FR3150950A1 - Eyebrow makeup composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener - Google Patents

Abstract

Eyebrow makeup composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener The present invention relates to an anhydrous composition for caring for and/or making up keratin materials, in particular the eyebrows and the skin around the eye and the eyebrows, comprising, in particular in a physiologically acceptable medium: (a) at least one non-glycerolated silicone resin; and (b) at least one glycerolated silicone resin; and (c) at least one silicone gum; and (d) at least one oily phase comprising at least one volatile hydrocarbon oil; and (e) a lipophilic thickener. It also relates to a method for coating keratin materials, in particular the eyebrows and the skin around the eye and the eyebrows, and more particularly to a method for making up said keratin materials, comprising the application thereto of the composition as defined above.

Description

Eyebrow makeup composition with a non-glycerolated silicone resin, a glycerolated silicone resin, a silicone gum, a volatile hydrocarbon oil and a thickener

The present application relates to the field of makeup of keratin materials, in particular eyebrows, including eyebrow hairs, the skin where said hairs are implanted and their contours.

In the field of eyebrow makeup, consumers have access to several types of solutions:
- eyebrow pencils, which are easy to use but only last one day. They are often based on a pigmented lead that colors by transferring material onto the skin.
- pens, which are also easy to use but only last a day. They are often made of water-based formulas containing dyes
- tattoo services in a salon, which are very painful, but last for several months.
- anhydrous gels such as the commercial products Semi-Permanent Brow Ink by Revlon (Mintel ID 9314122), Jason Wu-Brow Everlasting Love Eyebrow Gel® by JW Beauty (Mintel ID 9811090), L'Oréal Paris Unbelievabrow Longwear Brow Gel® (Mintel ID 10352772) comprising an MQ resin: TRIMETHYLSILOXYSILICATE and the commercial products Inked Waterproof Brow Gel® by Urban Decay (Mintel ID 7578707) and Up to 3 Day Styling Gel® by Maybelline (Mintel ID 10361806) comprising isododecane and the combination of an MQ resin: TRIMETHYLSILOXYSILICATE and a silicone polyamide: NYLON-611/DIMETHICONE COPOLYMER.

Users of makeup formulations for keratin materials such as eyebrows and the skin around the eye and eyebrows are looking for products with a longer hold over time, which is reflected in particular by a better resistance of the film to makeup remover oils. When it is present on the skin around the eye and eyebrows, it tends to make it difficult for eyebrow makeup to hold.

There remains a need to find new compositions for the care and/or make-up of keratin materials, particularly for eyebrows and the skin around the eye and eyebrows, which make it possible to obtain make-up with better retention of the deposit over time, particularly better resistance to make-up remover oils.

Unexpectedly, the inventors have found that it is possible to achieve these objectives by using a composition, preferably for the care and/or makeup of keratin materials, in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours, comprising, in particular in a physiologically acceptable medium:
(a) at least one non-glycerolated silicone resin; and
(b) at least one glycerolated silicone resin; and
(c) at least one silicone gum; and
(d) at least one oily phase comprising at least one volatile hydrocarbon oil; and
(e) a lipophilic thickener.

This discovery is the basis of the invention.

Objects of the invention

Thus, a first object of the present invention is a composition, preferably for the care and/or makeup of keratin materials, in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours, comprising, in particular in a physiologically acceptable medium:
(a) at least one non-glycerolated silicone resin; and
(b) at least one glycerolated silicone resin; and
(c) at least one silicone gum; and
(d) at least one oily phase comprising at least one volatile hydrocarbon oil; and
(e) a lipophilic thickener.

A second subject of the present invention is a process for coating keratin materials, in particular the eyebrows and the skin around the eye and eyebrows, and more particularly a process for making up said keratin materials, comprising the application thereto of the composition as defined above.

Definitions

In the context of the present invention, the term “keratin materials” is understood to mean in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours. This term “keratin materials”, within the meaning of the present invention, also extends to synthetic false eyebrows.

By "physiologically acceptable" is meant compatible with said keratin materials, which has a pleasant color, odor and feel and which does not generate unacceptable discomfort (tingling, tightness), likely to discourage the consumer from using this composition.

By "glycerolated silicone resin" is meant any silicone resin comprising at least one organosiloxane unit comprising one or more monoglycerol or polyglycerol group(s) in its chemical structure.

In particular, the glycerolated silicone resin contains at least one organosiloxane unit of the type RR'R''SiO _1/2 in which R, R' and R''', identical or different, denote hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group, and more particularly the glycerolated silicone resin contains at least one dimethylsiloxane unit R(CH ₃ ) ₂ SiO _1/2 comprising a hydrocarbon radical R comprising a monoglycerol group.

By “hydrocarbon radical” we mean a radical containing mainly hydrogen and carbon atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

By "monoglycerol group" is meant any group comprising in its chemical structure a group -O-CH ₂ -CHOH-CH ₂ OH

By "polyglycerol group" is meant any group comprising in its chemical structure a chain comprising a repetition of at least 2 glycerol units -(O-CH ₂ -CHOH-CH ₂ ) _m

Non-glycerolated silicone resin

The composition according to the invention comprises at least one non-glycerolated silicone resin (a).

More generally, the term resin means a compound whose structure is three-dimensional. Silicone resins are also called silicone resins or “siloxane resins”. Thus, for the purposes of the present invention, a polydimethylsiloxane is not a silicone resin.

The nomenclature of silicone resins (also called siloxane resins or silicone resins) is known as MDTQ, the resin being described according to the different siloxane monomeric units it comprises, each of the letters MDTQ characterizing a type of unit.

The letter M represents the Monofunctional unit of formula R ₁ R ₂ R ₃ SiO _1/2 , the silicon atom being linked to a single oxygen atom in the polymer comprising this unit.

The letter "D" signifies a difunctional unit R ₁ R ₂ SiO _2/2 in which the silicon atom is linked to two oxygen atoms.

The letter T represents a Trifunctional unit R ₁ SiO _3/2 .

Such resins are described for example in "Encyclopedia of Polymer Science and Engineering, vol. 15, John and Wiley and Sons, New York, (1989), pp. 265-270, and US 2,676,182, US 3,627,851, US 3,772,247, US 5,248,739 or US 5,082,706, US 5,319,040, US 5,302,685 and US 4,935,484.

In the M, D, T units defined above, R, namely R ₁ , R ₂ and R ₃ , represents a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group.

Finally, the letter Q signifies a tetrafunctional unit SiO _4/2 in which the silicon atom is linked to four oxygen atoms themselves linked to the rest of the polymer.

Various silicone resins with different properties can be obtained from these different units, the properties of these polymers varying according to the type of monomers (or units), the nature and number of the radical R, the length of the polymer chain, the degree of branching and the size of the pendant chains.

As non-glycerolated silicone resins (a) which can be used in the compositions according to the invention, it is possible to use, for example, silicone resins of type MQ, silicone resins of type T, silicone resins of type MQT, and their mixtures.

MQ Resins:

As an example of MQ type silicone resins, mention may be made of alkylsiloxysilicates of formula [(R ₁ ) ₃ SiO _1/2 ] _x (SiO _4/2 ) _y (MQ units) in which x and y are integers ranging from 50 to 80, and such that the R ₁ group represents a radical as defined above, and preferably is an alkyl group having from 1 to 8 carbon atoms, or a hydroxyl group, preferably a methyl group.

Examples of MQ silicone resins of the Trimethylsiloxysilicate type include those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name “KF-7312J®” by the company Shin-Etsu, “DC 749®”, “DC 593®” by the company Dow Corning.

T resins:

As an example of T-type silicone resins, mention may be made of polysilsesquioxanes of formula (RSiO _3/2 ) _x (T units) in which x is greater than 100 and such that the R group is an alkyl group having from 1 to 10 carbon atoms, said polysilsesquioxanes being able to further comprise Si-OH terminal groups.

Preferably, polymethylsilsesquioxane resins in which R represents a methyl group may be used, such as those marketed:
- by the company Wacker under the reference Resin MK® such as Belsil PMS MK®: polymer comprising repeating CH ₃ SiO _3/2 units (T units), which may also comprise up to 1% by weight of (CH ₃ ) ₂ SiO _2/2 units (D units) and having an average molecular weight of approximately 10,000 g/mol, or
- by the company SHIN-ETSU under the references KR-220L® which are composed of T units of formula CH ₃ SiO _3/2 and have Si-OH (silanol) end groups, under the reference KR-242A® which comprise 98% of T units and 2% of dimethyl D units and have Si-OH end groups or under the reference KR-251® comprising 88% of T units and 12% of Dimethyl D units and have Si-OH end groups.

MQT Resins:

As a resin comprising MQT units, those cited in document US 5,110,890 are known in particular.

A preferred form of MQT type resins are MQT-propyl resins (also called MQTPr). Such resins usable in the compositions according to the invention are in particular those described and prepared in the application
WO 2005/075542.

MQ-T-propyl resin preferably comprises the units:
(i) ((R ₁ ) ₃ SiO _1/2 ) _a
(ii) ((R ₂ ) ₂ SiO _2/2 ) _b
(iii) (R ₃ SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
with
R ₁ , R ₂ and R ₃ independently representing a hydrocarbon radical (in particular alkyl) having from 1 to 10 carbon atoms, a phenyl group, a phenylalkyl group or even a hydroxyl group and preferably an alkyl radical having from 1 to 8 carbon atoms or a phenyl group,
a, b, c and d being molar fractions,
a being between 0.05 and 0.5,
b being between zero and 0.3,
c being greater than zero,
d being between 0.05 and 0.6,
a + b + c + d = 1,
provided that more than 40 mol% of the R ₃ groups of the siloxane resin are propyl groups.

Preferably, the siloxane resin comprises the units:
(i) ((R ₁ ) ₃ SiO _1/2 ) _a
(ii) (R ₃ SiO _3/2 ) _c and
(iv) (SiO _4/2 ) _d
with R ₁ and R ₃ independently representing an alkyl group having from 1 to 8 carbon atoms, R ₁ preferably being a methyl group and R ₃ preferably being a propyl group,
a being between 0.05 and 0.5, preferably between 0.15 and 0.4,
c being greater than zero, preferably between 0.15 and 0.4,
d being between 0.05 and 0.6, preferably between 0.2 and 0.6, or between 0.2 and 0.55,
a + b + c + d = 1, and a, b, c and d being mole fractions,
provided that more than 40 mol% of the R ₃ groups of the siloxane resin are propyl groups.

The siloxane resins (a) which can be used according to the invention can be obtained by a process comprising the reaction of
A) an MQ resin comprising at least 80 mol% of ((R ₁ ) ₃ SiO _1/2 ) _a and (SiO _4/2 ) _d units
R ₁ representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
a and d being greater than zero,
the ratio a/d being between 0.5 and 1.5; and
B) a propyl resin T comprising at least 80 mol% of (R ₃ SiO _3/2 ) _c units,
R ₃ representing an alkyl group having from 1 to 8 carbon atoms, an aryl group, a carbinol group or an amino group,
c being greater than zero,
provided that at least 40 mol% of the R ₃ groups are propyl groups,
where the mass ratio A/B is between 95:5 and 15:85, preferably the mass ratio A/B is 30:70.

