JP7239885B2 - Alkenyl Group-Containing Polyoxyalkylene Derivatives, Silicone Modifiers, Polyoxyalkylene-Modified Silicones, and Cosmetic Oil Modifiers - Google Patents

Description

TECHNICAL FIELD The present invention relates to an alkenyl group-containing polyoxyalkylene derivative having an alkenyl group in the polyoxyalkylene structure. Further, it relates to a silicone modifier comprising an alkenyl group-containing polyoxyalkylene derivative, relates to a polyoxyalkylene-modified silicone obtained by the reaction of the silicone modifier and a hydrogen organopolysiloxane, and relates to a cosmetic oil modifier comprising the polyoxyalkylene-modified silicone. Regarding agents.

Alkenyl group-containing polyoxyalkylene derivatives use alkali catalysts, phosphazene compounds and double metal cyanide complex (DMC) catalysts, and alkylene oxides such as ethylene oxide and propylene oxide are added to initiators with active hydrogen such as allyl alcohol. By ring-opening addition, it is possible to synthesize low-molecular-weight products to high-molecular-weight products. It has an alkenyl group, which is a reactive group, and a polyoxyalkylene structure that allows a wide range of adjustment of hydrophilicity/hydrophobicity. Silicone modifiers, polymerization monomers, and reaction agents are used to adjust the hydrophilicity/hydrophobicity of products by reacting them with other substances. used as an emulsifying agent (Patent Documents 1 and 2).

Among them, silicone modifiers are used to synthesize polyoxyalkylene-modified silicones, which are compounds that react with hydrogen organopolysiloxane and have dimethylpolysiloxane as a basic skeleton, with polyoxyalkylene structures introduced into some of the methyl groups. be. Polyoxyalkylene-modified silicones are used as surfactants, urethane foam stabilizers, defoamers, leveling agents, etc. In urethane foam stabilizer applications, they are synthesized using a DMC catalyst and have a narrow molecular weight distribution. Alkenyl group-containing polyoxyalkylene derivatives have been proposed as silicone modifiers (Patent Document 3). It has been proposed (Patent Document 4).

By the way, vegetable oils represented by olive oil, grape seed oil, and macadamia nut oil have various cosmetic effects including moisturizing effect, and give an oily film feeling when blended with the skin, giving a moderately heavy and good feeling of use. Therefore, it is sometimes used in undiluted or highly formulated form in skin care oils and massage oils. Especially for massage oil, a large amount of oil is used compared to skin care, and since it is applied to the sides of the body, there is a demand for an oil with excellent handling properties that does not cause dripping. has been devised.
On the other hand, massage at beauty salons is performed in a warm environment, so the surface of the skin is often wet with sweat. In this case, since the massage oil made of vegetable oil contains a small amount of water, there are problems such as a sudden decrease in viscosity and insufficient thixotropy, resulting in problems such as dripping. there was a case. Furthermore, when the massage oil is spread on the skin and then applied to the skin, the oil feels light and watery, and the oil film cannot be felt.

Japanese Patent Laid-Open No. 1-101333 Japanese Patent Laid-Open No. 05-306152 JP-A-5-117352 JP 2004-181415 A

The object of the present invention is to prevent dripping even when the skin surface contains a small amount of water and to spread it on the side of the body during massage when the skin surface is moist. To prepare a massage oil containing a vegetable oil as a main component and capable of maintaining a good feeling of use when it is applied.

In view of the above problems, the present inventors have extensively studied, and as a result, the polyoxyalkylene-modified silicone obtained by reacting an alkenyl group-containing polyoxyalkylene derivative having a specific bias in molecular weight distribution with hydrogen polysiloxane is the above-mentioned. We have found that the problem can be solved and arrived at the present invention.

