JPH07304627A - Cosmetic - Google Patents

Abstract

PURPOSE:To obtain an aqueous cosmetic mixed with a silicone modified with a polyether, having no problem of a smell with time. CONSTITUTION:The cosmetic mixed with a silicone compound of the formula R<1>a, R<2>bSiO(4-a-b) [R<1> are the same or different 1-10C alkyl groups, aryl groups, aralkyl groups or fluorine-substituted alkyl groups; R<2> are organic groups of the general formula (CH2)k(CH=CH)m(CH2)nO (CxH2xO)yR<3> (R<3> is H or a 1-20C alkyl group or acyl group; (a), (b), (k), (m), (n), (x) and (y) are l.0<=a<=2.5, 0.005<=b<=1. (k) is an integer of >=2. (m) is 0 or 1; (n) is an integer of >=1. The total of k+m+n is an integer of >=6, (x) is 2-4 as an average value and (y) is 3-20 as an average value.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention not only has no odor in the drug substance itself, but also makes use of a polyether-modified silicone that has no odor even if it is added to an aqueous system as an emulsifier. Regarding fees.

[0002]

2. Description of the Related Art Polyether-modified silicone is excellent as an emulsifier, etc., and is conventionally produced by addition reaction of organohydrogensiloxane and polyoxyalkylene monoallyl ether in the presence of a catalyst such as chloroplatinic acid. . However, when the polyether-modified silicone thus obtained is used in an aqueous system such as an emulsified system, it has an odor over time, so that there is a drawback that the formulation is limited for use in cosmetics and the like. This is because the double bond at the end of the polyoxyalkylene monoallyl ether undergoes internal rearrangement during the addition reaction to produce polyoxyalkylene monopropenyl ether which is not reactive with the organohydrogensiloxane, and is formed by the normal addition reaction. This is because the polyether-modified silicone remains as an impurity, but when water acts on the polyether-modified silicone containing this impurity, the propenyl ether portion is hydrolyzed to generate propionaldehyde.

In order to solve this drawback, the product after the addition reaction is treated with an acidic aqueous solution to hydrolyze the propenyl ether moiety of the remaining polyoxyalkylene to remove the unsaturated group causing odor. A purification method is disclosed (see Japanese Patent Laid-Open No. 302302/1990). However, in this method, when the hydrolysis treatment is insufficient, the odor is not sufficiently removed, and it is difficult to maintain a product of stable quality. Further, when treating a polyether-modified silicone having a low polyoxyalkylene content, the odor can be reduced relatively easily, but a polyether-modified silicone having a high polyoxyalkylene content, that is, a large amount of odor can be generated. When treating an effective silicone, it is difficult to reduce the odor.

On the other hand, JP-B-5-81292 discloses a compound in which 3-methyl-1-butyn-3-ol or the like is used as an initiator, and an alkylene oxide is added to the initiator to cause an addition reaction with an organohydrogensiloxane. A polyether modified silicone obtained thereby is disclosed.
According to this method, the polyoxyalkylene compound used as a raw material has 4 carbon atoms adjacent to the terminal unsaturated group.
Since it is a primary carbon, the unsaturated group does not rearrange during the addition reaction with the organohydrogensiloxane and therefore does not produce an odor when added to an aqueous system. However, the polyoxyalkylene compound used in the reaction has a triple bond as an unsaturated group, and therefore the polyether-modified silicone produced by a normal addition reaction has a double bond adjacent to a silicon atom ( -Si-CH = CH-R). This structure having a vinyl silane skeleton is easily hydrolyzed under acidic conditions, and when mixed in an aqueous system, the main component itself has a property of hydrolyzing, which is not preferable.

Further, in Japanese Patent Publication No. 51-8440, a compound in which 3-methyl-1-buten-3-ol or the like is used as an initiator and an alkylene oxide is added thereto is used to carry out an addition reaction with an organohydrogensiloxane. A polyether modified silicone obtained thereby is disclosed.
This method is similar to Japanese Patent Publication No. 5-81292, in which the carbon atom adjacent to the terminal unsaturated group of the polyoxyalkylene compound is a quaternary carbon, and the unsaturated group is rearranged during the addition reaction with hydrogen siloxane. do not do. Further, since this unsaturated group is a double bond, the unsaturated group does not remain in the polyether-modified silicone produced by the normal addition reaction.
However, the unsaturated alcohol used as an initiator for obtaining the polyoxyalkylene compound is not readily available, and this polyether-modified silicone is not a method for mass-producing at low cost. The unsaturated alcohol as the initiator is a tertiary alcohol,
The addition reactivity of alkylene oxide to this is remarkably worse than in the case of using conventional allyl alcohol (primary alcohol), so that more severe reaction conditions are required and a heat deterioration product is by-produced, which is not preferable.

Further, when an alkylene oxide is added using a secondary or tertiary alcohol as an initiator, the reactivity is lower than that of the primary alcohol. However, the component to which 1 mol or more of alkylene oxide is added in the initial stage of the reaction has the property of higher reactivity than the initiator alcohol. Therefore, the polymerization proceeds smoothly from the molecule in which the alkylene oxide is added to the initiator alcohol,
As a result, the initiator alcohol, which has low reactivity, is not completely consumed but a part thereof remains. The initiator alcohol used here has a strong unpleasant odor due to the structure having an unsaturated group, and the polyoxyalkylene compound thus obtained cannot be used for cosmetics.