Advantageously, the mass ratio A/B is between 95.5 and 15.85. Preferably, the ratio A/B is less than or equal to 70:30. These preferred ratios have proven to allow comfortable deposits.

Preferably, the composition according to the invention comprises, as non-glycerolated silicone resin (a), at least one MQ type resin, more particularly of the Trimethylsiloxysilicate type, such as those marketed under the reference SR1000® by the company General Electric, under the reference TMS 803® by the company Wacker, under the name KF-7312J® by the company Shin-Etsu, DC 749®, DC 593® by the company Dow Corning, under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS.

In particular, a Trimethylsiloxysilicate type resin will be used in solution in isododecane, in particular in a solution of 75% by weight of active material in isododecane such as the commercial product sold under the reference SILSOFT 74 FLUID® by the company MOMENTIVE PERFORMANCE MATERIALS.

According to a particular embodiment of the invention, the non-glycerolated silicone resin(s) (a) is (are) present in the composition in an active material content ranging from 4 to 35% by weight relative to the total weight of the composition, preferably ranging from 6 to 30% by weight and more preferably from 8 to 25% by weight relative to the total weight of the composition.

Glycerolated silicone resin

The composition according to the invention comprises at least one glycerolated silicone resin (b).

The glycerolated silicone resin (b) comprises in its chemical structure one or more monoglycerol or polyglycerol group(s).*

According to a particular embodiment of the invention, the glycerolated silicone resin(s) (b) is (are) present in an active material content ranging from 0.1 to 40% by weight relative to the total weight of the composition, preferably ranging from 0.2 to 30% by weight and more preferably from 0.5 to 15% by weight relative to the total weight of the composition.

The glycerolated silicone resin(s) (b) according to the invention are preferably chosen from those of the following formula (1):
[Chem 1]
(R ¹ ₃ SiO _1/2 ) _a (R ² (CH ₃ ) ₂ SiO _1/2 ) _b (R ³ ₃ SiO _1/2 ) _c (R ¹ ₂ SiO _2/2 ) _d (R ¹ SiO _3/2 ) _e (SiO _4/2 ) _f (1)
in which
- each R ¹ , identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof;
- each R ² is a mono- or poly-glycerol group of the following general formula (2):

[Chem 2]
—(CH ₂ ) ₂ —C _l H _2l —O—(CH ₂ CH(OH)CH ₂ O) _i R ⁴ (2)
in which
- R ⁴ is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and
- the indices l and i are integers which satisfy the conditions 0 ≤ l ≤ 15 and
0 < i ≤ 5,
- each R ³ is an identical or different group of general formula (3), general formula (4), general formula (5) or general formula (6) below
[Chem 3]
—(CH ₂ ) ₂ —C _m H _2m —(SiOR ¹ ₂ )j—SiR ¹ ₃ (3)
[Chem 4]
—(CH ₂ ) ₂ —C _m H _2m —SiR ¹ _k1 —(OSiR ¹ ₃ ) _3−k1) (4)
[Chem 5]
—(CH ₂ ) ₂ —C _m H _2m —SiR ¹ _k1 —(OSiR ¹ _k2 (OSiR ¹ ₃ ) _3−k2 ) _3−k1 (5)
[Chem 6]
—(CH ₂ ) ₂ —C _m H _2m —SiR ¹ _k1 —(OSiR ¹ _k2 (OSiR ¹ _k3 (OSiR ¹ ₃ ) _3−k3 ) _3−k2 ) _3−k1 (6)
Or
- each R ¹ , identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof
- the indices m, j and k ₁ to k ₃ are integers that satisfy the conditions
0≤ m ≤ 5, 0 ≤ j ≤ 500, 0≤ k1 ≤ 2, 0 ≤ k ₂ ≤ 2 and 0 ≤ k ₃ ≤ 2;
- the indices a, b, c, d, e and f are numbers that satisfy the conditions
0 ≤ a ≤ 400, 0 <b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and
0.5 ≤ (a+b+c)/f ≤ 1.5.

The glycerolated silicone resins (b) according to the invention are described in patent application US20200332065A1 from SHIN ETSU.

According to a particular embodiment, the glycerolated silicone resin(s) (b) of formula (1) as defined above are chosen from those of which
- the indices b and c satisfy the conditions 0 < b ≤ 30 and 0 ≤ c ≤ 30;
- the index i in the general formula (2) of the monoglycerol or polyglycerol group R ² is an integer which satisfies the condition 0 < i ≤ 3.

According to a particular embodiment, the glycerolated silicone resin(s) (b) of formula (1) are in solid form at 25°C when the index c satisfies the condition 0 < c ≤ 400 and R ³ is a group of general formula (3) where the index j satisfies the condition 0 ≤ j ≤ 10.

According to a particular embodiment, the glycerolated silicone resin(s) (b) have a weight-average molecular weight ranging from 1000 to 100000.

The glycerolated silicone resin(s) (b) according to the invention are amphiphilic, i.e. have two parts of different polarity. In general, one is lipophilic (soluble or dispersible in an oily phase). The other is hydrophilic (soluble or dispersible in water). They are characterized by the value of their HLB (Hydrophilic Lipophilic Balance), the HLB being the ratio between the hydrophilic part and the lipophilic part in the molecule. The term HLB is well known to those skilled in the art and is described for example in “The HLB system. A time-saving guide to Emulsifier Selection” published by ICI Americas Inc; 1984). The HLB value of the glycerolated silicone resins according to the invention preferably varies from 0.1 to 15 according to the GRIFFIN method.

The glycerolated silicone resin(s) according to the invention can be obtained by a preparation process comprising the hydrosilylation step.
A) of a silicone resin containing a hydrosilyl group of formula (7) below.
[Chem 7]
(R ¹ ₃ SiO _1/2 ) _a H _n R ¹ _3-n SiO _1/2 ) _b+c (R ¹ ₂ SiO _2/2 ) _d (R ¹ SiO _3/2 ) _e (SiO _4/2 ) _f (7)
in which:
- each R ¹ , identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof;
- the indices a, b, c, d, e and f are integers which satisfy the conditions 0 ≤ a ≤ 400,
0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0< f ≤1000 and
0.5 ≤ (a+b+c)/f ≤ 1.5 ;
- n is an integer that satisfies the condition 1 ≤ n ≤ 3, with
B) one or more compounds which are selected from the compounds terminated by an alkenyl group of general formulas (8), (9), (10), (11) and (12) below.
[Chem 8]
CH ₂ ═CH-C _l H _2l -O-(CH ₂ CH(OH)CH ₂ O) _i R ⁴ (8)
[Chem 9]
CH ₂ ═CH-C _m H _2m -(SiOR ¹ ₂ ) _j -SiR ¹ ₃ (9)
[Chem 10]
CH ₂ ═CH—C _m H _2m —SiR ¹ _k1 —(OSiR ¹ ₃ ) _3-k1 (10)
[Chem 11]
CH ₂ ═CH—C _m H _2m —SiR ¹ _k1 —(OSiR ¹ _k2 (OSiR ¹ ₃ ) _3-k2 ) _3-k1 (11)
[Chem 12]
CH ₂ ═CH—C _m H _2m —SiR ¹ _k1 —(OSiR ¹ _k2 (OSiR ¹ _k3 (OSiR ¹ ₃ ) _3-k3 ) _3-k2 ) _3-k1 (12)
Or
- R4 is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom,
- the indices l, and i are integers which satisfy the conditions 0 ≤ l ≤ 15,
0 < i ≤ 5 ;
- the indices m, j and k1 to k3 are integers which satisfy the conditions 0 ≤ m ≤ 5,
0 ≤ j ≤ 500, 0 ≤ k1 ≤ 2, 0 ≤ k2 ≤2 and 0 ≤ k3 ≤ 2; said silicone resin containing a hydrosilyl group of formula (7) reacting with at least one compound of formula (8).

The hydrosilylation reaction is carried out in the presence of, for example, a platinum or rhodium catalyst. Preferred ranges for b, c, d, e, f, R ⁴ , l, m, i, j and k1 to k3 are as defined above.

Silicone resin containing a hydrosilyl group used as a starting material.

The silicone resin containing a hydrosilyl group of formula (7) may be in a solid or liquid form at 25°C, although in terms of film-forming ability, it is preferably solid. From the viewpoint of utility, the resin is preferably diluted with an organic solvent. The use of a solvent whose boiling point is higher than the reflux temperature during hydrolysis is preferred.

Examples of organic solvents used for dilution include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the viewpoints of storage stability and absence of volatility, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are preferred.

The silicone resin containing a hydrosilyl group of formula (7) is prepared:
(i) by hydrolyzing, in the presence of an acid catalyst, a mixture of one or more compounds selected from the organosilicon compounds of general formulae (13) and (14) below, one or more compounds selected from the organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) below and one or more compounds selected from the hydrolyzable silanes of general formula (17) below, the partial hydrolytic condensates of these hydrolyzable silanes and the metal salts of these hydrolyzable silanes.

[Chem 13]
R ¹ ₃ SiOSiR ¹ ₃ (13)
[Chem 14]
R ¹ ₃ SiX ¹ (14)
[Chem 15]
H _n R ¹ _(3-n) SiOSiR ¹ _(3-n) H _n (15)
[Chem 16]
H _n R ¹ _(3-n) SiX ² (16)
Or
- each R ¹ , identical or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof;
- X ¹ and X ² are hydrolyzable functional groups; and
- n satisfies the condition 1 ≤ n ≤ 3.

[Chem 17]
SiX ³ ₄ (17)
where X ³ is a hydrolyzable functional group),
(ii) by neutralizing the reaction system by adding a basic catalyst in an amount greater than the molar equivalent of the acid catalyst, and
iii) by then carrying out condensation.

In general formulas (13), (14), (15) and (16), the examples and preferred range for R ¹ are the same as those mentioned above.

In general formula (14), X ¹ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred.

In general formula (16), X ² is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred.

In general formula (17), X ³ is a hydrolyzable functional group that is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, an alkoxy group is preferred; from the viewpoints of availability and hydrolysis rate, a methoxy group or an ethoxy group is preferred. The hydrolyzable groups X ³ on the molecule may be the same or different groups.

Examples of organosilicon compounds of general formula (13) include 1,1,1,3,3,3-hexamethyldisiloxane, 1,1,1,3,3,3-hexaphenyldisiloxane, 1,1,3,3-tetramethyl-1,3-divinyldisiloxane, 1,1,1,3,3,3-hexaethyldisiloxane, 1,1,1,3,3,3-hexavinyldisiloxane, 1,1,1,3,3-pentavinylmethyldisiloxane, 1,1,1,3,3-n-octylpentamethyldisiloxane, 1,1,1,3,3-chloromethylpentamethyldiloxane, 1,1,3,3-tetramethyl-1,3-diallyldisiloxane and 1,3-dimethyl-1,1,3,3-tetravinyldisiloxane. Of these, 1,1,1,3,3,3-hexamethyldisiloxane and 1,1,1,3,3,3-hexaphenyldisiloxane are preferred.