（式（３）中、
ｄは１～２００、ｅは０～１００であり、ｅ／ｄは０～１であり、
Ｒ^３は、炭素数１～８の炭化水素基であり、
Ｒ^４およびＲ^５は、それぞれ独立して、水素原子または炭素数１～８の炭化水素基であり、ｅ＝０のときにはＲ^４とＲ^５との少なくとも一方は水素原子である。）

（４） （３）のポリオキシアルキレン変性シリコーンからなることを特徴とする、化粧料オイル改質剤。 That is, the present invention is as follows.
(1) An alkenyl group -containing polyoxyalkylene derivative in which _MH and _ML , which are represented by formula (1) and are calculated from a chromatogram obtained by gel permeation chromatography, satisfy the relationship of formula (2). hand,
In the presence of a composite metal cyanide catalyst, the alkenyl group-containing polyoxyalkylene derivative has a water content of 0.5 wt% or less with respect to an initiator having an alkenyl group having 2 to 8 carbon atoms and one hydroxyl group. An alkylene oxide having 3 to 4 carbon atoms in an amount of 0.01 wt% or less is subjected to ring-opening addition polymerization at 50 ° C. to 150 ° C.,
V ₁ is the supply rate during the supply of 5 to 20 wt% of the total supply amount of the alkylene oxide, V ₂ is the supply rate during the supply of 20 to 50 wt% of the total supply amount of the alkylene oxide, V ₁ /V ₂ = 1.1 to 2.0, V ₂ /V ₃ = 1.1 to 1.5, where V ₃ is the supply rate while supplying 50 to 100 wt% of the total supply amount. An alkenyl group-containing polyoxyalkylene derivative characterized by:

R ¹ O—(AO ¹ ) _a —[(AO ² ) _b /(EO) _c ]—R ² (1)

(In formula (1),
R ¹ represents an alkenyl group having 2 to 8 carbon atoms,
AO ¹ and AO ² represent an oxyalkylene group having 3 to 4 carbon atoms,
EO represents an oxyethylene group,
The average added mole number a of AO ¹ satisfies a>0,
The average added mole number b of AO ² and the average added mole number c of EO satisfy b ≥ 0 and c ≥ 0,
the sum of a, b and c is 10 to 100;
When the average added mole number b of AO ² and the average added mole number c of EO are greater than 0, (AO ² ) _b /(EO) _c is the oxyalkylene group having 3 to 4 carbon atoms AO ² and the oxyethylene indicating that the group EO is randomly added,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

0.20≦ _ML / _MH ≦0.60 (2)

(In formula (2), the length of the perpendicular from the maximum point K on the chromatogram to the baseline B is L, and the refractive index intensity is L / 20 on the chromatogram. Of the points, the earlier elution time is point O, the later elution time is point Q, and the intersection of a straight line G connecting point O and point Q and a perpendicular line drawn from the maximum point K to the baseline B is the point. P, the distance between point O and intersection P is _MH , and the distance between point Q and intersection P is _ML .)

(2) A silicone modifier comprising the alkenyl group-containing polyoxyalkylene derivative of (1).

(3) A polyoxyalkylene-modified silicone comprising a reaction product of the silicone modifier of (2) and the hydrogen organopolysiloxane represented by formula (3).

(In formula (3),
d is 1 to 200, e is 0 to 100, e/d is 0 to 1,
R ³ is a hydrocarbon group having 1 to 8 carbon atoms,
R ⁴ and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and when e=0, at least one of R ⁴ and R ⁵ is a hydrogen atom. )

(4) A cosmetic oil modifier comprising the polyoxyalkylene-modified silicone of (3).

By producing a polyoxyalkylene-modified silicone using the alkenyl group-containing polyoxyalkylene derivative according to the present invention, the massage oil containing the polyoxyalkylene-modified silicone as an oil modifier and containing vegetable oil as the main component is Even when the skin surface is wet, it does not easily drip and is easy to handle.
The polyoxyalkylene-modified silicones are suitable for use not only as cosmetic oil modifiers, but also as coating additives, plastic additives, and textile oils.

FIG. 1 is a model chromatogram diagram for explaining _ML and _MH defined in the present invention.

(silicone modifier)
The silicone modifier according to the present invention comprises a polyoxyalkylene compound represented by the following formula (1).

R ¹ O—(AO ¹ ) _a —[(AO ² ) _b /(EO) _c ]—R ² (1)

In formula (1), a (a>0) represents the average number of added moles of the oxyalkylene group AO ¹ having 3 to 4 carbon atoms, and b (b≧0) represents an oxyalkylene group having 3 to 4 carbon atoms. Indicates the average number of added moles of AO ² , and c (c≧0) indicates the average number of added moles of oxyethylene group EO.

