters, waxes, waxes, surfactants and the like. It may be surface-treated.

As the powder other than the colorant, if it is usually used as a raw material for cosmetics, it has a plate-like shape, a spindle-like shape, a needle-like shape, a smoke atom-like shape, a fine particle-grade particle size, a porous shape, and a non-porous shape. Inorganic powders, aluminum oxide, magnesium oxide, zirconium oxide, magnesium carbonate, calcium carbonate, aluminum silicate, magnesium silicate, magnesium aluminum silicate, mica, synthetic mica, synthetic Examples thereof include inorganic powders such as sericite, sericite, talc, kaolin, silica, silicon carbide, and boron nitride, and organic powders such as magnesium stearate, zinc stearate, N-acyllysine, and nylon, and one of these is used. Alternatively, two or more types can be used. Further, as these powders, one kind or a composite of two or more kinds may be used, and the surface treatment thereof may be subjected to an oil agent treatment, a silicone compound treatment, a water-soluble polymer treatment or the like.

Hereinafter, the present technique will be described in more detail with reference to Examples and Comparative Examples. It should be noted that these do not limit the present invention in any way.

[Production Example 1 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of cetyl 2-ethylhexaneate and 128 parts of hexamethylene diisocyanate were charged in a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After the addition was completed, the mixture was stirred at 80 ° C. for 5 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 10,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 2.5 N.

[Production Example 2 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of cetyl 2-ethylhexaneate and 128 parts of hexamethylene diisocyanate were charged in a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., and after stirring for 3 hours, 24 parts of ethylene glycol was added.
After the addition was completed, the mixture was stirred at 80 ° C. for 10 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 50,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 5N.

[Production Example 3 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 2450 parts of cetyl 2-ethylhexaneate and 128 parts of hexamethylene diisocyanate were charged in a 3 L three-necked flask and mixed uniformly.
0.9 part of dibutyltin dilaurate was added while controlling to 60 ° C., and after stirring for 3 hours, 24 parts of ethylene glycol was added while diluting with cetyl 2-ethylhexanoate.
After the addition was completed, the mixture was stirred at 80 ° C. for 15 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 100,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 7.5 N.

[Production Example 4 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 24 parts of ethylene glycol, 0.9 part of dibutyltin dilaurate, and 2450 parts of cetyl 2-ethylhexaneate were charged in a 3 L three-necked flask and mixed uniformly.
128 parts of hexaethylene diisocyanate was added while controlling to 60 ° C., and after the addition was completed, the mixture was stirred at 80 ° C. for 10 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 50,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 3N.

[Production Example 5 of Polyurethane Gel Composition of Component (A)]
899 parts of hydroxyl-terminated polybutadiene (molecular weight 2200), 24 parts of ethylene glycol, 0.9 part of dibutyltin dilaurate, and 2450 parts of cetyl 2-ethylhexaneate were charged in a 3 L three-necked flask and mixed uniformly.
While controlling the temperature to 60 ° C., 128 parts of hexaethylene diisocyanate was added, and after the addition was completed, the mixture was stirred at 80 ° C. for 15 hours, and then 18 parts of ethanol was added to complete the reaction.
The weight average molecular weight of polyurethane in the obtained polyurethane gel was 100,000 as measured by GPC (in terms of polystyrene). Further, 30 parts of the obtained gel was melted by heating at 85 ° C. with 70 parts of liquid paraffin, and the load value of the gel cooled to 30 ° C. was determined by a load measuring machine (manufactured by FUDOH), 2 cmφ spherical adapter, 2 cm /. In the case of min and 10 mm needle insertion conditions, it was 4.5 N.

[Manufacturing Comparative Example 1]
100 parts of crosslinked silicone gel (KSG-43 manufactured by Shin-Etsu Chemical Co., Ltd.) is used.
[Manufacturing Comparative Example 2]
35 parts of dextrin fatty acid ester (manufactured by Leopard ISK Chiba Flour Milling Co., Ltd.) and 65 parts of cetyl 2-ethylhexanoate were heated and cooled at 90 ° C. to prepare a polysaccharide gel.
[Manufacturing Comparative Example 3]
35 parts of crystalline polyethylene wax (manufactured by PERFORMALENE 655 New Phase Technology Co., Ltd.) and 65 parts of cetyl 2-ethylhexanoate were heated and cooled at 90 ° C. to prepare a wax oil gel.
The silicone gel of Production Comparative Example 1 lacks gloss and lacks restoring force. The polysaccharide gel of Production Comparative Example 2 has weak resilience and restoring power. The wax oil gel of Production Comparative Example 3 lacks gloss.