Further, Japanese Patent Publication No. 46-9353 discloses a method of using a long chain alkenol other than allyl alcohol or alkenonic acid as an unsaturated alcohol as an initiator for obtaining a polyoxyalkylene compound. . However, when an alkylene oxide is added to a long-chain alkenonic acid, the polyoxyalkylene group is bonded via an ester bond, and this structure is inferior in non-hydrolyzability, which is not preferable.
Although 3-cycloocten-1-ol etc. are illustrated as a specific example of a long-chain alkenol, these are compounds which have a double bond in the inside of a cyclic compound, and are inferior in reactivity with organohydrogensiloxane. It is a thing.
Further, the hydroxyl group also has a structure of a secondary alcohol and is inferior in reactivity with alkylene oxide, and therefore has the same problem as described above.

Also, Japanese Patent Publication No. 5-51619 discloses a silicone compound in which a silicon atom and a polyoxyalkylene group are bonded via an alkylene group having 3 to 10 carbon atoms. However, if this alkylene group is an organic group derived from an initiator alcohol having an unsaturated bond inside the cyclic compound as in the above-mentioned publication, the same problem as described above occurs. Further, even if it is a straight chain having an unsaturated group at the terminal, it has the same problem when it is an organic group derived from a secondary or tertiary alcohol, but no details are described.

[0009]

As described above, not only is it easily produced and has no odor in the drug substance itself, but the odor generated over time even when it is blended in an aqueous system as an emulsifier or the like. Satisfactory compounds have not yet been obtained with regard to polyether-modified silicones that do not. Therefore, none of the water-based cosmetics containing the polyether-modified silicone can satisfy the odor generated over time. The present invention has been made in an attempt to improve such a conventional technique.

[0010]

In view of the above situation, the present inventors have made diligent studies and as a result, have found a polyoxyalkylene compound obtained by addition-polymerizing an alkylene oxide with a primary long-chain alkenol having a double bond at the terminal as an initiator. It was found that, by addition-reacting this with organohydrogensiloxane, a polyether-modified silicone having no odor can be obtained without any special treatment step, and is suitable for use in cosmetics, thus completing the present invention. Came to.

The present invention relates to a cosmetic using a odorless silicone compound, and the present invention relates to a cosmetic of the general formula R ¹ _a R
Silicone compound represented by ² _b SiO _{(4-ab) / 2} [where R ¹
Are the same or different alkyl groups having 1 to 10 carbon atoms, aryl groups, aralkyl groups or fluorine-substituted alkyl groups, R ² is represented by the general formula-(CH ₂ ) _k (CH = CH) _m (CH ₂ ) _n O An organic group represented by (C _x H _2x O) _y R ³ , R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or an acyl group, and a, b, k, m, n,
x and y are 1.0 ≤ a ≤ 2.5 and 0.005 ≤ b ≤ 1.2, respectively.
And 1.7 ≦ a + b ≦ 2.7, k is an integer of 2 or more, m is 0 or 1, n is an integer of 1 or more, and the sum of k + m + n is an integer of 6 or more, x is 2 to 4 as an average value, y
Is an average value of 3 to 200], and further, the general formula R ¹ _a R ² _b SiO _{(4-ab) / 2} (where
R ¹ , R ² , a, and b are the same as those described above) and used as a starting material thereof in the general formula CH ₂ = CH (CH ₂ ) _k-2 (CH = CH) _m (C
H ₂ ) _n OH (where k, m and n are the same as above) The present invention relates to a cosmetic composition containing a silicone compound substantially free of unreacted alcohol.

The present invention will be described in detail below. The silicone compound used in the present invention has the general formula as described above.
R ¹ _a R ² _b SiO _{(4-ab) / 2} , wherein R ¹ is the same or different alkyl group having 1 to 10 carbon atoms, aryl group, aralkyl group or fluorine-substituted alkyl group, R ² is a general formula −
(CH ₂ ) _k (CH = CH) _m (CH ₂ ) _n O (C _x H _2X O) _y R ³ is an organic group,
R ³ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms or an acyl group, and a, b, k, m, n, x and y are 1.0 ≦ a ≦ 2.5, 0.005 ≦ b ≦ 1.2, and 1.7 ≦, respectively. a +
b ≦ 2.7, k is an integer of 2 or more, m is 0 or 1, n is 1
The above is an integer and the sum of k + m + n is an integer of 6 or more, x is 2 to 4 as an average value, and y is 3 to 3 as an average value.
200.

The silicone compound has the general formula CH
₂ = CH (CH ₂ ) _k-2 (CH = CH) _m (CH ₂ ) _n O (C _x H _2x O) _y A polyoxyalkylene compound represented by R ³ and a general formula R ¹ _a H _b SiO
It can be produced by addition reaction with an organohydrogensiloxane represented by _{(4-ab) / 2} . Further, the polyoxyalkylene compound is substantially free from unreacted alcohols represented by the general formula CH ₂ = CH (CH ₂ ) _k-2 (CH = CH) _m (CH ₂ ) _n OH, which is the raw material. If anything,
A silicone compound substantially free of this alcohol is obtained.