The sum of a, b, and c is set to 10 or more, more preferably 15 or more, from the viewpoint of the oil reforming effect (good feeling in use and suppression of dripping when a small amount of water is contained). In addition, if the sum of a, b and c exceeds 100, the viscosity increases and adversely affects the production of the polyoxyalkylene-modified silicone. is particularly preferred.

In formula (1), R ¹ is an alkenyl group having 2 to 8 carbon atoms. From the viewpoint of ease of production of the silicone modifier and reactivity with silicone, R ¹ preferably has 2 to 5 carbon atoms, and particularly preferably an allyl group or a methallyl group.

In formula (1), R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and is preferably a hydrogen atom from the viewpoint of ease of production of the alkenyl group-containing polyoxyalkylene derivative.

The alkenyl group-containing polyoxyalkylene derivative of the present invention is defined by a chromatogram obtained using a differential refractometer in gel permeation chromatography (GPC). This chromatogram is a graph showing the relationship between refractive index intensity and elution time. The silicone modifier of the present invention has a left-right asymmetric chromatogram and satisfies the relationship of formula (2). Note that the closer to 1 the value of M _L /M _H is, the more symmetrical the shape of the chromatogram is.

0.20≦ _ML / _MH ≦0.60 (2)

Here, FIG. 1 is a model diagram of a chromatogram obtained by gel permeation chromatography of an alkenyl group-containing polyoxyalkylene derivative, the horizontal axis is the elution time, and the vertical axis is obtained using a differential refractometer. Shows refractive index intensity.

When the sample solution is injected into the gel permeation chromatograph and developed, elution starts from the molecules with the highest molecular weight, and the elution curve rises as the refractive index intensity increases. After that, after passing the maximum point K where the refractive index intensity is maximum, the elution curve descends.

Further, in the gel permeation chromatography of the alkenyl group-containing polyoxyalkylene derivative of the present invention, if there are a plurality of maximum points of refractive index intensity in the chromatogram, the point with the highest refractive index intensity among them is defined as the maximum point K. . Furthermore, when there are a plurality of maximum points of the same refractive index intensity, the maximum point K of the refractive index intensity is the one with the later elution time. At this time, peaks due to the developing solvent used in gel permeation chromatography, etc., and pseudo peaks due to baseline fluctuations due to the column and apparatus used are excluded.

M _L /M _H is calculated from the chromatogram as follows.
(1) Draw a perpendicular line from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and let L be the length of the perpendicular line.
(2) Of the two points on the chromatogram where the refractive index intensity is L/20, point O is the earlier elution time, and point Q is the later elution time.
(3) Let P be the intersection of a straight line G connecting the points O and Q and a perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) Let the distance between the point O and the intersection point P be M _H , and the distance between the intersection point P and the point Q be M _L .

The alkenyl group-containing polyoxyalkylene derivative of the present invention satisfies M _L /M _H of 0.20≦M _L /M _H ≦0.60. When _ML / _MH is more than 0.60, the distribution of the polyoxyalkylene chain structure of the polyoxyalkylene-modified silicone becomes small, and the oil modification effect is not exhibited. From this point of view, M _L /M _H is 0.60 or less, and more preferably 0.50 or less.

In addition, the smaller the M _L /M _H ratio, the greater the bias toward the high molecular weight side in the molecular weight distribution, which leads to an increase in viscosity and the like. If M _L /M _H is less than 0.20, the viscosity becomes too high, which adversely affects the production of silicone modifiers and polyoxyalkylene-modified silicones, which is undesirable. From this point of view, M _L /M _H is set to 0.20 or more, and more preferably 0.30 or more.

In the present invention, gel permeation chromatography (GPC) for determining _ML and _MH was performed using SHODEX (registered trademark) as a system.
GPC101 GPC dedicated system, SHODEX RI-71s as a differential refractometer, SHODEX KF-G as a guard column, and HODEX KF804L as a column are continuously mounted, the column temperature is 40 ° C, and tetrahydrofuran is flowed at a flow rate of 1 ml / min as a developing solvent. , 0.1 ml of a 0.1% by weight tetrahydrofuran solution of the resulting reactant is injected, and a chromatogram represented by refractive index intensity and elution time is obtained using the BORWIN GPC calculation program.