[Evaluation of gel]
From the polyurethane gels obtained by the above-mentioned production method, the polyurethane gel composition of Production Example 2 was evaluated with respect to the gel load value for various oils widely used in cosmetics and the transparency of the gel (Test Examples 1 to 1). 6). The results are shown in Table 1. In addition, various evaluation methods are as follows. The gel load value of the component (A) polyurethane gel composition of Production Examples 1 to 5 was 2.5 to 7.5 N, and the weight average molecular weight was 10,000 to 100,000.

[Measurement of load value and evaluation of gel strength]
The polyurethane gel composition of Production Example 2 and various oils shown in Table 1 were heated and dissolved at 85 ° C. and cooled to 30 ° C. to prepare an elastic gel (Test Examples 1 to 6). The load value of the gel was measured using a load measuring machine (manufactured by FUDOH) under the conditions of a 2 cmφ spherical adapter, 2 cm / min, and a 10 mm needle. The gel strength was evaluated by this. As a result of Test Examples 1 to 4, it was confirmed that the load value tends to be higher as the oil agent has a smaller number of hydroxyl groups in the molecule. It is considered that this is because the hydroxyl group in the oil agent affects the hydrophilic group portion in the hydrophilic group-associating thickening mechanism of the polyurethane gel, resulting in a decrease in thickening.

[Measurement and evaluation of transparency]
For the transparency of various gels (Test Examples 1 to 6) shown in Table 1, the transmittance at 700 nm was measured using a transmittance measuring machine (manufactured by Shimadzu Corporation). As a result, in all the gels of Test Examples 1 to 6, 90% or more showed good transparency (⊚).

[Measurement and evaluation of self-restoring force]
The self-restoring force was evaluated using the polyurethane gel composition of Production Example 2 and the dextrin fatty acid ester gel of Production Comparative Example 2. Each measurement sample is diluted with cetyl 2-ethylhexanoate so that the pure content becomes 10.5% by mass, heated at 85 ° C., poured into a jar, and cooled to 30 ° C. to make it elastic. A gel was prepared. From the time when a load of 5 g was applied to the prepared sample using a texture analyzer (manufactured by Ei Seiki Co., Ltd.) with a 2 cmφ spherical adapter, 7 times at a speed of 1 mm / min and under the condition of inserting a 5 mm needle. By repeating the same operation, it was confirmed that the gel structure was not destroyed by the load and that it had a restoring force. A schematic diagram of the measurement is shown in FIG.
As a result, in the dextrin fatty acid ester gel of Production Comparative Example 2, the gel structure was destroyed by repeated loading and the same curve was not obtained, whereas in the polyurethane gel composition of Production Example 2, the gel was formed by repeated loading. By following the same curve without collapsing, it was found that the gel has high resilience. Further, since the value of the load value itself was also higher than that of the dextrin fatty acid ester gel of Production Comparative Example 2, it was found that the elasticity was excellent.

From the above studies, it was found that the component (A) polyurethane gel composition used in the present technique is a highly novel gel having excellent transparency, high elasticity, and excellent self-restoring force.