Examples of R ^{1 in} the general formula R ¹ _a R ² _b SiO _{(4-ab) / 2} include a methyl group, an ethyl group, a propyl group, a butyl group,
Aliphatic hydrocarbon groups such as pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group; alicyclic hydrocarbon groups such as cyclopentyl group, cyclohexyl group; aryl groups such as phenyl group, tolyl group; benzyl Group, an aralkyl group such as a phenethyl group, a fluorine-substituted alkyl group such as a trifluoropropyl group, a heptadecafluorodecyl group, and the like, but it is particularly preferable that the methyl group in all R ¹ is 50 mol% or more. .

R ² is of the general formula-(CH ₂ ) _k (CH = CH) _m (CH ₂ ) _n O (C _x H
_2X O) _y R ³ is an organic group, wherein k, m and n in the formula are each k is an integer of 2 or more, m is 0 or 1, and n is an integer of 1 or more, and k + m + n The total is 6 or more. However, preferably m is 0 and the sum of k + n is 8-20, or m is 1 and n is 1 or more and the sum of k + m + n is 7-20. More preferably, m is 0 and the sum of k + n is 8, or k is 5, m is 1 and n is 1.

In the addition reaction of a polyoxyalkylene having a double bond at the terminal with an organohydrogensiloxane, the non-reactive impurities in which the double bond is rearranged are hydrolyzable, so that they are mixed in an aqueous system. As described above, the odor is generated over time. However, in the unsaturated group-containing polyoxyalkylene compound as an impurity remaining during this addition reaction, if the unsaturated group is not adjacent to the oxygen atom, it does not show chemical hydrolyzability. When polyoxyalkylene monoallyl ether is used in the above example, the propenyl ether derivative produced as an impurity is hydrolyzed because its unsaturated group has a structure adjacent to an oxygen atom. In the present invention, the total of k + m + n is set to 6 or more. The reason for this is that, as a result of analysis by a nuclear magnetic resonance spectrum, when the total number is less than 6, the terminal double bond is rearranged to a position adjacent to the oxygen atom. Since it produces a product, it has a hydrolyzable structure and causes an odor. However, if the total of k + m + n is 6 or more, even if the double bond at the terminal is rearranged, it becomes an oxygen atom. It is a point to find that it does not form a compound having an unsaturated group adjacent to each other, and thus does not generate odor over time.

Even if the total of k + m + n is 6 or more, when m is 1 and n is 0, this compound has an unsaturated group adjacent to the oxygen atom from the beginning. Since n is hydrolyzable with or without double bond rearrangement, n must not be 0. For confirmation of the position of the unreacted unsaturated group, nuclear magnetic resonance spectrum (NM
R), especially ¹³ C-NMR is effective. k + m + n
When the sum of the above is 6 or more, the carbon atoms resulting from the terminal double bond have signals around 114 and 139 ppm. on the other hand,
About 120-135ppm in the case of the structure in which the double bond is internally rearranged
Signal in the range of. When an unsaturated group adjacent to the oxygen atom is generated, it has a signal near 145 and 105 ppm. Therefore, the presence or absence of a hydrolyzable by-product can be confirmed by checking whether or not it has a signal around 145 and 105.

Further, x in the formula is a value of 2 to 4 as an average value, but one kind or two kinds or more may be arbitrarily selected from ethylene oxide unit, propylene oxide unit and butylene oxide unit. Further, these alkylene oxide units may be either block polymers or random polymers. Furthermore, in order to impart sufficient hydrophilicity to the silicone compound according to the present invention, the content of ethylene oxide units in the alkylene oxide units is preferably 50 mol% or more. y has an average value of 3 to 200, and preferably has an average value of 5 to 100. When y is less than 3 as an average value, the molecular weight of the polyoxyalkylene group is too small and sufficient hydrophilicity cannot be obtained.

Examples of R ³ are hydrogen atom; aliphatic hydrocarbon group such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group and decyl group; Examples thereof include an acyl group such as an acetyl group, a propionyl group, a butyryl group, and a decanoyl group, but a hydrogen atom, a methyl group, and an acetyl group are preferable.

Further, a in the general formula R ¹ _a R ² _b SiO _{(4-ab) / 2} is 1.0 to 2.5, preferably 1.2 to 2.3. When a is less than 1.0, the polyoxyalkylene content is too high, so that the stickiness is strongly felt, and the slipperiness as an oil agent is deteriorated. Also, a is 2.5
If it is larger than the above range, the hydrophilicity becomes poor, so that stable emulsification cannot be maintained. b is 0.005 to 1.2, preferably 0.01 to 1.0. If b is less than 0.005, the hydrophilicity becomes poor, and stable emulsification cannot be maintained.
On the other hand, when b is more than 1.2, the polyoxyalkylene content is too high, so that the stickiness is strongly felt and the slipperiness as an oil agent is deteriorated. a + b is
It is 1.7 to 2.7, preferably 1.9 to 2.3.

The general formula CH ₂ ═CH (C
H ₂ ) _k-2 (CH = CH) _m (CH ₂ ) _n O (C _x H _2x O) _y R ³ is a polyoxyalkylene compound represented by the general formula CH ₂ = CH (CH ₂ ) _k-2 (CH = CH) _m
It is obtained by reacting a long-chain primary alcohol having a double bond at the terminal represented by (CH ₂ ) _n OH with an alkylene oxide. In this case, a certain amount of long chain 1 as an initiator
The primary alcohol and the alkylene oxide may be charged all at the same time, but it is preferable to react 1 to 4 mol of the alkylene oxide with 1 mol of the initiator alcohol, isolate and purify once, and then subject to the reaction again. Unreacted initiator alcohol can be reduced by isolation and purification. For use in cosmetics, it is preferable that substantially no unreacted initiator alcohol is contained, and specifically, the content is 1% by weight or less, preferably 0.5% by weight or less.