Examples of organosilicon compounds of general formula (14) include trimethylchlorosilane, triethylchlorosilane, ethyldimethylchlorosilane, trivinylchlorosilane, dimethylvinylchlorosilane, triphenylchlorosilane, dimethylphenylchlorosilane, methyldiphenylchlorosilane, trimethylmethoxysilane, trimethylethoxysilane, triethylmethoxysilane, triethylethoxysilane, triphenylmethoxysilane and triphenylethoxysilane. Among these, trimethylchlorosilane and trimethylethoxysilane are preferred.

Examples of organosilicon compounds containing a hydrosilyl group of general formula (15) include 1,1,3,3-tetramethyldisiloxane and 1,1,1,3,3-pentamethyldisiloxane. 1,1,3,3-Tetramethyldisiloxane is particularly preferred.

Furthermore, in general formulas (15) and (16), n satisfies the condition
1≤ n ≤ 3. In general formula (15), the "n" associated with the H and R ¹ bonded to one silicone atom and the "n" associated with the H and R ¹ bonded to the other silicone atom may be the same or different.

Examples of organosilicon compounds containing a hydrosilyl group of general formula (16) include dimethylchlorosilane, diphenylchlorosilane, dimethylmethoxysilane and dimethylethoxysilane. Dimethylchlorosilane and dimethylmethoxysilane are particularly preferred.

Examples of hydrolyzable silane of general formula (17) include tetrachlorosilane, tetramethoxysilane and tetraethoxysilane. Examples of partial hydrolysis condensates of hydrolyzable silane include tetramethoxysilane condensates and tetraethoxysilane condensates. Examples of metal salts of hydrolyzable silane include water glass, sodium silicate and potassium silicate. Tetraethoxysilane and tetraethoxysilane condensates are particularly preferred.

In this invention, to a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16) and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes may be added before hydrolysis under an acid catalyst, or a mixture of one or more compounds selected from organosilicon compounds of general formula (18) or general formula (19) may be added after such hydrolysis and before the rehydrolysis described later.

[Chem 18]
R ¹ SiX ⁴ ₃ (18)
[Chem 19]
R ¹ ₂ SiX ⁵ ₂ (19)
Or
- each R ¹ is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by a halogen, a group substituted by an amino or a group substituted by a carboxyl thereof;
- X ⁴ and X ⁵ are hydrolyzable functional groups

In general formulas (18) and 19), the examples and preferred ranges for R ¹ are the same as those mentioned above.

In general formula (18), X ⁴ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X ⁴ on the same molecule may be the same or different.

In general formula (19), X ⁵ is a hydrolyzable functional group which is directly bonded to a silicon atom. Examples include halogen atoms such as chlorine and bromine atoms, alkoxy groups such as methoxy, ethoxy, propoxy and butoxy groups, alkenoxy groups, acyloxy groups, amide groups and oxime groups. Among these, from the viewpoints of availability and hydrolysis rate, a methoxy group, an ethoxy group or a chlorine atom is preferred. The hydrolyzable groups X ⁵ on the same molecule may be the same or different.

Examples of silicon compounds of general formula (18) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, pentyltriethoxysilane, phenyltriethoxysilane, benzyltriethoxysilane, chloropropyltriethoxysilane, bromopropyltriethoxysilane, cyclohexyltrimethoxysilane, triopropyltrimethoxysilane and methyltrichlorosilane. Among these, methyltrimethoxysilane, methyltriethoxysilane and methyltrichlorosilane are preferred.

Examples of silicon compounds of general formula (19) include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dipentyldiethoxysilane, diphenyldiethoxysilane, dibenzyldiethoxysilane, dichloropropyldiethoxysilane, dibromopropyldiethoxysilane, dicyclohexyldimethoxysilane, difluoropropyldimethoxysilane and dimethyldichlorosilane. Among these, dimethyldimethoxysilane, dimethyldiethoxysilane and dimethyldichlorosilane are preferred.

A specific example of a method for preparing the silicone resin containing a hydrosilyl group serving as a raw material in the present invention is described. A solvent (in particular, an organic solvent) and a hydrolysis raw material (a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14), one or more compounds selected from organosilicon compounds containing a hydrosilyl group of general formulae (15) and (16), and one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes) are charged into a reactor, an acid is added as a catalyst, and water is added dropwise with stirring. It is also possible in this case to add the organic solvent after completing the dropwise addition of the water. Since hydrolysis is preferably carried out under acidic conditions, the addition of an acid catalyst is essential.

The temperature during the dropwise addition of water is preferably 0 to 80°C, and more preferably 0 to 50°C. By maintaining the temperature in this range, the heat of reaction of the hydrolysis reaction on the starting product of hydrolysis in the system can be kept low. The amount of water added dropwise, expressed as a molar ratio per mole of hydrolyzable functional groups (alkoxy groups, etc.), is 0.6 to 2, and preferably 1.0 to 1.8. By maintaining the amount of water added in this range, it is possible to further suppress the deactivation of hydrosilyl groups.

In order to suppress a decrease in the reaction rate due to the retention and increase in the viscosity of the uniform reaction system during the hydrolysis reaction, it is preferable to use an organic solvent as the solvent in the hydrolysis reaction. It is also desirable to use a solvent whose boiling point is higher than the reflux temperature during the hydrolysis.

Examples of organic solvents include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type organic solvents such as acetone, methyl ethyl ketone, diethyl ketone, and methyl isobutyl ketone; and aliphatic hydrocarbons such as hexane, heptane, octane, and cyclohexane.

In some cases, an alcoholic solvent of 1 to 10 carbon atoms may be used concomitantly. Examples include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol, and 1,2-propylene glycol. Since alcoholic solvents undergo alcohol exchange reactions with hydrolyzable groups such as alkoxy groups, the use of a long-chain alcoholic solvent limits the rate of the hydrolysis reaction. Therefore, methanol, ethanol, 1-propanol and 2-propanol are particularly preferred.

The solvent used is included in an amount, relative to the overall reaction system, of 1 to 80% (here and below, "%" refers to the weight percentage), and in particular of 5 to 50%. Within this range, the reaction system remains uniform and the reaction proceeds efficiently.

Examples of acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. The acid catalyst may be used in small amounts, with an amount in the range of 0.001 to 10% of the overall reaction system being preferred.

After adding the water dropwise as mentioned above, the hydrolysis reaction is carried out by heating the system at a temperature of 50 to 150°C, preferably 80 to 120°C, for about 2 to 8 hours. Meanwhile, by carrying out the reaction at a temperature lower than the boiling point of the organic compound containing hydrosilyl groups used, the deactivation of the hydrosilyl groups can be further suppressed.

After carrying out the hydrolysis in this manner on the starting product of the above hydrolysis in the presence of an acid catalyst, the system is cooled to a temperature of between 10 and 100°C, preferably between 10 and 60°C, more preferably between 10 and 30°C, and even more preferably to 25°C.

After the above hydrolysis, the system is neutralized at 10 to 40°C with a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal hydroxide. At this time, by using a strong basic catalyst and a weak basic catalyst together, the deactivation of the hydrosilyl group is suppressed and the condensation reaction of the organosilicon resin is further promoted. Examples of such strong basic catalysts include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide. Examples of weakly basic catalysts include sodium carbonate, calcium carbonate and sodium bicarbonate. As for the combinations of a strong basic catalyst with a weak basic catalyst, from the viewpoint of the ease of obtaining a high molecular weight, a combination of sodium hydroxide and calcium carbonate is desirable. With this combination, the molecular weight increases sufficiently, which makes it possible to more reliably obtain a high molecular weight organosilicon resin containing hydrosilyl groups.

The basic catalyst should be used in an amount greater than the molar equivalent of the acid catalyst. Carrying out the neutralization with an amount of basic catalyst greater than the molar equivalent of the acid catalyst promotes the condensation reaction of the organosilicon resin, thereby increasing the molecular weight and obtaining a high-molecular organosilicon resin containing hydrosilyl groups. The amount of basic catalyst used is preferably in the range of 1.0 to 3.0 molar equivalents of the acid catalyst. Adjusting the addition amount in this range promotes the condensation reaction of the organosilicon resin containing hydrosilyl groups, thereby obtaining a resin of a target molecular weight.

After neutralization, the formed alcohols, the solvent and the excess water can be driven off by heating at 95 to 120°C under normal or reduced pressure. Then, after confirming that the formed alcohols, the solvent and the excess water have been driven off, the condensation reaction is carried out by heating at 120 to 150°C for about 2 to 5 hours. An organosilicon resin containing a hydrosilyl group is thus obtained.

In the above-described process for preparing a silicone resin containing a hydrosilyl group, the ratio of the combined molar amount of the compounds of general formulae (13), (14), (15) and (16) to the molar amount of SiO _4/2 units in the compound of general formula (17), expressed as the molar ratio ((13)+(14)+(15)+(16)):(19), is preferably 0.3:1 to 2:1, and more preferably 0.6:1 to 1.3:1.

Furthermore, the ratio of the combined molar amount of the compounds of general formulae (13) and (14) to the combined molar amount of the compounds of general formulae (15) and (16), expressed as the molar ratio ((13)+(14)):((15)+(16)), is preferably 0.3:1.0 to 2.0:1.0, and more preferably 0.6:1.0 to 1.3:1.0. By setting the values within these ranges, the amount of hydrosilyl groups included in the hydrosilyl group-containing organosilicon resin can be quantitatively varied more precisely. In the present invention, by thus varying the amounts in which the compounds of general formulae (15) and (16) are loaded, it is possible to quantitatively vary the amount of hydrosilyl groups included on the organosilicon resin.

In the above-described process for preparing a silicone resin containing hydrosilyl groups, after having carried out the hydrolysis, in the presence of an acid catalyst, of a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14) with one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, it is possible to also gradually add, dropwise, one or more compounds selected from organosilicon compounds containing a hydrosilyl group, of general formulae (15) and (16).

Then, rehydrolysis is carried out. At this stage, the rehydrolysis reaction is preferably carried out by heating at a temperature below the boiling point of the silicone compound containing hydrosilyl groups, for example at a temperature preferably between 40 and 150°C, and more preferably between 40 and 120°C, for about 2 to 8 hours. When the reaction is carried out in this temperature range, the deactivation of the hydrosilyl groups can be further suppressed.

In the process of preparing the silicone resin containing hydrosilyl groups, the reaction of formula (20) below, in which some of the hydrosilyl groups become deactivated, may occur.
[Chem 20]
(20)
where R is a monovalent hydrocarbon group of 1 to 10 carbon atoms, and n' is an integer from 1 to 3.

However, by appropriately fixing the order in which the raw materials are added, i.e., by hydrolyzing a mixture of one or more compounds selected from organosilicon compounds of general formulae (13) and (14) with one or more compounds selected from hydrolyzable silanes of general formula (17), partial hydrolysis condensates of these hydrolyzable silanes and metal salts of these hydrolyzable silanes, and then adding one or more compounds selected from hydrosilyl group-containing organosilicon compounds of general formulae (15) and (16) and carrying out rehydrolysis, the above reaction (20) can be kept to a minimum. This reaction can be further suppressed by cleverly changing the amounts in which the raw materials are added and the type of catalyst used.