[Examples 1 to 17 and Comparative Examples 1 to 4: Water-in-oil face gel cream]
The compositions shown in Table 2 were produced by the following production methods, and each sample was evaluated by the following evaluation method, and the results are also shown in Table 2. As the component (A) polyurethane gel composition, the polyurethane gel composition of Production Example 2 produced above was used.
The water-in-oil face gel creams of Examples 1 to 17 have a combination of the component (A) polyurethane gel composition and the component (B) water-based component to achieve gel strength, emulsion stability, spread and spread, and softness of the back skin. It was an excellent water-in-oil solid composition. For example, the water-in-oil face gel creams of Examples 1 to 11, 16 and 17 may be surfactant-free by combining at least the component (A) polyurethane gel composition and the component (B) water-based component. It was a water-in-oil solid composition having excellent gel strength, emulsification stability, spreading and spreading, and softness of the back skin.
On the other hand, in the compositions of Comparative Examples 1 and 2 in which the component (A) polyurethane gel composition was not used, good emulsification stability could not be obtained and water could be separated in the lower layer. That is, a water-in-oil solid composition) could not be obtained. Further, the compositions of Comparative Examples 3 and 4 using the emulsifier were water-in-oil face gel creams having emulsion stability but not good gel strength, spreading and spreading, and softness of the back skin.
Water-in-oil face gel cream (water-in-oil solid composition) of Examples 4 to 11 in which the component (A) polyurethane gel composition and the component (B) water-based component further contain the component (C) water-soluble salts. ) Was able to improve the emulsifying property and the gel strength. For example, the water-in-oil face gel creams of Examples 4 and 5 have a higher gel strength value than the water-in-oil face gel cream of Example 1, and the water-in-oil face gel cream of Example 1 has a higher value. Emulsification stability was higher than that. The same experiment was conducted except that calcium chloride was used instead of the sodium chloride used in Example 8. As a result, the gel strength was equal to or higher than that of sodium chloride (about 5%), and the water-in-oil solid composition was higher. I was able to get things.
In addition, Examples 12 to 15 water-in-oil face gel cream (water-in-oil solid composition) in which the component (A) polyurethane gel composition and the component (B) water-based component further contain the component (D) surfactant. Even when the product) was contained (for example, Examples 12 to 15), it was possible to maintain a certain degree of gel strength and spread and spread required for the water-in-oil solid composition.

Based on the above, in the present technology, by incorporating the component (A) polyurethane gel composition and the component (B) water-based component, an oil having excellent emulsion stability, excellent usability and excellent composition strength. A medium-water solid composition can be provided.
Further, in the present technology, by further containing the water-soluble salt of the component (C) in the above (A) and the component (B), a water-in-oil solid having a better usability and a better composition strength. The composition can be provided.
Further, in the present technology, it is also possible to provide a water-in-oil solid composition in which the component (D) is further contained in the component (A) and the component (B), and the surfactant can be provided. It is also possible to provide a water-in-oil solid composition utilizing the properties. Further, the water-in-oil solid composition of the present technology has an excellent property that it can be surfactant-free even though it is a water-in-oil solid composition.

[Production method]
(1) Ingredients 1 to 7 are heated to 90 ° C. and uniformly mixed and dissolved.
(2) Ingredients 8 to 13 are added to (1) at 80 ° C., defoamed and taken out.
(3) Dissolved at 80 ° C., poured into a container and filled to obtain a water-in-oil face gel cream.

[evaluation]
(Measuring method of composition strength)
For each sample, 3 pieces of each sample were left at 30 ° C. for 1 hour, and the maximum pushing load value was measured when a 3 mm needle was inserted at a speed of 6 cm / min using a 10 mmφ disk type adapter, and 3 pieces were measured. The average load value of was calculated and judged according to the following four-step judgment criteria.
A: 0.5N (Newton) or more B: 0.35 or more and less than 0.5N C: 0.2 or more and less than 0.35N D: less than 0.2N

(Emulsion stability evaluation method)
Each sample was stored in a constant temperature bath at 40 ° C. for one month, and the change in appearance was judged according to the following four-step judgment criteria based on the state immediately after filling.
A: Good without change B: There is a slight change in appearance such as seepage of oil, but there is no problem as a cosmetic product C: There is a change in appearance and usability.
D: There is a clear change, or it is difficult to maintain the shape immediately after filling.

For each sample, 20 cosmetics evaluation panel members each evaluated each item of "good spreadability" and "softness of the back skin" on a 7-point scale according to the following evaluation criteria, and all panels were further evaluated. Judgment was made according to the following criteria using the average score of.

[Evaluation criteria]
(Evaluation result): (Score)
Very good: 6 points Good: 5 points Somewhat good: 4 points Normal: 3 points Somewhat bad: 2 points Bad: 1 points Very bad: 0 points
[criterion]
(Average score): (Judgment)
5.0 or higher: A
3.5 or more and less than 5.0: B
1.5 or more and less than 3.5: C
Less than 1.5: D

Example 18 Water-in-oil cleansing gel component (% by mass)
1. 1. Polyurethane gel composition 30 of Production Example 1
2. 2. Rice bran oil 30
3. 3. Meadowfoam oil 25
4. Potassium myristate 5
5. Dipropylene glycol 5
6. Caprylyl glycol 0.1
7. Remaining amount of purified water (manufacturing method)
A: Ingredients 5 to 7 are uniformly dissolved at 80 ° C.
B: Ingredients 1 to 4 are uniformly dissolved at 90 ° C.
C: Add A to B with stirring at room temperature and emulsify.
After dissolving D: C to 80 ° C., it was poured into a jar-shaped container at 70 ° C. and cooled and solidified to obtain a water-in-oil cleansing gel.