As the catalyst used in the reaction of the long-chain primary alcohol with alkylene oxide, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metals such as sodium and potassium, sodium methoxide, Sodium ethoxide, sodium butoxide,
Examples thereof include alkali metal alkoxides such as potassium methoxide, potassium ethoxide and potassium butoxide, and Lewis acids such as aluminum chloride, iron chloride, titanium chloride and boron fluoride-etherate complex.

The silicone compound used in the present invention comprises the polyoxyalkylene compound obtained as described above and an organohydrogensiloxane represented by the general formula R ¹ _a H _b SiO _{(4-ab) / 2} . It is produced by addition reaction in the presence of a platinum catalyst (eg, chloroplatinic acid, alcohol-modified chloroplatinic acid, chloroplatinic acid-vinylsiloxane complex, etc.) or a rhodium catalyst. The organohydrogensiloxane used here may be linear, branched or cyclic, but is preferably mainly linear in order to promote the addition reaction smoothly.

When carrying out the addition reaction, an organic solvent may be used if necessary. For example, aliphatic alcohols such as methanol, ethanol, 2-propanol, butanol; aromatic hydrocarbons such as benzene, toluene, xylene; aliphatic or alicyclic hydrocarbons such as n-pentane, n-hexane, cyclohexane; dichloromethane. , Halogenated hydrocarbons such as chloroform, carbon tetrachloride and the like can be mentioned, but it is particularly preferable to use ethanol or 2-propanol for use in cosmetics.

The silicone compound according to the present invention is characterized by not only having no odor in the drug substance itself, but also producing no odor over time even when blended in an aqueous system. It can be suitably used for any of the emulsified cosmetics. As a use, it can be applied to cosmetics in which conventional polyether-modified silicone is used, and can also be applied as an oil, a moisturizer, an antistatic agent, a powder processing agent, a thickener, an emulsifier, and the like. Specifically, hair care products such as shampoos, rinses, treatments and setting agents; makeup products such as lipsticks, foundations and eyeliners; hand creams, hand lotions, suntan lotions,
Examples thereof include skin care products such as emulsion.

[0026]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The unsaturated group content was determined by adding an excess amount of iodine bromide acetic acid solution to the sample, allowing the solution to stand for a certain period of time, adding an aqueous potassium iodide solution, and performing back titration with an aqueous sodium thiosulfate solution.

(Synthesis Example 1) Organohydrogensiloxane 72 represented by the following average composition formula (1) was used in a reactor.
6 parts by weight,

[Chemical 1] Obtained by adding ethylene oxide to 7-octen-1-ol, the unreacted 7-octen-1-ol content is
There is no odor at 0.5 wt% or less, and the following average composition formula (2)
The polyoxyalkylene compound represented by CH ₂ = CH (CH ₂ ) ₆ O (C ₂ H ₄ O) ₇ H (2) 872 parts by weight and ethanol 400 parts by weight were charged, and 2% by weight of chloroplatinic acid 0.2 parts by weight of an ethanol solution was added, and the mixture was reacted under reflux of the solvent for 5 hours.

After the reaction was completed, the reaction product was heated under reduced pressure to distill off the solvent, and then filtered to obtain the target product represented by the following average composition formula.

[Chemical 2] The product was a pale yellow, transparent, odorless liquid and had a viscosity of 92 cSt (25 ° C).

The degree of unsaturation of the product was measured to be 0.006
Mol / 100 g (unsaturation degree of the raw material polyoxyalkylene compound was 0.229 mol / 100 g), and contained about 4.8% by weight of unreacted polyoxyalkylene compound. When ¹³ C-NMR of the product was measured, signals at 123, 124, 129, 130, 131, and 132 ppm were detected as a part attributable to the unsaturated group. The signals due to the terminal double bond of the starting polyoxyalkylene compound were 114 and 139 ppm. Therefore, the unreacted polyoxyalkylene compound contained in this product does not have a structure having a double bond at the terminal, and CH ₃ CH = CH ( CH ₂ ) ₅ O (C ₂ H ₄ O) ₇ H and CH ₃ CH ₂ CH = CH (CH ₂ ) ₄ O (C ₂ H
It is identified as a compound having a structure of ₄ O) ₇ H. 145 more
, And no signal was detected around 105 ppm, which confirmed that the hydrolyzable structure represented by CH ₃ (CH ₂ ) ₅ CH = CHO (C ₂ H ₄ O) ₇ H was not formed. It was