The amount of hydrosilyl groups included in the thus obtained hydrosilyl group-containing organosilicon resin is easily adjustable, and it is even possible to introduce a large amount of hydrosilyl groups, by varying the amount of the hydrosilyl group-containing organosilicon compound that is charged. Furthermore, by varying the amount of hydrolysis starting materials used, the type and amount of acid catalyst added, the reaction temperature and time, the amount of solvent added and the addition method, the molecular weight range, shape and other characteristics of the organosilicon resin can be adjusted, thereby preparing a hydrosilyl group-containing organosilicon resin for the intended application.

The hydrosilyl group-containing silicone resin obtained as described above has the average formula (7) above and is composed of Q units (SiO _4/2 ) and M units ((R ¹ ₃ SiO _1/2 ) and (H _n R ¹ _3-n SiO _1/2 )) as essential components, and also of D units (R ¹ ₂ SiO _2/2 ) and T units (R ¹ SiO _3/2 ) as optional components. It may be in the form of a solid or a liquid at 25°C, although from the viewpoint of film formability, it is preferably a solid. Examples include MQ resins, MTQ resins, MDQ resins and MDTQ resins. The weight average molecular weight is preferably in the range of 2,000 to 30,000, although the range of 3,000 to 15,000 is more preferred from the standpoint of performance and ease of performing operations such as filtration. The weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GPC).

Process for the preparation of glycerol silicone resin (b)

A specific example of a process for preparing the glycerolated silicone resin (b) according to the invention is described below.

As mentioned above, the glycerolated silicone resin (b) according to the invention can be obtained by the hydrosilylation step
(A) of a silicone resin containing a hydrosilyl group of average formula (7) below:
(R¹ ₃SiO_1/2)_has(H_nR¹ _3-nSiO_1/2)_b+c(R¹ ₂SiO_2/2)_d(R¹SiO_3/2)_e(SiO_4/2)_f(7)
in which
- each R¹is an identical or different alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a halogen-substituted group, an amino-substituted group or a carboxyl-substituted group thereof;
- the indices a, b, c, d, e and f are integers that satisfy the conditions
0 ≤ a ≤ 400, 0 < b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0< f ≤ 1000 and 0.5 ≤ (a+b+c)/f ≤ 1.5;
- n is an integer that satisfies the condition 1 ≤ n ≤ 3 with
(B) one or more compounds which are selected from alkenyl-terminated compounds of general formulas (8), (9), (10), (11) and (12) below.
CH₂═CH-C_LH_2l-O-(CH₂CH(OH)CH₂O)iR⁴(8)
CH₂═CH-C_mH_2m-(SiOR¹ ₂)_I-SiR¹ ₃(9)
CH₂═CH—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3-k1(10)
CH₂═CH—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ ₃)_3-k2)3-k1(11)
CH₂═CH—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_{3-k3)3-k2)3-k1}(12)
Or
- R⁴is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom,
- the indices l and i are integers which satisfy the conditions 0 ≤ l ≤ 15,
and 0 < i ≤ 5 ;
- the indices m, j and k₁to k₃are integers that satisfy the conditions
0 ≤ m ≤ 5, 0 ≤ j ≤ 500, 0 ≤ k1 ≤ 2, 0 ≤ k2 ≤ 2 and 0 ≤ k3 ≤2; said comprises a compound of general formula (8).

The organosilicon resin containing hydrosilyl groups of average composition formula (7) and the compound having terminal alkenyl groups of general formula (8), (9), (10), (11) or (12) are mixed in a molar ratio, expressed as hydrosilyl groups/terminal unsaturated groups, which is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2.

The addition reaction is preferably carried out in the presence of a platinum or rhodium catalyst. Specific examples include chloroplatinic acid, alcohol-modified chloroplatinic acid, and chloroplatinic acid-vinyl siloxane complexes. When an excessive amount of the catalyst is included, discoloration of the sample occurs, and thus the amount of platinum or rhodium is preferably 50 ppm or less, and more preferably 20 ppm or less.

Furthermore, if necessary, the addition reaction can be carried out in the presence of an organic solvent. Examples of the organic solvent include cyclic organopolysiloxanes such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane and dodecamethylcyclohexasiloxane; aromatic hydrocarbons such as toluene and xylene; ketone-type solvents such as acetone, methyl ethyl ketone, diethyl ketone and methyl isobutyl ketone; aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane; and aliphatic alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-methylbutanol, 2-pentanol, 1-hexanol, 2-methylpentanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, phenol, benzyl alcohol, ethylene glycol and 1,2-propylene glycol. From the viewpoint of reactivity, ethanol, 1-propanol and 2-propanol are preferred.

The amount of solvent used is preferably 1 to 80%, and more preferably 5 to 50%, of the overall reaction system. Within the above range, the reaction system is kept uniform and the reaction proceeds efficiently.

The conditions of the addition reaction are not particularly limited, although refluxing at a temperature of 50 to 150°C, particularly 80 to 120°C, for about 1 to 10 hours is preferred.

After the addition reaction, the step of removing the rhodium or platinum catalyst used with the activated carbon can be included. The amount of activated carbon used is preferably 0.001 to 5.0%, and especially 0.01 to 1.0%, of the overall system. By setting the amount of activated carbon in this range, the discoloration of the sample can be better suppressed.

After the addition reaction, if necessary, the step of removing the remaining hydrosilyl groups can be included. Especially in cases where use in applications such as cosmetic preparations is intended, there is a possibility that these hydrosilyl groups will deactivate over time due to dehydrogenation reactions, which is a problem from a safety point of view. It is therefore preferable to include a step of maintaining the hydrosilyl groups.

An example of a step for removing hydrosilyl groups is the method of hydrolyzing unreacted hydrosilyl groups by adding a basic catalyst such as an alkali metal carbonate, an alkali metal bicarbonate or an alkali metal hydroxide, and then neutralizing by adding an amount of acid catalyst equal to the molar equivalent of the basic catalyst. Specific examples of the basic catalyst include strong basic catalysts such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and barium hydroxide; and weak basic catalysts such as sodium carbonate, calcium carbonate and sodium bicarbonate. From the viewpoint of promoting the dehydrogenation reaction, the use of a strong basic catalyst is particularly preferred, with sodium hydroxide being particularly preferred. Acid catalysts include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. In general, instead of using the acid or base alone, it is preferable to use them with water and heat them to a temperature not higher than the boiling point of water.

After the addition reaction, if necessary, a deodorization step to reduce the odor can be included. When use in applications such as cosmetic preparations in particular is intended, because the product acquires an odor over time, it is preferable to include a deodorization step. The deodorization mechanism of common polyether-modified silicones can be explained as follows. When an addition reaction between an allyl-etherified polyether and a hydrogen polyorganosiloxane is carried out in the presence of a platinum catalyst, the allyl groups rearrange internally as side reactions, forming a propenyl-etherified polyether. This propenyl-etherified polyether has no reactivity with the polyorganosiloxane hydrogen, and therefore remains in the system as an impurity. It is believed that when water acts on this propenyl etherified polyether, the propenyl ether hydrolyzes, giving rise to propionaldehyde, which has an unpleasant odor. It is known that the above hydrolysis reaction is further promoted in the presence of an acid catalyst. Therefore, when the polyether-modified silicone is used in a water-based cosmetic preparation, due to the oxidative deterioration of the polyether, the preparation tends to become acidic over time, promoting the above-described hydrolysis reaction and causing an unpleasant odor.

Typical examples of the deodorization step include two approaches. The first is that, by adding an acid catalyst to the solution after the addition reaction, all the propenyl ether remaining in the system is hydrolyzed and the propionaldehyde that forms is removed by strip purification (JP No. 2137062).

Specific examples of the acid catalyst used in the first approach include hydrochloric acid, sulfuric acid, sulfurous acid, fuming sulfuric acid, oxalic acid, p-toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, formic acid, acetic acid, propionic acid, benzoic acid, and citric acid. These acids are used in combination with water. In cases where it is necessary to remove the acid that has been used, it is preferable to use a low-boiling acid, such as hydrochloric acid, formic acid, acetic acid, or trifluoroacetic acid. Similarly, from the point of view of treatment efficiency, it is preferable to use a strong acid such as hydrochloric acid or trifluoroacetic acid.

The treatment temperature is preferably set at 80°C or less in order to avoid oxidation of hydrophilic groups. The amount of acidic aqueous solution added is preferably set at 0.1 to 100% relative to the organosilicon resin modified by organic groups. The use of 5 to 30% is more preferred.

From the viewpoint of productivity, the method of adding an aqueous solution to the post-reaction solution so as to adjust the pH to 7 or less and performing strip purification after stirring under heating is preferred. Strip purification can be carried out at normal temperature or under reduced pressure. The temperature conditions are preferably set at 120°C or less. In order to effectively purify the strip under these temperature conditions, it is preferable to perform this operation under reduced pressure; when performed at normal pressure, the operation is preferably performed under a flow of inert gas such as nitrogen or argon.

The second approach is that in which, by adding hydrogen to the solution after the addition reaction, the unsaturated double bonds are alkylated (subjected to a hydrogenation reaction) and the formation of propionaldehyde over time is stably controlled (U.S. Pat. No. 5,225,509;
JP-A H07-330907).

Hydrogenation reactions include methods involving the use of hydrogen and methods involving the use of metal hydrides, and there are also homogeneous reactions and heterogeneous reactions. These methods can be used alone, but it is also possible to use them in combination. However, given the advantage that there is no trace of the catalyst used in the product, a heterogeneous catalytic hydrogenation reaction using a solid catalyst is preferred.

The solid catalyst is, for example, nickel, palladium, platinum, rhodium, cobalt, chromium, copper, iron and the like, in uncombined form or in compound form. In this case, it is not necessary to use a catalyst support. However, when a catalyst support is used, the support may be, for example, activated carbon, silica, silica-alumina, alumina or zeolite. These catalysts can be used alone, but it is also possible to use them in combination. The preferred catalyst is Raney nickel, which is economically advantageous. Since Raney nickel is generally developed and used with an alkali, it is necessary to carefully measure the pH of the reaction system. In addition, the reaction system becomes weakly alkaline, which is particularly effective for deodorization when the hydrolysis reaction is carried out with an acidic aqueous solution.

It is preferable to carry out the hydrogenation reaction at a pressure generally between 1 and 100 MPa and between 50 and 200 °C. The hydrogenation reaction can be carried out in batches or continuously. When it is a batch process, the reaction time depends on, for example, the amount of catalyst and the temperature, but it is generally between 3 and 12 hours. The hydrogen pressure can be adjusted to an appropriate fixed pressure. The end point of the hydrogenation reaction is the point at which the hydrogen pressure has stopped changing, and it can therefore be determined by carefully monitoring a pressure gauge.

The amount of aldehyde included in the glycerol silicone resin which has been purified by this acid treatment and hydrogenation treatment can be set at 70 ppm or less, preferably 20 ppm or less, and more preferably 10 ppm or less.