The alkenyl group-containing polyoxyalkylene derivative of the present invention is obtained by ring-opening addition of an alkylene oxide having 3 to 4 carbon atoms in the presence of a double metal cyanide catalyst (hereinafter abbreviated as a DMC catalyst), or It is produced by further ring-opening addition of 3 to 4 alkylene oxides and ethylene oxide.

In the production of the alkenyl group-containing polyoxyalkylene derivative, preferably, an initiator having an alkenyl group having 2 to 8 carbon atoms in the molecule and one hydroxyl group and a DMC catalyst are added to a reaction vessel, and an inert gas atmosphere is added. With stirring, an alkylene oxide having 3 to 4 carbon atoms is continuously or intermittently added for addition polymerization. The alkylene oxide having 3 to 4 carbon atoms may be added under pressure or under atmospheric pressure. The same applies to the subsequent addition polymerization of alkylene oxide having 3 to 4 carbon atoms and ethylene oxide.

At this time, the average supply rate of propylene oxide is not limited, but it is desirable to change it according to the amount of alkylene oxide charged. Specifically, V ₁ is the speed (supply amount per unit time) during which 5 to 20 wt% of the total amount of alkylene oxide is supplied, and the speed during which 20 to 50 wt% of the total amount of alkylene oxide is supplied. is V ₂ and V ₃ is the rate during which 50 to 100 wt % of the total amount of alkylene oxide is supplied, V ₁ /V ₂ =1.1 to 2.0, V ₂ /V ₃ =1. It is preferable to control the average feed rate of the alkylene oxide so as to be 1 to 1.5.

The reaction temperature is preferably 50°C to 150°C, more preferably 80°C to 120°C. If the reaction temperature is higher than 150°C, the catalyst may be deactivated. If the reaction temperature is lower than 50°C, the reaction rate will be slow and the productivity will be poor.

Although there are no particular restrictions on the trace amount of water contained in the initiator and the alkylene oxide, it is desirable that the amount of water contained in the initiator is 0.5 wt% or less, and that of the alkylene oxide is 0.01 wt% or less. .

The amount of the DMC catalyst used is not particularly limited, but is preferably 0.0001 to 0.1 wt%, more preferably 0.001 to 0.05 wt%, relative to the silicone modifier to be produced. The DMC catalyst may be introduced all at once into the reaction system, or may be successively introduced in divided portions. After completion of the polymerization reaction, the composite metal complex catalyst is removed. Removal of the catalyst can be carried out by known methods such as filtration, centrifugation, and treatment with a synthetic adsorbent.

A known DMC catalyst can be used in the present invention, and for example, it can be represented by formula (4).

Mf[M'x(CN)y]g( _H2O )h.( ^R6 )i
... (4)

In formula (4), M and M' are metals, ^R6 is an organic ligand, f, g, x and y are positive integers that vary depending on the valence and coordination number of the metal, and h and i are It is a positive integer that varies depending on the coordination number of the metal.

Metals M include Zn(II), Fe(II), Fe(III), Co(II), Ni(II), Al(III), Sr(II), Mn(II), Cr(III), Cu(II), Sn(II), Pb(II), Mo(IV), Mo(VI), W(IV), W(VI), etc., among which Zn(II) is preferably used.

Metal M′ includes Fe(II), Fe(III), Co(II), Co(III), Cr(II), Cr(III), Mn(II), Mn(III), Ni(II) , V(IV), V(V), etc. Among them, Fe(II), Fe(III), Co(II), and Co(III) are preferably used.

As the organic ligand ^R6 , alcohols, ethers, ketones, esters, etc. can be used, and alcohols are more preferable. Preferred organic ligands are water-soluble, and specific examples include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N,N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether ( diglyme) and the like. Zn ₃ [Co(CN) ₆ ] ₂ coordinated with tert-butyl alcohol is particularly preferred.