The silicone compound (1 g) obtained above and 10 ⁻⁴ N hydrochloric acid (1 g) were weighed in a 20 ml vial and sealed with a rubber septum with an aluminum cap.
Then, after aging at 60 ° C. for 24 hours, 1 μL was accurately sampled with a syringe, and the aldehyde compound was quantified using a gas chromatograph with a hydrogen flame ionization detector. As a result, CH ₃ (CH ₂ ) ₅ CH = CHO (C ₂ H ₄ O) ₇ H as impurities
Was produced, the content of other aldehyde compounds was 100 ppm or less, not to mention the aldehyde compound [CH ₃ (CH ₂ ) ₆ CHO] produced by hydrolysis. Further, when the rubber septum was removed and the odor was sensory examined, no offensive odor was observed. As described above, in spite of the residual unreacted unsaturated group remaining, not only the silicone compound drug substance itself has no odor, but also a compound that does not odor due to aging even when water is added is obtained. It was

(Comparative Synthesis Example 1) The organohydrogensiloxane 72 represented by the above average composition formula (1) was added to the reactor.
6 parts by weight, a polyoxyalkylene compound represented by the average composition formula (3) CH ₂ = CH (CH ₂ ) ₄ CH (CH ₃ ) O (C ₂ H ₄ O) ₇ H (3) 872 parts by weight, and 400 parts by weight of ethanol was charged, 0.2 parts by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added, and the mixture was reacted under reflux of the solvent for 5 hours. The reaction product was heated under reduced pressure to remove the solvent and then filtered to obtain a product represented by the following average composition formula.

[Chemical 3] The product was light yellow and transparent and had a viscosity of 95 cSt (25 ° C). However, the polyoxyalkylene compound represented by the average composition formula (3) contains 2% by weight of unreacted 7-octen-2-ol because it is produced by using a secondary alcohol as an initiator, and has strong irritation. There was a smell. Therefore, the obtained silicone compound also had an irritating odor and was not suitable for cosmetic use.

(Comparative Synthesis Example 2) An organohydrogensiloxane represented by the following average composition formula (4) was added to a reactor.
478 parts by weight,

[Chemical 4] Obtained by adding ethylene oxide to isoprenol,
The polyoxyalkylene compound CH ₂ = C (CH ₃ ) CH ₂ CH ₂ O (C ₂ H ₄ O having an unreacted isoprenol content of 0.5% by weight or less and no odor and having the following average composition formula (5) ) ₁₀ H (5) 160 parts by weight and ethanol 400 parts by weight were charged, 0.2 part by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added, and the mixture was reacted under reflux of the solvent for 5 hours.

After completion of the reaction, the reaction product was heated under reduced pressure to distill off the solvent, and then filtered to obtain a product represented by the following average composition formula.

[Chemical 5] The product was a pale yellow, transparent, odorless liquid and had a viscosity of 460 cSt (25 ° C).

The unsaturation of the product was measured to be 0.004
Mol / 100 g (unsaturation degree of the raw material polyoxyalkylene compound was 0.190 mol / 100 g), and contained about 8% by weight of unreacted polyoxyalkylene compound. Product
^{When 1} H-NMR was measured, it was found to be 4.7 (somewhat broad singlet peak) and 5.4 as the part attributable to the unsaturated group.
(Triplet peak), 6.2 (doublet peak) pp
A signal of m was detected. The proton signal due to the terminal double bond of the raw polyoxyalkylene compound is
It was 4.7 ppm [C H ₂ = C (CH ₃ ) CH ₂ CH ₂ OX: X is a polyoxyethylene residue], and some components in which the double bond is not rearranged remain as they are. The peak at 5.4 ppm can be assigned to CH ₃ C (CH ₃ ) = C H CH ₂ OX in which the double bond is internally rearranged. In addition, the peak at 6.2 ppm has CH ₃ CH (CH
₃ ) CH = C H OX can be assigned.

From the integral ratio of each signal, the residual ratio of each component is CH ₂ = C (CH ₃ ) CH ₂ CH ₂ OX: 39 wt% (A) CH ₃ C (CH ₃ ) = CHCH ₂ OX: 28 % By weight (B) CH ₃ CH (CH ₃ ) CH = CHOX: 33% by weight (C) Among these unreacted substances, the structure of (C) has a double bond adjacent to an oxygen atom, and it is considered that when it is mixed in an aqueous system, it is hydrolyzed to produce isovaleraldehyde. Then, as in Synthesis Example 1, hydrochloric acid water was added and aged. As a result of gas chromatographic analysis, 1020 ppm of isovaleraldehyde was detected.
A strong irritating odor was observed in the sample after aging.

As described above, 1 having a double bond at the end
Even when polyoxyethylene is added using a primary alcohol as an initiator and a polyether-modified silicone is produced using this, a by-product having hydrolyzability when it is an unsaturated alcohol having 5 or less carbon atoms. Cause Therefore, the obtained polyether-modified silicone will generate an irritating odor when it is blended in an aqueous system even if the substance itself has no odor, which is not preferable for cosmetic use.

Synthesis Example 2 Obtained by adding 726 parts by weight of the organohydrogensiloxane represented by the average compositional formula (1) and ethylene oxide and propylene oxide to 7-octen-1-ol in a reactor and unreacted. 7-octen-1-ol content of 0.5% by weight or less and no odor, and polyoxyalkylene compound CH ₂ = CH (CH ₂ ) ₆ O (C ₂ H ₄ ) represented by the following average composition formula (6). O) ₁₀ (C ₃ H ₆ O) ₃ H (6) 1780 parts by weight and 600 parts by weight of ethanol were charged, 0.3 parts by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added to the mixture, and the mixture was refluxed with a solvent to give 5 Reacted for hours.