It is also possible to combine the two types of deodorization steps mentioned above. In the approach that involves acid treatment, decomposition and removal of the aldehyde compound is possible, but since there is a limit to the complete removal of unsaturated double bonds, the formation of odorous aldehyde from this cannot be completely suppressed. In the approach that involves a hydrogenation reaction, by removing the unsaturated double bonds, it is possible to reduce the amount of aldehyde compound that is formed due to it. However, the aldehyde condensate that is formed with the condensation of a portion of the aldehyde remains in the system even after such treatment has been carried out and removal by strip purification is also difficult. Therefore, by alkylating the unsaturated double bonds that remain when the solution following the addition reaction is subjected to hydrogenation, and then decomposing the aldehyde condensate in the system by adding an acid catalyst, complete deodorization is possible.
(WO2002/05588).

The weight average molecular weight of the glycerol silicone resin of the average formula (1) preferably ranges from 1000 to 100000; from the viewpoint of performance and ease of operations such as filtration, the weight average molecular weight preferably ranges from 3000 to 50000. Here and below, the weight average molecular weight can be determined as the weight average molecular weight equivalent to polystyrene in gel permeation chromatography (GPC).

The glycerolated silicone resin (b) according to the invention is in a form at 25°C which can be solid or liquid; from the point of view of the formability of the film, it is preferably solid.

In particular, the glycerolated silicone resin (b) according to the invention of formula (1) for which the indices b and c satisfy the conditions 0 < b ≤ 30 and 0 ≤ c ≤ 30, the index i in the general formula (2) is an integer which satisfies the condition 0 < i ≤ 3 and the index j in the general formula (3) satisfies the condition 0 ≤ j ≤ 10 is in the form of a solid at 25°C and preferably has a weight-average molecular mass which preferably varies from 1000 to 100000 and more preferably from 3000 to 50000.

The glycerolated silicone resins (b) according to the invention have a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, preferably from 0.1 to 15, and more preferably from 1.0 to 8.0.

According to a preferred form, the composition of the invention comprises at least one glycerolated silicone resin of formula (1) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type corresponding to the following formula (21):

[Chem 21]
[(CH ₃ ) ₃ SiO _1/2 ] _a [R(CH ₃ ) ₂ SiO _1/2 ] _b (SiO _4/2 ) _f (21)
Or
- R denotes the 3-glyceroxypropyl group of structure
-C ₃ H ₆ OCH ₂ -CH(OH)CH ₂ OH;
- the indices a, b and f are integers which satisfy the conditions 0 ≤ a ≤ 400,
0 < b ≤ 30, 0 < f ≤ 1000 and 0.5 ≤ (a+b)/f ≤ 1.5.

According to a particularly preferred form, the glycerolated silicone resin (b) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil.

For the purposes of the invention, the term “volatile oil” means any oil capable of evaporating on contact with the skin in less than one hour, at room temperature and atmospheric pressure. The volatile oil is a volatile cosmetic compound, liquid at room temperature, having in particular a non-zero vapor pressure, at room temperature and atmospheric pressure, in particular having a vapor pressure ranging from 2.66 Pa to 40,000 Pa, in particular ranging from 2.66 Pa to 13,000 Pa, and more particularly ranging from 2.66 Pa to 1,300 Pa.

The volatile oil in accordance with the invention may be chosen from the group consisting of hydrocarbon oils, silicone oils, and their mixtures.

By “hydrocarbon oil” is meant an oil containing mainly hydrogen and carbon atoms and possibly one or more functions chosen from hydroxyl, ester, ether and carboxylic functions.

For the purposes of the present invention, the term "silicone oil" denotes an oil comprising at least one Si-O group, and more particularly an organopolysiloxane.

The volatile hydrocarbon oils which can be used in the compositions according to the invention can be chosen from branched C8-C16 alkanes.

Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example oils sold under the trade names Isopar® or Permetyl®. Isododecane will be used more preferably.

As an example of a volatile silicone oil that can be used in the invention, mention may be made of volatile silicone oils, such as linear or cyclic volatile silicone oils, in particular those having a viscosity of 2 to 8 mm ² /s (cSt), and containing in particular from 2 to 7 silicon atoms, these silicones optionally comprising alkyl or alkoxy groups containing from 1 to 10 carbon atoms. As volatile silicone oils that can be used in the invention, mention may be made in particular of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, heptamethylhexyltrisiloxane, heptamethyloctyltrisiloxane, hexamethyldisiloxane, octamethyltrisiloxane, decamethyltetrasiloxane and dodecamethylpentasiloxane; and mixtures thereof. Decamethylcyclopentasiloxane (D5) will be used more preferably.

According to a particularly preferred form, the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution at 49.5% by weight of active material in isododecane like the product manufactured under the trade name X-25-9138A® by SHIN ETSU with a weight average molecular mass of 11,000.

According to a preferred form, in order to improve the resistance of the composition of the invention to sebum, the composition of the invention comprises at least one glycerolated silicone resin and at least one non-glycerolated silicone resin in a weight ratio of the amount of glycerolated silicone resin to the amount of non-glycerolated silicone resin greater than or equal to 0.8, and more preferably greater than or equal to 1.0.

Volatile hydrocarbon oil

The composition according to the invention comprises an oily phase (d) comprising at least one volatile hydrocarbon oil.

Oil is any fatty substance in liquid form at room temperature (25°C) and atmospheric pressure (760 mm Hg or 10 ⁵ Pa).

The term "oil phase" means an organic liquid phase at room temperature (25 °C) and atmospheric pressure which is immiscible in water. It comprises at least one oil and any ingredient soluble or miscible in said phase.

The volatile hydrocarbon oils which can be used in the compositions according to the invention can be chosen from branched C8-C16 alkanes.

Examples include C8-C16 isoalkanes of petroleum origin (also called isoparaffins) such as isododecane (also called 2,2,4,4,6-pentamethylheptane), isodecane, isohexadecane, and for example oils sold under the trade names Isopar® or Permetyl®.

C8-C16 branched esters such as isohexyl neopentanoate may also be mentioned. Other volatile hydrocarbon oils such as petroleum distillates, in particular those sold under the name Shell Solt® by the company SHELL, may also be used.

The volatile hydrocarbon oils which can be used in the compositions according to the invention can be chosen from volatile linear alkanes comprising from 6 to 14 carbon atoms.

As an example of linear alkanes suitable for the invention, mention may be made of the alkanes described in the patent applications of the company Cognis WO 2007/068371, or WO2008/155059 (mixtures of distinct alkanes differing by at least one carbon). These alkanes are obtained from fatty alcohols, themselves obtained from copra or palm oil.

As examples of linear C6-C14 alkanes suitable for the invention, mention may be made of n-hexane (C6); n-heptane (C7), n-octane (C8), n-nonane (C9), n-decane (C10), n-undecane (C11), n-dodecane (C12), n-tridecane (C13), n-tetradecane (C14), and mixtures thereof.

These include n-dodecane (C12) and n-tetradecane (C14) sold by Sasol under the references PARAFOL 12 97® and PARAFOL 14 97® respectively, as well as their mixtures.

According to another embodiment, a mixture of n-dodecane and n-tetradecane is used. In particular, the dodecane/tetradecane mixture in the weight ratio 85/15 marketed by the company BIOSYNTHIS under the reference VEGELIGHT 1214® can be used.

According to yet another embodiment, a mixture of volatile linear C9-C12 alkanes with INCI name: C9-12 ALKANE is used, such as the product marketed by the company BIOSYNTHIS under the reference VEGELIGHT SILK®.

According to yet another embodiment, a mixture of n-undecane (C11) and n-tridecane (C13) is used, such as those obtained in examples 1 and 2 of application WO2008/155059 from the company Cognis and such as that sold under the trade name CETIOL ULTIMATE® by the company BASF.

According to a particularly preferred embodiment, the volatile hydrocarbon oil is chosen from branched C8-C16 alkanes, and more particularly isododecane, the mixture of volatile linear C9-C12 alkanes and the mixture of n-undecane (C11) and n-tridecane (C13).

According to a particularly preferred embodiment, the composition of the invention comprises at least one volatile oil chosen from C8-C16 isoalkanes of petroleum origin (also called isoparaffins), in particular isododecane.

The volatile hydrocarbon oil or oils are preferably present in the composition of the invention at contents less than or equal to 80% by weight, preferably 40 to 70% by weight relative to the total weight of said composition.

Silicone rubber

The composition according to the present invention comprises at least one silicone gum (c).

If two or more silicone gums (c) are used, they may be the same or different.

By silicone gum is meant more particularly polyorganosiloxanes, in particular polydimethylsiloxanes, linear non-crosslinked, optionally hydroxylated, phenylated, or vinylic, or combinations thereof. It should be noted that the silicone gums used according to the invention are not silicone elastomers.

More particularly, the silicone gum (c) is chosen from polyorganosiloxanes with a molecular mass by weight greater than or equal to 180,000 g/mol.

Molecular masses by weight are measured in a conventional manner in the field, for example using gel permeation chromatography coupled with static light scattering (GPC-MALLS).

The silicone gum (c) preferably has a dynamic viscosity at 25°C and atmospheric pressure of 100 to 1000 mPa.s.

It may be preferable that the silicone gum (b) does not have a functional group such as an amino group.

The silicone gum (c) can be chosen in particular from silicones of formula:
[Chem 22]

in which:
R1, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,
R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical, and
n and p being integers chosen such that the molecular mass of the silicone gum is greater than or equal to 180000 g/mol.

In general, n and p can each take values ranging from 0 to 3000, knowing that n and p are not simultaneously zero.

According to a particular mode, the silicone gum(s) (c) can be used alone.

According to a particular form of the invention, the silicone gum (c) is in the form of a solution in an organic solvent, preferably chosen from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular C8-C16 such as isododecane, methylene chloride, pentane, dodecane, tridecane, tetradecane or their mixtures.

Particularly preferably, the solvent for the silicone gum (c) is chosen from C8-C16 isoparaffins, in particular isododecane.

When the silicone gum (c) of the invention is in the form of a solution in an organic solvent such as those described above, the proportion of silicone gum preferably represents from 5 to 40% by weight, and more preferably from 10 to 30% by weight relative to the total weight of the solution.

Preferably, the silicone gum(s) (c) according to the invention is (are) present at active material contents ranging from 5 to 30% by weight, and more particularly from 8 to 15% by weight relative to the total weight of the composition.

As silicone gums (c) which can be used according to the present invention, mention may be made of those for which:
- the substituents R1 to R6 represent a methyl group, the group X represents a methoxy group, and n and p are such that the molecular weight of the polymer is 600,000 g/mol, such as the product sold under the name Mirasil C-DPDM® by the company Bluestar;
- the substituents R1 to R6 represent a methyl group, the group X represents a hydroxyl group, and n and p are such that the molecular weight of the polymer is 600,000 g/mol, such as the product sold under the name SGM 36® by the company Dow Corning, the product marketed or manufactured under the name XIAMETER® PMX-1401 FLUID® by the company Dow Corning, in the form of a 13% by weight solution in cyclopentasiloxane, the product marketed or manufactured under the name XIAMETER PMX-1503 FLUID® by the company Dow Corning, in the form of a 12% by weight solution in polydimethylsiloxane, the product marketed or manufactured under the name XIAMETER® PMX-1403 FLUID by the company Dow Corning, in the form of a 13% by weight solution in polydimethylsiloxane,
- dimethicones of the type (polydimethylsiloxane) (methylvinylsiloxane), such as SE63® sold by GE Bayer Silicones, poly(dimethylsiloxane)(diphenyl)(methylvinylsiloxane) copolymers and mixtures thereof.