The obtained water-in-oil cleansing gel was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Example 19 Water-in-oil stick-shaped sunscreen component (% by mass)
1. 1. Polyurethane gel composition of Production Example 2 18
2. 2. Polyethylene wax (melting point 83-92 ° C) * 1 5
3. 3. Candelilla wax (melting point 70-75 ° C) 1
4. Glyceryl tri2-ethylhexanoate Remaining amount 5. Propylene glycol dicaprate 5
6. Di2-ethylhexyl succinate 3
7. Diglyceryl triisostearate 5
8. Dimethicone (10CSt) 5
9. p-Methoxycinnamic acid-2-ethylhexyl 5
10.2,4,6-Trianilino-para- (Carbo-2'-
Ethylhexyl 1'-oxy) -1,3,5-triazine 0.5
11. Fine particle zinc oxide (0.03 μm) 10
12. Titanium oxide (0.5 μm) 0.5
13. Dimethicone Polyol Crosspolymer 30% Dimethicone Mixture * 2 3
14. Decamethylcyclopentasiloxane 5
15. PEG-9 Polydimethylsiloxyethyl Dimethicone * 3 0.3
16. Glycerin 2
17.1,3-butylene glycol 4
18. Methyl paraoxybenzoate 0.1
19.1,2-Pentanediol 0.1
20. Purified water 25
21. Fragrance 0.1
* 1: PERFORMALENE 500 (manufactured by New Phase Technology)
* 2: Silicone KSG-210 (manufactured by Shin-Etsu Chemical Co., Ltd.)
* 3: Silicone KF-6028P (manufactured by Shin-Etsu Chemical Co., Ltd.)
(Production method)
A: Ingredients 16 to 20 are uniformly dissolved at 80 ° C.
B: Components 1 to 7 are uniformly dissolved at 110 ° C., components 8 to 12 are added, and the mixture is uniformly mixed and dispersed up to room temperature.
C: Add A to B with stirring at room temperature and emulsify.
D: Add components 13 to 15 to C, mix components 21 uniformly, melt to 85 ° C, pour into a mold container (made of aluminum) at 70 ° C, cool and solidify, attach to the container, and stick-shaped tan. I got a stop.