After the completion of the reaction, the reaction product was heated under reduced pressure to distill off the solvent and then filtered to obtain the target product represented by the following average composition formula.

[Chemical 6] The product is a colorless, transparent, odorless liquid with a viscosity of
It was 160 cSt (25 ° C).

The degree of unsaturation of the product was measured to be 0.017
Mol / 100 g (the degree of unsaturation of the starting polyoxyalkylene compound was 0.135 mol / 100 g), and contained about 12% by weight of unreacted polyoxyalkylene compound. Product
^{When 13} C-NMR was measured, signals of 123, 124, 129, 130, 131, and 132 ppm were detected as a part attributable to the unsaturated group. The signals due to the terminal double bond of the raw material polyoxyalkylene compound are 114 and 139 ppm, and these signals can be attributed to the same as those shown in Synthesis Example 1. Also, no signal was detected around 145 and 105 ppm, which is hydrolyzable.CH ₃ (CH ₂ ) ₅ CH = CHO (C ₂ H ₄ O) ₁₀ (C ₃ H ₆ O) ₃ H It was confirmed that the body did not form.
As a result of adding an aqueous hydrochloric acid solution and aging in the same manner as in Synthesis Example 1, the content of not only CH ₃ (CH ₂ ) ₆ CHO but also other aldehyde compounds was 100 ppm or less. Further, when the rubber septum was removed and the odor was sensory examined, no offensive odor was observed.

(Synthesis Example 3) The organohydrogensiloxane represented by the average composition formula (7) was used in the reactor.

[Chemical 7] 786 parts by weight and 2,7-octadiene-1-ol obtained by adding ethylene oxide, and the content of unreacted 2,7-octadiene-1-ol is 0.5% by weight or less and has no odor. Polyoxyalkylene compound represented by average composition formula (8) CH ₂ = CH (CH ₂ ) ₃ CH = CHCH ₂ O (C ₂ H ₄ O) ₁₀ H (8) 1870 parts by weight and 2-propanol 700 parts by weight Then, 0.3 part by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added, and the mixture was reacted for 5 hours under reflux of the solvent.

After the reaction was completed, the reaction product was heated under reduced pressure to distill off the solvent, and then filtered to obtain the desired product represented by the following average composition formula.

[Chemical 8] The product was a pale yellow, transparent, odorless liquid and had a viscosity of 520 cSt (25 ° C).

When the degree of unsaturation of the product was measured, it was 0.035.
Mol / 100 g (unsaturation degree of the raw material polyoxyalkylene compound was 0.354 mol / 100 g), and contained about 14% by weight of unreacted polyoxyalkylene compound. Product
^{When 13} C-NMR was measured, signals at 115, 124, 125, 127, 130, 131, 132, 133, and 138 ppm were detected as the part attributable to the unsaturated group. The signals due to the terminal double bond of the raw polyoxyalkylene compound are 115 and 138 ppm, and the signals due to the internal double bond are 127 and 13 respectively.
It is 3 ppm. Therefore, in addition to the unreacted terminal double bond and unrearranged internal double bond remaining, a product in which the terminal double bond was internally rearranged was confirmed. But 145
No signal was detected at around 10 and 105 ppm, which confirmed that there was no double bond adjacent to the hydrolyzable oxygen atom. Aqueous hydrochloric acid solution was added in the same manner as in Synthesis Example 1, and as a result, the detected amount of aldehyde compound was 100 p.
It was below pm. Further, when the rubber septum was removed and the odor was sensory examined, no offensive odor was observed.

(Synthesis Example 4) Organohydrogensiloxane represented by the average composition formula (9) was used in the reactor.

[Chemical 9] 846 parts by weight and ethylene oxide added to 9-decen-1-ol, the content of unreacted 9-decen-1-ol is 0.5% by weight or less, and there is no odor. 10) Polyoxyalkylene compound CH ₂ = CH (CH ₂ ) ₈ O (C ₂ H ₄ O) ₄₀ CH ₃ (10) 7020 parts by weight and 2-propanol 2000 parts by weight were charged, and platinum chloride was added thereto. 0.5 part by weight of an ethanol solution containing 2% by weight of acid was added, and the mixture was reacted for 5 hours under reflux of the solvent.

After the completion of the reaction, the reaction product was heated under reduced pressure to distill off the solvent and then filtered to obtain the target product represented by the following average composition formula.

[Chemical 10] The product was odorless, pale yellow and solid with a melting point of 50-60 ° C.

The degree of unsaturation of the product was measured to be 0.006
Mol / 100 g (the degree of unsaturation of the starting polyoxyalkylene compound was 0.052 mol / 100 g), and contained about 13% by weight of unreacted polyoxyalkylene compound. Product
^{When 13} C-NMR was measured, signals at 121, 122, 128, 129, ^{130, and} 131 ppm were detected as a part attributable to the unsaturated group. The signals due to the terminal double bond of the raw material polyoxyalkylene compound were 113 and 138 ppm. Therefore, an unreacted polyoxyalkylene compound having a double bond at the terminal did not exist, and a product in which the double bond was internally rearranged was confirmed. However, no signal was detected at around 145 and 105 ppm, which confirmed that there was no double bond adjacent to the hydrolyzable oxygen atom. As a result of adding an aqueous hydrochloric acid solution and aging in the same manner as in Synthesis Example 1, the detected amount of the aldehyde compound was 100 ppm or less. Furthermore, when the rubber septum was removed and the smell was sensory examined,
No offensive odor was observed.