An alkenyl group-containing polyoxyalkylene derivative produced using a DMC catalyst has an alkyl group having 1 to 4 carbon atoms at the end represented by formula (1) by Williamson etherification reaction with an organic halide in the presence of a base. It can be used for the production of silicone modifiers with Specific examples of the base used in the etherification reaction include sodium hydroxide, potassium hydroxide, sodium hydride, potassium carbonate and the like. The organic halide is a compound in which an alkyl group having 1 to 4 carbon atoms and a halogen atom are bonded. Specific examples include methyl chloride and butyl chloride.

Further, in the production of alkenyl group-containing polyoxyalkylene derivatives, an initiator having an alkyl group having 1 to 4 carbon atoms and one hydroxyl group in the molecule and a DMC catalyst may be used to conduct addition polymerization of alkylene oxide. In that case, after the addition polymerization of the alkylene oxide, in the presence of a base, by Williamson etherification reaction with a compound in which an alkenyl group having 3 to 5 carbon atoms and a halogen atom are bonded, the terminal represented by the formula (1) has 1 to 1 carbon atoms. Silicone modifiers with 4 alkyl groups can be prepared. Specific examples of organic halides include allyl chloride, allyl iodide, methallyl chloride, and allyl bromide.

(polyoxyalkylene-modified silicone)
The polyoxyalkylene-modified silicone of the present invention comprises a reactant of a silicone modifier represented by formula (1) and a hydrogen organopolysiloxane represented by formula (3).

(hydrogen organopolysiloxane)
In formula (3), d is 1-200 and e is 0-100. d is set to 200 or less, preferably 150 or less, more preferably 100 or less, from the viewpoint of viscosity of the modified silicone and ease of mixing with vegetable oil. Also, d is set to 1 or more, but 2 or more is more preferable. From the viewpoint of the viscosity of the modified silicone and the effect of modifying the oil, e is set to 100 or less, preferably 50 or less, more preferably 20 or less, and particularly preferably 10 or less. From the viewpoint of the oil reforming effect, e/d is set to 1 or less, preferably 0.4 or less, more preferably 0.2 or less, and may be 0.0.

R ³ represents a hydrocarbon group having 1 to 8 carbon atoms. Examples of such hydrocarbon groups include alkyl groups, cycloalkyl groups and alkenyl groups, with alkyl groups being preferred. Specific compound names include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group and the like, and methyl group is particularly preferred.

R ⁴ and R ⁵ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms. Examples of such hydrocarbon groups include alkyl groups, cycloalkyl groups and alkenyl groups, with alkyl groups being preferred. Specific compound names include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, octyl group and the like, preferably methyl group. When e=0, at least one of ^R4 or ^R5 is a hydrogen atom.

(Vegetable oil)
Vegetable oils that are liquid at 25° C. that can be used in the present invention include olive oil, grape seed oil, macadamia nut oil, avocado oil, apricot kernel oil, almond oil, argan oil, castor oil, jojoba oil, camellia oil, sunflower oil, sunflower oil and the like.

EXAMPLES The present invention will be described in detail below with reference to Examples, but the technical scope of the present invention is not limited to these. In addition, the analysis of the synthetic product was performed by the method shown below.

(analysis method)
Degree of unsaturation: Analyzed according to JIS K 1557-3.
Kinematic Viscosity: Analyzed according to JIS K 2283.
Gel permeation chromatography:
SHODEX GPC101 GPC dedicated system as a system, SHODEX as a differential refractometer
RI-71S, SHODEX KF-GS as a guard column, and three HODEX KF804L columns are continuously mounted, the column temperature is 40 ° C., tetrahydrofuran is flowed as a developing solvent at a flow rate of 1 ml / min, and the reaction product obtained is 0.1. Analysis was carried out by injecting 0.1 ml of wt % tetrahydrofuran solution and obtaining a chromatogram represented by refractive index intensity and elution time using the BORWIN GPC calculation program.