The obtained water-in-oil stick-shaped sunscreen was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Example 20 Water-in-oil type control color component (mass%)
1. 1. Polyurethane gel composition of Production Example 1 10
2. 2. Dextrin palmitate * 4 3
3. 3. Di-2-ethylhexanoate neopentyl glycol 10
4. Tritridecyl trimeritoate 5
5. Liquid paraffin 5
6. Organic modified clay mineral * 5 0.7
8. Octyldodecanol 2
7. Sorbitan sesquioleate 0.5
8. Polyoxyethylene sorbitan monooleate 0.3
9. Propylene glycol dicaprate 5
10. Silicone treated Bengala coated mica titanium * 6 5
11. Silicone treated talc * 7 2
12. Silicone treated Bengala * 8 0.1
13. Phenoxyethanol 0.3
14. Ethanol 4
15. Remaining amount of purified water * 4: Leopard KL2 (manufactured by Chiba Flour Milling Co., Ltd.)
* 5: Benton 38V (manufactured by NL Industry)
* 6: Gemtone Tan Opal (manufactured by BASF) treated with 5% methylhydrogen * 7: Talc JA-46R (manufactured by Asada Flour Milling Co., Ltd.) treated with 5% methylhydrogen (manufacturing method)
A: Ingredients 1 to 12 are mixed and dispersed at 85 ° C.
B: Components 13 to 15 are mixed and dispersed at 30 ° C.
C: While stirring A at room temperature, B is added and emulsified.
D: C was dissolved at 80 ° C., filled in a container and cooled to room temperature to obtain a water-in-oil type control color.
The water-in-oil control color thus obtained was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Example 21 Water-in-oil pouring lip (gold plate molding)
Ingredient (% by mass)
1. 1. Polyethylene wax (melting point 83-92 ° C) * 1 3
2. 2. Polyurethane gel composition of Production Example 4 15
3. 3. Octyldodecyl stearate 10
4. Isotridecyl isononanoate 5
5. Di (phytosteryl / octyldodecyl) lauroyl glutamate 20
6. Hydrogenated glyceryl abietic acid 1
7. Vaseline 10
8. Polybutene 5
9. Heavy liquid isoparaffin 10
10. Didimethylpolysiloxane (10CSt) 2
11. Diisostearyl malate Remaining amount 12. Phenoxyethanol 0.1
13. Methyl paraoxybenzoate 0.1
14. Dimethylsilylation treatment Haze-like anhydrous silicic acid * 8 2
15. Red No. 202 0.2
16. Yellow No. 4 0.4
17. Black iron oxide 0.1
18. Jojoba oil 0.1
19.1,3-butylene glycol 1
20. Purified water 5
* 8: Aerosil R-972 (manufactured by Nippon Aerosil)
(Production method)
A: Ingredients 1 to 11 are uniformly dissolved at 100 ° C.
B: Ingredients 12 to 18 are added to A, mixed and dispersed uniformly at 50 ° C., and 19, 20 are added and emulsified.
C: B was heated and dissolved at 90 ° C., poured into a gold plate (made of aluminum) at 85 ° C., cooled and solidified, and poured to obtain a water-in-oil lip.

The water-in-oil type poured lip thus obtained was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Example 21 Eye color component (% by mass)
1. 1. Squalene 7
2. 2. Decamethylcyclopentasiloxane 15
3. 3. Didimethylpolysiloxane (2CSt) 5
4.2-Cetyl 2-ethylcaproate 5
5. Polyurethane gel composition 25 of Production Example 5
6. Methylphenylpolysiloxane * 9 3
7. Glyceryl tricaprylate 3
8. Glyceryl tricaprylate 3
9. Octiltriethoxysilane treated titanium oxide coated synthetic phlogopite * 10 3
10. Fluorine compound treated mica titanium * 115
11. Silicone treated red No. 226 * 12 1
12. Silicic acid anhydride 2
13.1,3-butylene glycol 3
14. Ethanol 2
15. Remaining amount of purified water * 10: HELIOS R100R (manufactured by Topy Industries, Ltd.) treated with octyltriethoxysilane 3%
* 11: FLAMENCO SPARKLE GOLD (manufactured by BASF) treated with 3% perfluorotriethoxysilane
* 12: Methylhydrogen 5% treatment (manufacturing method)
A: Ingredients 1 to 7 are mixed at 90 ° C.
B: Ingredients 8 to 12 are added to A, and the mixture is mixed and dispersed at 40 ° C.
C: Ingredients 13 to 15 are mixed and dissolved at 30 ° C.
D: While stirring B, C is added and emulsified.
E: D was heated and dissolved in a container at 85 ° C. and then filled at 75 ° C. to obtain an eye color.

The obtained water-in-oil eye color was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Example 22 Water-in-oil foundation component (% by mass)
1. 1. Polyurethane gel composition 5 of Production Example 3
2. 2. Fischer-Tropsch Wax * 13 6
3. 3. Di-2-ethylhexanoate neopentyl glycol 5
4. Tri-2-ethylhexanoate glyceryl 5
5. Octyl salicylate 5
6. Octyl methoxycinnamate 7
8. Diethylaminohydroxybenzoyl hexyl benzoate 1
7. Sorbitan sesquiisostearate 0.5
8. Hydrogenated lecithin 0.3
9. Isododecane 10
10. Octiltriethoxysilane treated titanium oxide * 14 15
11. Octyltriethoxysilane Yellow iron oxide * 15 3
12. Octiltriethoxysilane treated Bengala * 16 1.5
13. Octyltriethoxysilane treated black iron oxide * 17 1
14. Octiltriethoxysilane treated talc * 18 2
15. Nylon powder * 19 5
16. Phenoxyethanol 0.3
17.1,3-butylene glycol 4
18. Remaining amount of purified water * 13: CIREBELLE 108 (manufactured by SASOL)
* 14: Octilt triethoxysilane 3% treatment * 15: Octilt triethoxysilane 5% treatment * 16: Octilt triethoxysilane 5% treatment * 17: Octilt triethoxysilane 5% treatment * 18: Octilt triethoxysilane 2% treatment * 19: Nylon SP-500 (manufactured by Toray Industries, Inc.)
(Production method)
A: Ingredients 1 to 15 are mixed and dispersed at 90 ° C.
B: Components 16 to 18 are mixed and dispersed at 30 ° C.
C: While stirring A at room temperature, B is added and emulsified.
D: C was dissolved at 85 ° C., filled in a container at 80 ° C. and cooled to room temperature to obtain a water-in-oil foundation.