(Synthesis Example 5) The organohydrogensiloxane represented by the average composition formula (11) was used in the reactor.

[Chemical 11] 643 parts by weight, obtained by adding ethylene oxide to 9-decen-1-ol, the content of unreacted 9-decen-1-ol is 0.5% by weight or less, and there is no odor. ) Polyoxyalkylene compound 1930
By weight, 2000 parts by weight of 2-propanol were added, 0.5 parts by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added, and the mixture was reacted for 5 hours under reflux of the solvent.

After completion of the reaction, the reaction product was heated under reduced pressure to distill off the solvent, and then filtered to obtain the target product represented by the following average composition formula.

[Chemical 12] The product was odorless, pale yellow and solid with a melting point of 50-60 ° C.

The degree of unsaturation of the product was measured to be 0.004
Mol / 100 g (the degree of unsaturation of the raw material polyoxyalkylene compound was 0.052 mol / 100 g), and contained about 10% by weight of unreacted polyoxyalkylene compound. Product
^{When 13} C-NMR was measured, signals at 121, 122, 128, 129, ^{130, and} 131 ppm were detected as a part attributable to the unsaturated group. The signals due to the terminal double bond of the raw material polyoxyalkylene compound were 113 and 138 ppm. Therefore, an unreacted polyoxyalkylene compound having a double bond at the terminal did not exist, and a product in which the double bond was internally rearranged was confirmed. However, no signal was detected at around 145 and 105 ppm, which confirmed that there was no double bond adjacent to the hydrolyzable oxygen atom. As a result of adding an aqueous hydrochloric acid solution and aging in the same manner as in Synthesis Example 1, the detected amount of the aldehyde compound was 100 ppm or less. Furthermore, when the rubber septum was removed and the smell was sensory examined,
No offensive odor was observed.

(Synthesis Example 6) An organohydrogensiloxane represented by the average composition formula (12) was used in a reactor.

[Chemical 13] Unreacted 7-octene-1-obtained by adding ethylene oxide to 404 parts by weight and 7-octen-1-ol
A polyoxyalkylene compound represented by the average composition formula (13) having an ol content of 0.5% by weight or less and no odor, CH ₂ = CH (CH ₂ ) ₆ O (C ₂ H ₄ O) ₁₀ H (13) 170 1 part by weight and 100 parts by weight of ethanol were charged, 0.2 part by weight of an ethanol solution containing 2% by weight of chloroplatinic acid was added, and the mixture was reacted under reflux of the solvent for 5 hours.

After completion of the reaction, the reaction product was heated under reduced pressure to distill off the solvent, and then filtered to obtain the target product represented by the following average composition formula.

[Chemical 14] The product was a pale yellow, transparent, odorless liquid and had a viscosity of 580 cSt (25 ° C).

The degree of unsaturation of the product was measured to be 0.005
Mol / 100 g (unsaturation degree of the raw material polyoxyalkylene compound was 0.176 mol / 100 g), and contained about 10% by weight of unreacted polyoxyalkylene compound. Product
^{When 13} C-NMR was measured, signals of 123, 124, 129, 130, 131, and 132 ppm were detected as a part attributable to the unsaturated group. The signals due to the terminal double bond of the raw material polyoxyalkylene compound were 114 and 139 ppm. Therefore, an unreacted polyoxyalkylene compound having a double bond at the terminal did not exist, and a product in which the double bond was internally rearranged was confirmed. However, no signal was detected at around 145 and 105 ppm, which confirmed that there was no double bond adjacent to the hydrolyzable oxygen atom. As a result of adding an aqueous hydrochloric acid solution and aging in the same manner as in Synthesis Example 1, the detected amount of the aldehyde compound was 100 ppm or less. Furthermore, when the rubber septum was removed and the smell was sensory examined,
No offensive odor was observed.

Example 1 Foundation (1) Octamethylcyclotetrasiloxane 35% by weight (2) Glyceryltriisooctanate 3% by weight (3) Polyether-modified silicone compound of Synthesis Example 2 2% by weight (4) Ceresin Wax 10% by weight (5) Pigment 30% by weight (6) Ion-exchanged water 2% by weight (7) Glycerin 12% by weight (8) 1,3-Butylene glycol 6% by weight (1) to (4) at 80 ° C After heating and dissolving, (5) was added and dispersed at 80 ° C with a homogenizer. Further, the mixture of (6) to (8) previously heated to 80 ° C. was added to emulsify and then cooled to room temperature to obtain an emulsified foundation. The foundation had no odor change with time even after being left at 50 ° C. for 30 days.

Comparative Example 1 A foundation was obtained in the same manner as in Example 1 except that the polyether-modified silicone compound of Example 1 was replaced with the polyether-modified silicone compound synthesized in Comparative Synthesis Example 1. This foundation had an unpleasant odor at the time of production and was not preferable as a cosmetic product.