(Synthesis Example 1: Synthesis of double metal cyanide complex (DMC) catalyst)
Into 2.0 ml of aqueous solution containing 2.1 g of zinc chloride, 15 ml of aqueous solution containing 0.84 g of potassium hexacyanocobaltate K ₃ Co(CN) ₆ was dropped at 40° C. over 15 minutes while stirring. After completion of dropping, 16 ml of water and 16 g of tert-butyl alcohol were added, the temperature was raised to 70° C., and the mixture was stirred for 1 hour. After cooling to room temperature, a filtration operation (first filtration) was performed to obtain a solid. 14 ml of water and 8.0 g of tert-butyl alcohol were added to this solid, and the mixture was stirred for 30 minutes and filtered (second filtration) to obtain a solid.

Again, 18.6 g of tert-butyl alcohol and 1.2 g of methanol were added to this solid, and after stirring for 30 minutes, a filtration operation (third filtration) was performed, and the obtained solid was dried at 40° C. under reduced pressure for 3 hours. to obtain 0.7 g of DMC catalyst.

(Synthesis Example 2: Synthesis of Silicone Modifier Z-1)
700 g of allyl alcohol (manufactured by Showa Denko) and 7 g of sodium methylate (manufactured by Nippon Soda) were charged into a 5-liter autoclave equipped with a stirrer, a nitrogen inlet tube, and a thermocouple. After purging with nitrogen, the temperature was raised to 100° C., and 2,150 g of propylene oxide (manufactured by Sumitomo Chemical) was charged over 20 hours under conditions of 0.5 MPa or less. Remaining propylene oxide was removed by vacuum treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, moisture was removed under nitrogen bubbling at 80°C, and after adding 14 g each of Kyoward #300 and #700 (manufactured by Kyowa Chemical Industry Co., Ltd.), 80°C, -0.097 MPa (gauge pressure) Then, adsorption treatment was carried out for 1 hour under nitrogen bubbling, and 2,360 g of tripropylene glycol allyl ether (degree of unsaturation: 4.11 meq/g, Mn: 240) was obtained by filtration.

Subsequently, 400 g of tripropylene glycol allyl ether and 0.05 g of the DMC catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, a nitrogen inlet tube, and a thermocouple. After purging with nitrogen, the temperature was raised to 120° C., and 50 g of propylene oxide was charged over 1 hour under conditions of 0.3 MPa or less. At this time, changes over time in pressure and temperature in the reactor were measured. After 5 hours, the pressure in the reactor dropped sharply. Thereafter, while maintaining the inside of the reaction vessel at 120° C., propylene oxide was gradually introduced under the condition of 0.6 MPa or less, and the total amount of 2,050 g of propylene oxide was continuously added under pressure while stirring. At this time, it took 10 hours to introduce 2,050 g of propylene oxide. After pressure reduction treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour, filtration was carried out to obtain 2,400 g of silicone modifier Z-1. The degree of unsaturation of the resulting modifier was 0.65 meq/g and Mn: 1,440.
Also, when M _L /M _H was calculated from the chromatogram obtained by gel permeation chromatography, it was 0.42.

(Synthesis Example 3: Synthesis of Silicone Modifier Z-2)
A 5-liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple was charged with 700 g of methallyl alcohol (Zibo Chemical) and 7 g of sodium methylate. After purging with nitrogen, the temperature was raised to 100° C., and 1,700 g of propylene oxide was charged over 20 hours under conditions of 0.5 MPa or less. Remaining propylene oxide was removed by vacuum treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, moisture was removed by nitrogen bubbling at 80°C, and after adding 12 g each of Kyoward #300 and #700, 80°C, −0.097 MPa (gauge pressure) or less, nitrogen bubbling. Adsorption treatment was carried out for 1 hour in the atmosphere, and 1,990 g of tripropylene glycol methallyl ether (degree of unsaturation: 4.02 meq/g, Mn: 360) was obtained by filtration.