The obtained water-in-oil foundation was excellent in gel strength, emulsification stability, spreading and spreading, and softness of the back skin.

Claims (13)

A water-in-oil solid composition comprising the following components (A), component (B), and component (D) .
The component (A) is a polyurethane gel composition containing the component (A-1) polyurethane and the component (A-2) oil.
The component (A-1) is
(I) (a) Hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO-R ^3-
Polyurethane obtained by reaction with glycol represented by OH (in the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond), or
(Ii) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) Diisocyanate compound, and (b) HO-R ³ -OH (R ³ in the formula may have an ether bond. It is a polyurethane obtained by reacting with a glycol represented by (representing a C2-C6 alkylene group).
The component (B) is an aqueous component and is
The component (D) is a surfactant, and the content thereof is 1% by mass or less in the composition .
Water-in-oil solid composition. The water-in-oil solid composition according to claim 1, wherein the component (A-1) polyurethane is an oil-soluble polyurethane. The water-in-oil solid composition according to claim 1 or 2, wherein the component (A-1) polyurethane has a weight average molecular weight of 10,000 to 100,000. The water-in-oil solid composition according to any one of claims 1 to 3, wherein the component (A-2) oil is a liquid oil at 25 ° C. The water-in-oil solid composition according to any one of claims 1 to 4, wherein the component (A-2) oil contains an ester oil having 0 or 1 hydroxyl group. The item according to any one of claims 1 to 5, wherein the water-based component of the component (B) contains one or more selected from water, a monohydric alcohol having 1 to 3 carbon atoms, and a polyhydric alcohol. Water-in-oil solid composition. Any one of claims 1 to 6, wherein the content mass ratio of the component (A) polyurethane gel composition and the component (B) water-based component is component (A) / component (B) = 0.05 to 50. The water-in-oil solid composition according to the section. Any of claims 1 to 7, wherein the content mass ratio of the component (A-1) polyurethane and the component (B) water-based component is component (A-1) / component (B) = 0.015 to 15. The water-in-oil solid composition according to item 1. The water-in-oil solid composition according to any one of claims 1 to 8, further comprising the component (C) a water-soluble salt. The water-in-oil solid composition according to any one of claims 1 to 9, wherein the water-in-oil solid composition is a cosmetic or an external preparation for skin . A cosmetic or skin external preparation containing the water-in-oil solid composition according to any one of claims 1 to 9 . A method for producing a water-in-oil solid composition containing a component (A) polyurethane gel composition, a component (B) a water-based component, and a component (D) a surfactant .
The polyurethane gel composition of the component (A) is a polyurethane gel composition containing the polyurethane of the component (A-1) and the oil agent of the component (A-2).
The component (A-1) is
(I) (a) Hydrogenated polybutadiene having an isocyanate group at the terminal and (b) HO- R ^3-
Polyurethane obtained by reaction with glycol represented by OH (in the formula, R ³ represents a linear or branched C2-C6 alkylene group which may have an ether bond), or
(Ii) (c) Hydrogenated polybutadiene having a hydroxyl group at the terminal, (d) Diisocyanate compound, and (b) HO-R ³ - OH (R ³ in the formula may have an ether bond. It is a polyurethane obtained by reacting with a glycol represented by (representing a C2-C6 alkylene group).
The component (B) is an aqueous component and is
The content of the component (D) surfactant is 1% by mass or less in the composition.
Production method. The method for producing a water-in-oil solid composition according to claim 12, wherein the polyurethane gel composition is used for making the composition raw material into a water-in-oil type and solidifying it.

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