According to a particularly preferred form, the silicone gum (c) is a polydimethylsiloxane with the INCI name DIMETHICONE of the following formula:
[Chem 22]

in which n is less than or equal to 3000, and particularly in the form of a solution in isododecane, and more particularly in the form of a 25% by weight solution in isododecane such as the product marketed or manufactured under the name SILSOFT B3820 BLEND® by the company MOMENTIVE PERFORMANCE MATERIALS.

Lipophilic thickener

The composition according to the invention comprises at least (e) one lipophilic thickener.

“Lipophilic thickener” means any liposoluble or lipodispersible molecule in the oily phase of the composition capable of increasing the viscosity of the composition.

As a lipophilic thickener, at least one lipophilic clay should preferably be used.

Clay refers to a material based on hydrated silicates and/or aluminosilicates with a lamellar structure.

Clays can be natural or synthetic and are made lipophilic by treatment with an alkyl ammonium salt such as a C10 to C22 ammonium chloride, particularly steralkonium chloride or di-stearyl di-methyl ammonium chloride.

They can be chosen from bentonites, in particular bentonites, hectorites and montmorillonites, beidellites, saponites, nontronites, sepiolites, biotites, attapulgites, vermiculites and zeolites.

Preferably, they are chosen from hectorites and bentonites.

According to a particularly preferred form, a lipophilic clay chosen from hydrophobic modified bentonites and hydrophobic modified hectorites will be used, in particular by a C10 to C22 quaternary ammonium chloride, such as:
- a bentonite modified by stearalkonium chloride such as the commercial products sold under the name CLAYTONE AF®, GARAMITE VT®, TIXOGEL® LG-M, TIXOGEL® MP 250 TIXOGEL® VZ, TIXOGEL® VZ-V XR, by the company BYK Additives Inc; the commercial products sold under the name VISCOGEL® B3, VISCOGEL® B4, VISCOGEL® B7, VISCOGEL® B8, VISCOGEL® ED, VISCOGEL® GM, VISCOGEL® S4, VISCOGEL® SD by the company Bentec SPA;
- a bentonite modified by stearalkonium chloride in the presence of at least propylene carbonate and at least one oil such as the commercial products DUB VELVET GUM® from the company STEARINERIE DUBOIS FILS,
MYGLYOL GEL T® from the company Cremer Oleo, TIXOGEL® CGT 6030, TIXOGEL® DBA 6060, TIXOGEL® FTN, TIXOGEL® FTN 1564, TIXOGEL® IPM, TIXOGEL® LAN, TIXOGEL® LAN 1563 from the company BYK Additives Inc;
- a hectorite modified with distearyl dimethyl ammonium chloride (INCI name: DISTEARDIMONIUM HECTORITE) such as, for example, that marketed under the name BENTONE® 38VCG RHEOLOGICAL ADDITIVE by the company Elementis Specialities;
- a hectorite modified with distearyl dimethyl ammonium chloride in the presence of at least propylene carbonate or triethyl citrate and at least one oil such as the commercial products sold under the name BENTONE® GEL DOA V, BENTONE® GEL EUG V, BENTONE® GEL IHD V, BENTONE® GEL ISD V, BENTONE® GEL MIO V® BENTONE® GEL PTM V® BENTONE® SS-71 V, BENTONE® VS-5 PC V, BENTONE® VS-5 by the company Elementis Specialities; the commercial products sold under the name CREAGEL BENTONE CPS/HECTONE CPS, CREAGEL BENTONE ID/HECTONE ID by the company Créations Couleurs; the commercial products sold under the name NS GEL DM1®, NS GEL PTIS®, NS MGEL 1152® by the company Next Step Laboratories Stop.

We will use more particularly a hectorite modified by distearyl dimethyl ammonium chloride (INCI name: DISTEARDIMONIUM HECTORITE) such as, for example, that marketed under the name BENTONE® 38VCG RHEOLOGICAL ADDITIVE by the company Elementis Specialities.

The lipophilic thickener or thickeners may be present in the composition at concentrations ranging, preferably, from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition.

Cosmetic additives

The composition may contain classic cosmetic additives such as coloring matters, preservatives, perfumes, antioxidants, moisturizing agents, lipophilic active ingredients such as vitamins, lipophilic UV filters, fillers.

Of course, the person skilled in the art will take care to choose any additional additives and/or their quantity in such a way that the advantageous properties of the composition according to the invention are not, or not substantially, altered by the envisaged addition.

Coloring materials

The composition according to the invention may additionally comprise at least one coloring material.

1. Matières colorantes pulvérulentes

According to a particular form of the invention, the coloring matter can be chosen from powdery coloring matters, liposoluble dyes, and their mixtures.

1. Powdered coloring matter

Powdered coloring materials can be chosen from mineral pigments, organic pigments, pearlescent agents and their mixtures.

“Pigments” means white or colored particles, mineral or organic, insoluble in an aqueous medium, intended to color and/or opacify the composition and/or the resulting deposit. These pigments may be white or colored, mineral and/or organic.

According to a particular embodiment, the pigments used according to the invention are chosen from mineral pigments.

By "mineral pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the inorganic pigment chapter. Among the mineral pigments useful in the present invention, mention may be made of zirconium or cerium oxides, as well as zinc, iron (black, yellow or red) or chromium oxides, manganese violet, ultramarine blue, chromium hydrate and ferric blue, titanium dioxide, metal powders such as aluminum powder and copper powder. The following mineral pigments may also be used: Ta ₂ O ₅ , Ti ₃ O ₅ , Ti ₂ O ₃ , TiO, ZrO ₂ in mixture with TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , CeO ₂ , ZnS.

The size of the pigment useful in the context of the present invention is generally greater than 100 nm and can range up to 10 μm, preferably from 200 nm to
5μm, and more preferably from 300 nm to 1μm.

According to a particular form of the invention, the pigments have a size characterized by a D [50] greater than 100 nm and which can range up to 10 μm, preferably from 200 nm to 5 μm, and more preferably from 300 nm to 1 μm.

The sizes are measured by static light scattering using a commercial granulometer of the Master Sizer 3000® type from Malvern, allowing to understand the particle size distribution of all the particles over a wide range from 0.01 μm to 1000 μm. The data are processed on the basis of the classical theory of Mie scattering. This theory is the most suitable for size distributions ranging from submicron to multimicron, it allows to determine an “effective” particle diameter. This theory is notably described in the work of Van de Hulst, H.C., “Light Scattering by Small Particles”, Chapters 9 and 10, Wiley, New York, 1957.

D [50] represents the maximum size that 50% of the particles have by volume.

According to a particular form of the invention, the mineral pigment comprises a lipophilic or hydrophobic coating, the latter being preferably present in the oily phase of the composition according to the invention.

According to a particular embodiment of the invention, the pigments may be coated according to the invention with at least one compound chosen from metallic soaps; N-acylated amino acids or their salts; lecithin and its derivatives; isopropyl trisostearyl titanate; isostearyl sebacate; natural plant or animal waxes; polar synthetic waxes; fatty esters; phospholipids; and mixtures thereof.

According to a particular embodiment, the pigments may be coated according to the invention with an N-acylated amino acid or one of its salts which may comprise an acyl group having from 8 to 22 carbon atoms, such as for example a 2-ethyl hexanoyl, caproyl, lauroyl, myristoyl, palmitoyl, stearoyl, cocoyl group.

The amino acid may be, for example, lysine, glutamic acid or alanine. The salts of these compounds may be aluminum, magnesium, calcium, zirconium, zinc, sodium or potassium salts. Thus, according to a particularly preferred embodiment, the pigments may be coated with an N-acylated amino acid derivative which may in particular be a glutamic acid derivative and/or one of its salts, and more particularly a stearoyl glutamate, such as, for example, aluminum stearoyl glutamate. As examples of pigments treated with aluminum stearoyl glutamate, mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference NAI® by the company MIYOSHI KASEI.

According to a preferred embodiment, the pigments according to the invention may be coated with isopropyl triisostearyl titanate. As examples of pigments treated with isopropyl titanium triisostearate (ITT), mention may be made of titanium dioxide pigments and black, red and yellow iron oxide pigments sold under the commercial reference BWBO-I2® (Iron Oxide CI77499 and Isopropyl Titanium Triisostearate), BWYO-I2® (Iron Oxide CI77492 and Isopropyl Titanium Triisostearate) and BWRO-I2® (Iron Oxide CI77491 and Isopropyl Titanium Triisostearate) by the company KOBO.

Among the mineral pigments, mention may also be made of nacres. They may be chosen from white nacreous pigments such as mica coated with titanium or bismuth oxychloride, colored nacreous pigments such as titanium mica with iron oxides, titanium mica with in particular ferric blue or chromium oxide, titanium mica with an organic pigment of the aforementioned type as well as nacreous pigments based on bismuth oxychloride.

The pigments which can be used according to the invention can also be organic pigments.

By "organic pigment" is meant any pigment that meets the definition of the Ullmann encyclopedia in the organic pigment chapter. The organic pigment may in particular be chosen from nitroso, nitro, azo, xanthene, quinoline, anthraquinone, phthalocyanine, metal complex type compounds, isoindolinone, isoindoline, quinacridone, perinone, perylene, diketopyrrolopyrrole, thioindigo, dioxazine, triphenylmethane, quinophthalone.

The organic pigment(s) may be chosen, for example, from carmine, carbon black, aniline black, melanin, azo yellow, quinacridone, phthalocyanine blue, sorghum red, the blue pigments codified in the Color Index under the references CI 42090, 69800, 69825, 73000, 74100, 74160, the yellow pigments codified in the Color Index under the references CI 11680, 11710, 15985, 19140, 20040, 21100, 21108, 47000, 47005, the green pigments codified in the Color Index under the references CI 61565, 61570, 74260, the pigments oranges codified in the Color Index under the references CI11725, 15510, 45370, 71105, the red pigments codified in the Color Index under the references CI 12085, 12120, 12370, 12420, 12490, 14700, 15525, 15580, 15620, 15630, 15800, 15850, 15865, 15880, 17200, 26100, 45380, 45410, 58000, 73360, 73915, 75470, and the pigments obtained by oxidative polymerization of indole, phenolic derivatives as described in patent FR2 679 771.

These pigments may also be in the form of composite pigments as described in patent EP1184426. These composite pigments may be composed in particular of particles comprising an inorganic core at least partially covered with an organic pigment and at least one binder ensuring the fixing of the organic pigments on the core.

The pigment can also be a lake. By lake we mean insolubilized dyes adsorbed on insoluble particles, the whole thus obtained remaining insoluble during use.