(Example 2) Hair rinse (1) Cetyltrimethylammonium chloride 2% by weight (2) Distearyldimethylammonium chloride 8% by weight (3) Polyether-modified silicone compound of Synthesis Example 6 10% by weight (4) Glycerin 10 Wt% (5) Polyethylene glycol (molecular weight 300) 8 wt% (6) Ion-exchanged water 62 wt% (1) to (3) and (6) were heated to 80 ° C and dissolved. to this
(4) and (5) were added with stirring to obtain a hair rinse. This hair rinse had no change in odor even after being left at 50 ° C for 30 days.

Comparative Example 2 A hair rinse was obtained in the same manner as in Example 2 except that the polyether modified silicone compound of Example 2 was replaced with the polyether modified silicone compound synthesized in Comparative Synthesis Example 2. Although this hair rinse had no unpleasant odor immediately after its production, it had a strong unpleasant odor after being left at 50 ° C. for 3 days.

Example 3 Hair Treatment Lotion (1) Polyether-modified silicone compound of Synthesis Example 1 2% by weight (2) Dipalmityldimethylammonium chloride 1% by weight (3) Ethanol 40% by weight (4) Propylene glycol 6 wt% (5) Dimethyl polysiloxane (viscosity at 25 ℃ 6cSt) 1 wt% (6) Ion-exchanged water 50 wt% (1) ~ (3) and (5) were dissolved and mixed in advance ( A lotion was obtained by adding the solutions of 4) and 6). The odor of this lotion did not change with time even after standing at 50 ° C for 30 days.

(Example 4) Hand cream (1) Ion-exchanged water 6% by weight (2) L-sodium aspartate 2% by weight (3) Glycerin 57% by weight (4) Sorbitol 70% aqueous solution 10% by weight (5) Decamethylcyclopentasiloxane 10% by weight (6) Dimethylpolysiloxane (viscosity at 25 ° C. 6 cSt) 10% by weight (7) Polyether-modified silicone compound of Synthesis Example 6 5% by weight (5) to (7) at 80 ° C. After being heated and dissolved in, the mixed solution of (1) to (4), which had been heated to 80 ° C. in advance, was added and emulsified and dispersed to obtain a hand cream. This hand cream is 30 at 50 ℃
The odor did not change with time even after being left for a day.

Example 5 Emulsion (1) Octamethylcyclotetrasiloxane 10% by weight (2) Dimethylpolysiloxane (viscosity at 25 ° C. 6 cSt) 10% by weight (3) Cetylisooctanate 2% by weight (4) Liquid paraffin (120 cSt) 2% by weight (5) Sorbitan diisostearate 3% by weight (6) Polyether-modified silicone compound of Synthesis Example 6 3% by weight (7) Ion-exchanged water 64% by weight (8) Sodium dextran sulfate 1 % (9) Sodium chondroitin sulfate 2% by weight (10) Glycerin 3% by weight (1) to (6) are heated to 80 ° C. A mixed solution of (7) to (10), which had been heated to 80 ° C. in advance, was added to this and emulsified and dispersed to obtain an emulsion. This emulsion did not change its odor with time even after being left at 50 ° C for 30 days.

[0059]

The polyether-modified silicone compound used in the present invention comprises a polyoxyalkylene compound obtained by reacting an alkylene oxide with a long-chain primary alcohol having a double bond at the terminal and an organohydrogensiloxane. It is easily synthesized by an addition reaction and has no odor in the drug substance itself without a special treatment step, and also has no odor generated over time even when it is blended in an aqueous system. Therefore, a cosmetic which is useful for cosmetics and has no odor problem using this silicone compound was provided.

Claims (6)

[Claims] 1. A silicone compound represented by the general formula R ¹ _a R ² _b SiO _{(4-ab) / 2} [wherein R ¹ is the same or different carbon number 1
To 10 are an alkyl group, an aryl group, an aralkyl group or a fluorine-substituted alkyl group, R ² is represented by the general formula-(CH ₂ ) _k (CH = CH) _m (CH ₂ ) _n O (C _x H _2x O) _y the organic group represented by R ^3, R ³ is an alkyl group or an acyl group of a hydrogen atom or a C 1~20, a, b, k, m,
n, x and y are 1.0 ≦ a ≦ 2.5 and 0.005 ≦ b ≦, respectively.
1.2 and 1.7 ≦ a + b ≦ 2.7, k is an integer of 2 or more, m
Is 0 or 1, n is an integer of 1 or more, the sum of k + m + n is an integer of 6 or more, and x is 2 to 4 as an average value,
y is an average value of 3 to 200]. 2. The cosmetic according to claim 1, wherein m is 0 and the silicone compound having a total of k + n of 8 to 20 is blended. 3. m is 1, and the sum of k + m + n is 7 to
20. The silicone compound of 20 is blended.
Cosmetics described in. 4. The general formula R ¹ _a R ² _b SiO _{(4-ab) / 2} (wherein R ¹ , R 2
² , a and b are the same as those mentioned above) and used as a starting material thereof in the general formula CH ₂ = CH (CH ₂ ) _k-2 (CH = CH) _m (CH ₂ ) _n OH (wherein Cosmetics prepared by blending a silicone compound substantially free of unreacted alcohol, represented by k, m, and n). 5. The cosmetic according to claim 4, wherein a silicone compound substantially free of an unreacted product of the alcohol in which m is 0 and the sum of k + n is 8 to 20 is blended. 6. m is 1 and the total of k + m + n is 7 to
The cosmetic according to claim 4, which comprises a silicone compound which is substantially free of unreacted alcohol of 20.