Inorganic substrates on which dyes are adsorbed include, for example, alumina, silica, calcium sodium borosilicate or calcium aluminium borosilicate, and aluminium.

Organic dyes include cochineal carmine. Other products known under the following names include: D&C Red 21 (CI 45 380), D&C Orange 5 (CI 45 370), D&C Red 27 (CI 45 410), D&C Orange 10 (CI 45 425), D&C Red 3 (CI 45 430), D&C Red 4 (CI 15 510), D&C Red 33 (CI 17 200), D&C Yellow 5 (CI 19 140), D&C Yellow 6 (CI 15 985), D&C Green (CI 61 570), D&C Yellow 1 O (CI 77 002), D&C Green 3 (CI 42 053), D&C Blue 1 (CI 42 090).

Examples of lacquers include the product known as D&C Red 7 (CI 15850:1).

1. Matières colorantes liposolubles

Preferably, the pulverulent coloring material(s) is (are) present, preferably, in the composition in a content of less than or equal to 50% by weight, preferably from 25 to 40% by weight, more particularly from 3 to 15% by weight relative to the total weight of the composition.

1. Fat-soluble coloring matters

A composition according to the invention may comprise at least one liposoluble coloring matter and preferably at a rate of at least 0.01% by weight relative to the total weight of the composition.

For obvious reasons, this quantity is likely to vary significantly with regard to the intensity of the desired color effect and the color intensity provided by the coloring materials considered and its adjustment clearly falls within the skills of those skilled in the art.

For the purposes of the invention, the term “fat-soluble coloring matter” means any generally organic compound, natural or synthetic, soluble in an oily phase or solvents miscible with a fatty substance and capable of coloring.

As liposoluble dyes suitable for the invention, mention may in particular be made of liposoluble dyes, synthetic or natural, such as, for example, DC Red 17, DC Red 21, DC Red 27, DC Green 6, DC Yellow 11, DC Violet 2, DC Orange 5, Sudan red, carotenes (β-carotene, lycopene), xanthophylls (capsanthin, capsorubin, lutein), palm oil, Sudan brown, quinoline yellow, annatto, curcumin.

Preferably, the composition according to the invention comprises at least one powdery coloring material of the mineral pigment type, in particular chosen from metal oxides, and more particularly chosen from titanium dioxides, black, red or yellow iron oxides, coated or not, and their mixtures.

According to a particularly preferred embodiment, the composition according to the invention comprises at least one pulverulent coloring material chosen from titanium dioxides coated according to the invention with isopropyl triisostearyl titanate, black, red or yellow iron oxides coated with isopropyl triisostearyl titanate, and mixtures thereof.

Cosmetic applications

The composition used according to the invention may be a care and/or makeup composition for keratin materials, in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours.

According to a particularly preferred form, the composition of the invention is anhydrous.

For the purposes of the invention, the expression “anhydrous composition” denotes respectively a composition which contains less than 5% by weight of water, preferably less than 2% by weight of water, or even less than 0.5% of water relative to its total weight, and in particular a composition free of water.

More specifically, the composition according to the invention is an eyebrow care and/or makeup product such as a mascara.

Such compositions are in particular prepared according to the general knowledge of those skilled in the art.

Packaging and application set or kit

The present invention also relates to a set, or kit, for packaging and applying a cosmetic composition for coating keratin materials comprising:
- a packaging device comprising said cosmetic composition for coating keratin materials as previously described,
- an applicator of said composition.

According to another aspect, the invention also relates to a makeup set comprising:
i) an applicator
ii) a composition in accordance with the invention placed inside a container.

The container may delimit one or more compartment(s). The container may for example be in the form of a tube.

Such an applicator may be integral with a cap mounted reversibly on said container between a position for closing said container and a makeup position.

Alternatively, such an applicator may be irreversibly mounted on said container. Examples of applicators include those of the felt or brush type which may be made of synthetic fibers.

It is understood that within the framework of the present invention, the weight percentages given for a compound or a family of compounds are always expressed by weight relative to the total weight of the composition.

Throughout the application, the expression “has a” or “includes a” must be understood as meaning “has at least one” or “comprises at least one”, unless otherwise specified.

It is understood that the following examples are provided for illustrative purposes and are in no way limiting of the scope of the protection conferred by this application.

Preparation examples

Example 1: Preparation of a 60% solution of decamethylcyclopentasiloxane silicone resin modified with 3-glyceroxypropyl groups

A reactor was charged with 1300 g of a 50% solution of decamethylcyclopentasiloxane of a powdered organosilicon resin containing hydrosilyl groups, of average composition formula (E4) (weight average molecular weight, 4480; hydrogen gas evolution amount, 8.0 mL/g), 30.7 g of the glycerol monoallyl ether of formula (E5), 1300 g of 2-propanol and 0.7 g of a 0.5% chloroplatinic acid solution in 2-propanol, and the reaction was carried out by heating for 6 hours at 100°C. The solvent was then removed by heating under reduced pressure. Then, 325 g of ethanol was added, after which 6.5 g of 5% aqueous sodium hydroxide solution was added, thereby hydrolyzing the unreacted hydrosilyl groups, after which neutralization was carried out by adding 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of 0.01 N aqueous hydrochloric acid was added, thereby hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene, and neutralization was carried out with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was heated under reduced pressure to remove the solvent and filtration was carried out, giving a decamethylcyclopentasiloxane solution of the 3-glyceroxypropyl modified silicone resin of formula (E6). The solution had a clear and colorless appearance.

The decamethylcyclopentasiloxane solution of this silicone resin modified with 3-glyceroxypropyl groups was heated to 120 to 130°C under reduced pressure to remove the decamethylcyclopentasiloxane. The product thus obtained was a solid powder which had an HLB of 0.9.
(Me ₃ SiO _1/2 ) _27.8 (HMe ₂ SiO _1/2 ) _1.6 (SiO _4/2 ) _35.3 (E4)
CH ₂ ═CH-CH ₂ -O-(CH ₂ CH(OH)CH ₂ O)-H (E5)
(Me ₃ SiO _1/2 ) _27.8 (R ² Me ₂ SiO _1/2 ) _1.6 (SiO _4/2 ) _35.3 (E6)
R ² = -CH ₂ -CH ₂ -CH ₂ -O-(CH ₂ CH(OH)CH ₂ O)-H

Example 2: Preparation of a 60% by weight solution of isododecane of a silicone resin modified with 3-glyceroxypropyl groups

A reactor was charged with 1300 g of a 50% isododecane solution of a powdered organosilicon resin containing a hydrosilyl group, of average composition formula (E4) (weight average molecular weight, 4480; amount of hydrogen gas evolution, 8.0 mL/g), 30.7 g of the glycerol monoallyl ether of formula (E5), 1300 g of 2-propanol and 0.7 g of a 0.5% chloroplatinic acid solution in 2-propanol, and the reaction was carried out by heating for 6 hours at 100°C. The solvent was then removed by heating under reduced pressure. Then, 325 g of ethanol was added, after which 6.5 g of 5% aqueous sodium hydroxide solution was added, thereby hydrolyzing the unreacted hydrosilyl groups, after which neutralization was carried out by adding 0.8 g of concentrated hydrochloric acid. After neutralization, 195 g of 0.01 N aqueous hydrochloric acid was added, thereby hydrolyzing the allyl ether groups on the unreacted polyoxyalkylene, and neutralization was carried out with 3.3 g of 5% aqueous sodium bicarbonate. The reaction product was then heated under reduced pressure to drive off the solvent and filtration was carried out, thereby giving an isododecane solution of the 3-glyceroxypropyl-modified silicone resin of formula (E6).
(Me ₃ SiO _1/2 ) _27.8 (HMe ₂ SiO _1/2 ) _1.6 (SiO _4/2 ) _35.3 (E4)
CH ₂ ═CH-CH ₂ -O-(CH ₂ CH(OH)CH ₂ O)-H (E5)
(Me ₃ SiO _1/2 ) _27.8 (R ² Me ₂ SiO _1/2 ) _1.6 (SiO _4/2 ) _35.3 (E6)
R ² = -CH ₂ -CH ₂ -CH ₂ -O-(CH ₂ CH(OH)CH ₂ O)-H.

Examples of eyebrow makeup composition

The following compositions were prepared.

Ingredients Ex 3 (invention) Ex 3a
(excluding invention) SILICONE RESIN
(3-GLYCEROXYPROPYL) DIMETHYLSILOXY TRIMETHYLSILOXYSILICATE OF FORMULA (21) IN 50% SOLUTION IN ISODODECANE
(X-25-9138A® BY SHIN ETSU)
(glycerolated silicone resin) 9.09
(4.54% by weight of active matter) 0
TRIMETHYLSILOXYSILICATE IN 75% SOLUTION IN ISODODECANE
(SILSOFT 74 FLUID® - MOMENTIVE PERFORMANCE MATERIALS)
(non-glycerolated silicone resin) 18
(13.5% by weight of active matter) 18
(13.5% by weight of active matter) DIMETHICONE IN 25% SOLUTION IN ISODODECANE
(SILSOFT B3820 BLEND® - MOMENTIVE PERFORMANCE MATERIALS)
(silicone gum) 48
(12% by weight of active matter) 48
(12% by weight of active matter) DISTEARDIMONIUM HECTORITE
(BENTONE 38 VCG® RHEOLOGICAL ADDITIVE -ELEMENTIS) 5
5
PROPYLENE CARBONATE 1.65
1.65
TITANIUM DIOXIDE (AND) ISOPROPYL TITANIUM TRIISOSTEARATE
(BTD-401® - KOBO) 2.47 2.47 RED IRON OXIDES (AND) ISOPROPYL TITANIUM TRIISOSTEARATE
(BWRO-I2® - KOBO) 0.59 0.59 YELLOW IRON OXIDES (AND) ISOPROPYL TITANIUM TRIISOSTEARATE
(BWYO-I2® - KOBO) 0.9 0.9
BLACK IRON OXIDES (AND) ISOPROPYL TITANIUM TRIISOSTEARATE
(BWBO-I2® - KOBO) 1.12 1.12 ISODODECANE qsp 100 qsp 100

Protocol for the preparation of compositions

Disteardimonium hectorite was pre-dispersed in isododecane. All ingredients were added to an Olsa-type tank, heated to 70°C and homogenized for 30 minutes, then cooled to room temperature (25°C).

In vitro tests for measuring hold: resistance to make-up remover oil

Test protocol

A layer of each formula example was deposited on Supplale in a 1x2 cm rectangle with a brush. The deposit was allowed to dry for 1 hour. 5 colorimetric data measurements were performed on each deposit before application of the makeup remover (T ₀ ) with a Konica CM 700d spectrophotometer (Minolta). The mean values of L ₀ *, a ₀ * and b ₀ * were measured under illuminant D65 (average daylight including UV rays).

3 drops of Shu Uemura – Ultime 8 Huile Démaquillante® cleansing oil were applied to the deposit obtained with each example formula. The deposit to be evaluated was rubbed in a circular motion 4 times. It was rinsed with water and then dabbed with a tissue to remove excess water. The operation was repeated 5 times on each deposit. 5 colorimetric data measurements (T ₅ ) were performed on each deposit by measuring the average values of L ₅ *, a ₅ * and b ₅ * under illuminant D65. The operation was repeated 5 times on each deposit previously made. The resistance to cleansing oil of each example composition was evaluated by calculating the ΔE* according to the following equation:

[Math 1]:
ΔE =

The results obtained are shown in the table below.

Formula Example 3
invention Example 3a
outside invention
without glycerol resin Resistance to makeup remover oil
ΔE
12.0 ± 1.93
25.49 ± 0.99 The results of the comparative tests showed that example 3 of the invention comprising the combination of the non-glycerolated silicone resin TRIMETHYLSILOXYSILICATE, the glycerolated silicone resin 3-GLYCEROXYPROPYL) DIMETHYLSILOXY TRIMETHYLSILOXYSILICATE and a silicone gum exhibited excellent resistance to make-up remover oil unlike example 3a outside the invention without glycerolated silicone resin.

Claims (34)

Composition, preferably for the care and/or makeup of keratin materials, in particular eyebrows including eyebrow hairs, the skin where said hairs are implanted and their contours, comprising, in particular in a physiologically acceptable medium:
(a) at least one non-glycerolated silicone resin; and
(b) at least one glycerolated silicone resin; and
(c) at least one silicone gum; and
(d) at least one oily phase comprising at least one volatile hydrocarbon oil; and
(e) a lipophilic thickener. Composition according to claim 1, where the non-glycerolated silicone resin (a) is chosen from MQ type silicone resins, T type silicone resins, MQT type silicone resins, and mixtures thereof. Composition according to claim 1 or 2, comprising at least one non-glycerolated silicone resin (a) chosen from silicone resins of MQ type, in particular of Trimethylsiloxysilicate type. Composition according to claim 3, where the non-glycerolated resin (a) of the Trimethylsiloxysilicate type is in solution in isododecane, in particular in solution at 75% by weight of active material in isododecane. Composition according to any one of the preceding claims, where the non-glycerolated silicone resin(s) (a) is (are) present in an active material content ranging from 4 to 35% by weight relative to the total weight of the composition, preferably ranging from 6 to 30% by weight and more preferably from 8 to 25% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, where the glycerolated silicone resin(s) (b) is (are) present in an active material content ranging from 0.1 to 40% by weight relative to the total weight of the composition, preferably ranging from 0.2 to 30% by weight and more preferably from 0.5 to 15% by weight relative to the total weight of the composition. Composition according to any one of the preceding claims, where the glycerolated silicone resin (b) contains at least one organosiloxane unit of the type RR'R''SiO _1/2 in which R, R' and R''', identical or different, denote hydrocarbon radicals of which at least one of said radicals contains a monoglycerol group or a polyglycerol group. Composition according to claim 7, where the glycerolated silicone resin (b) contains at least one dimethylsiloxane unit R(CH ₃ ) ₂ SiO _1/2 comprising a hydrocarbon radical R comprising a monoglycerol group. Composition according to any one of the preceding claims, where the glycerolated silicone resin(s) (b) are chosen from those of the following formula (1):
(R¹ ₃SiO_1/2)_has(R²(CH₃)₂SiO_1/2)_b(R³ ₃SiO_1/2)_c(R¹ ₂SiO_2/2)_d(R¹SiO_3/2)_e(SiO_4/2)_f(1)
in which
- each R¹, the same or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof;
- each R²is a mono- or poly-glycerol group of the following general formula (2)
—(CH₂)₂—C_LH_2l—O—(CH₂CH(OH)CH₂O)_iR⁴(2)
in which
- R⁴is a substituted or unsubstituted monovalent hydrocarbon group or a hydrogen atom, and
- the indices l and i are integers which satisfy the conditions 0 ≤ l ≤ 15 and
0 < i ≤ 5,
- each R³is an identical or different group of general formula (3), general formula (4), general formula (5) or general formula (6) below
—(CH₂)₂—C_mH_2m—(SiOR¹ ₂)j—SiR¹ ₃(3)

—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ ₃)_3−k1)(4)

—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ ₃)_{3−k2)3−k1}(5)

—(CH₂)₂—C_mH_2m—SiR¹ _k1—(OSiR¹ _k2(OSiR¹ _k3(OSiR¹ ₃)_{3−k3)3−k2)3−k1}(6)
Or
- each R¹, the same or different, is an alkyl, aryl or aralkyl group of 1 to 30 carbon atoms, or a group substituted by halogen, a group substituted by amino or a group substituted by a carboxyl thereof
- the indices m, j and k1 to k3 are integers that satisfy the conditions
0≤ m ≤ 5, 0 ≤ j ≤ 500, 0≤ k1 ≤ 2, 0 ≤ k2 ≤ 2 and 0 ≤ k3 ≤ 2 ;
- the indices a, b, c, d, e and f are numbers that satisfy the conditions
0 ≤ a ≤ 400, 0 <b ≤ 200, 0 ≤ c ≤ 400, 0 ≤ d ≤ 320, 0 ≤ e ≤ 320, 0 < f ≤ 1000 and
0.5 ≤ (a+b+c)/f ≤ 1.5. Composition according to claim 9, where the glycerolated silicone resin(s) (b) of formula (1) are chosen from those of which
- the indices b and c satisfy the conditions 0 < b ≤ 30 and 0 ≤ c ≤ 30;
- the index i in the general formula (2) of the polyglycerol group R ² is an integer which satisfies the condition 0 < i ≤ 3. Composition according to claim 9 or 10, where the glycerolated silicone resin(s) (b) of formula (1) have a weight-average molecular mass which preferably varies from 1000 to 100,000 and more preferably from 3000 to 50,000. Composition according to any one of claims 9 to 11, where the glycerolated silicone resin(s) (b) of average formula (1) are in solid form at 25°C when the index c satisfies the condition 0 < c ≤ 400 and R ³ is a group of general formula (3) where the index j satisfies the condition 0 ≤ j ≤ 10. Composition according to any one of claims 9 to 12, wherein the glycerolated silicone resin or resins (b) has (have) a hydrophilic-lipophilic balance (HLB), as determined by the Griffin formula, ranging from 0.1 to 15, and more preferably from 1.0 to 8.0. Composition according to any one of claims 9 to 13, comprising at least one glycerolated silicone resin (b) of formula (1) of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type corresponding to the following formula (21):
[(CH ₃ ) ₃ SiO _1/2 ] _a [R(CH ₃ ) ₂ SiO _1/2 ] _b (SiO _4/2 ) _f (21)
Or
- R denotes the 3-glyceroxypropyl group of structure
-C ₃ H ₆ OCH ₂ -CH(OH)CH ₂ OH;
- the indices a, b and f are integers which satisfy the conditions 0 ≤ a ≤ 400,
0 < b ≤ 30, 0 < f ≤ 1000 and 0.5 ≤ (a+b)/f ≤ 1.5. Composition according to claim 14, where the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution in at least one volatile oil. Composition according to claim 15, where the glycerolated silicone resin of the (3-Glyceroxypropyl) Dimethylsiloxy Trimethylsiloxysilicate type of formula (21) is in the form of a solution at 49.5% by weight of active material in isododecane. Composition according to any one of the preceding claims, comprising at least one glycerolated silicone resin (a) and at least one non-glycerolated silicone resin (b) in a weight ratio of the amount of glycerolated silicone resin to the amount of non-glycerolated silicone resin greater than or equal to 0.8, and more preferably greater than or equal to 1.0. Composition according to any one of the preceding claims, comprising at least one volatile hydrocarbon oil chosen from C8-C16 isoalkanes of petroleum origin, in particular isododecane. Composition according to any one of the preceding claims, wherein the volatile hydrocarbon oil or oils are preferably present in contents of less than or equal to 80% by weight, preferably from 40 to 70% by weight relative to the total weight of said composition. Composition according to any one of the preceding claims, where the silicone gum (c) is chosen from silicones of formula
in which:
R1, R2, R5 and R6 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms,
R3 and R4 are, together or separately, an alkyl radical containing from 1 to 6 carbon atoms, a vinyl radical, an amine radical or a hydroxyl radical,
X is an alkyl radical containing from 1 to 6 carbon atoms, a hydroxyl radical or an amine radical, and
n and p being integers chosen such that the molecular mass of the silicone gum (c) is greater than or equal to 180000 g/mol. Composition according to claim 20, where n and p vary from 0 to 3000, knowing that n and p are not zero simultaneously. Composition according to any one of the preceding claims, where the silicone gum (c) is in the form of a solution in an organic solvent, preferably chosen from volatile silicones, polydimethylsiloxane oils, polyphenylmethylsiloxane oils, isoparaffins, in particular C8-C16 such as isododecane, methylene chloride, pentane, dodecane, tridecane, tetradecane or their mixtures, more particularly the solvent is isododecane. Composition according to claim 22, where the proportion of silicone gum (c) in the organic solvent solution represents from 5 to 40% by weight, and more preferably from 10 to 30% by weight relative to the total weight of said solution. Composition according to any one of the preceding claims, where the silicone gum(s) (c) is (are) present at active material contents ranging from 5 to 30% by weight, and more particularly from 8 to 15% by weight. Composition according to any one of the preceding claims, where the silicone gum (c) is a polydimethylsiloxane with the INCI name DIMETHICONE of the following formula:

in which n is less than or equal to 3000, and particularly said gum is in the form of a solution in isododecane, and more particularly in the form of a 25% by weight solution in isododecane. Composition according to any one of the preceding claims, where the lipophilic thickener (e) is a lipophilic clay, and more particularly a hectorite modified with distearyl dimethyl ammonium chloride with the INCI name: DISTEARDIMONIUM HECTORITE. Composition according to any one of the preceding claims, where the lipophilic thickener or thickeners (e) are present at concentrations ranging, preferably from 0.5 to 10% by weight and more preferably from 1 to 6% relative to the total weight of the composition. Composition according to any one of the preceding claims, additionally comprising at least one coloring material, preferably.
chosen from powdery coloring matters, fat-soluble dyes, and their mixtures. Composition according to claim 28, where the pulverulent coloring matter(s) is (are) present in a content of less than or equal to 50.0% by weight, preferably ranging from 25 to 40% by weight, more particularly from 3 to 15% by weight relative to the total weight of the composition. Composition according to claim 28 or 29, where the pulverulent coloring material(s) is (are) chosen from metal oxides, and more particularly chosen from titanium dioxides, black, red or yellow iron oxides, coated or not, and mixtures thereof. Composition according to claim 30, comprising at least one pulverulent coloring matter chosen from titanium dioxides coated with isopropyl triisostearyl titanate, black, red or yellow iron oxides coated with isopropyl triisostearyl titanate, and mixtures thereof. Composition according to any one of the preceding claims, characterized in that it is anhydrous. Set, or kit, for packaging and applying a cosmetic composition for coating keratin materials comprising:
- a packaging device comprising the composition as defined in any one of claims 1 to 32;
- an applicator of said composition. Process for coating, in particular for curling keratin materials, in particular eyebrows and the skin around the eye and eyebrows, comprising the application to said keratin fibres of a composition as defined according to any one of claims 1 to 32.