Subsequently, 400 g of tripropylene glycol methallyl ether and 0.05 g of the DMC catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, a nitrogen inlet tube, and a thermocouple. After purging with nitrogen, the temperature was raised to 120° C., and 50 g of propylene oxide was charged over 1 hour under conditions of 0.3 MPa or less. At this time, changes over time in pressure and temperature in the reactor were measured. After 5 hours, the pressure in the reactor dropped sharply. Then, while maintaining the inside of the reaction tank at 120° C., propylene oxide was gradually introduced under conditions of 0.6 MPa or less, and the total amount of 1,950 g of propylene oxide was continuously added under pressure while stirring. At this time, it took 10 hours to introduce 1,950 g of propylene oxide. After pressure reduction treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour, filtration was carried out to obtain 2,300 g of silicone modifier Z-2. The degree of unsaturation of the resulting modifier was 0.64 meq/g and Mn: 1,480.
Also, when M _L /M _H was determined from the chromatogram obtained by gel permeation chromatography, it was 0.44.

(Synthesis Example 4: Synthesis of Silicone Modifier Z-3)
400 g of tripropylene glycol allyl ether and 0.05 g of the double metal cyanide complex catalyst obtained in Synthesis Example 1 were charged into a 5-liter autoclave equipped with a stirrer, a nitrogen inlet tube, and a thermocouple. After purging with nitrogen, the temperature was raised to 120° C., and 50 g of propylene oxide was charged over 1 hour under conditions of 0.3 MPa or less. At this time, changes over time in pressure and temperature in the reactor were measured. After 5 hours, the pressure in the reactor dropped sharply. After that, while maintaining the inside of the reactor at 120° C., 1,650 g of propylene oxide and 1,500 g of ethylene oxide were gradually added under conditions of 0.6 MPa or less, and continuously added under pressure over 13 hours while stirring. bottom. After pressure reduction treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour, filtration was carried out to obtain 3,480 g of silicone modifier Z-3. The degree of unsaturation of the resulting modifier was 0.44 meq/g and Mn: 2,080.
Also, when M _L /M _H was calculated from the chromatogram obtained by gel permeation chromatography, it was 0.38.

(Synthesis Example 5: Synthesis of Silicone Modifier Z'-1)
A 5 liter autoclave equipped with a stirrer, nitrogen inlet tube, and thermocouple was charged with 100 g of allyl alcohol and 5 g of sodium methylate. After purging with nitrogen, the temperature was raised to 100° C., and 3,300 g of propylene oxide was charged over 50 hours under conditions of 0.5 MPa or less. Remaining propylene oxide was removed by vacuum treatment at 75 to 85° C. and −0.097 MPa (gauge pressure) for 1 hour. After neutralization with hydrochloric acid, moisture was removed under nitrogen bubbling at 80°C, and after adding 3.3 g each of Kyoward #300 and #700, the temperature was reduced to -0.097 MPa (gauge pressure) or less at 80°C. Adsorption treatment was performed for 1 hour under nitrogen bubbling, and 3,150 g of silicone modifier Z'-1 (unsaturation: 0.64 meq/g, Mn: 1,460) was obtained by filtration.
Further, _ML / _MH was 1.15 when calculated from the chromatogram obtained by gel permeation chromatography.

(Synthesis Example 6: Synthesis of polyether-modified silicone A-1)
Hydrogendimethylpolysiloxane (HMS-082 (manufactured by Gelest), SiH equivalent per gram = 1.08 meq/g was added to a 300-ml four-necked flask equipped with a stirrer, a nitrogen blowing tube, a thermocouple and a condenser tube. , d = 75, e = 6.5) 65 parts by mass and the silicone modifier Z-1 (151 parts by mass, unsaturated equivalent: 0.65 meq/g) synthesized in Synthesis Example 2 were charged, and platinum chloride was used as a catalyst. A solution of acid hexahydrate in isopropyl alcohol (1×10 ⁻³ mol/liter) was charged so as to give 50 ppm in terms of platinum, and the reaction was carried out at 90° C. while stirring in a nitrogen atmosphere. Sampling was performed, and an isopropyl alcohol solution of N/10 potassium hydroxide was added to continue the reaction until hydrogen gas was no ^longer generated. This was confirmed, and polyether-modified silicone A-1 of Example 1 having a kinematic viscosity of 105 Pa·s at 100°C was obtained.

(Synthesis Example 7: Synthesis of polyether-modified silicone A-2)
The procedure was carried out in the same manner as in Synthesis Example 6, except that the silicone modifier Z-2 (132 parts by mass, unsaturated equivalent: 0.64 meq/g) synthesized in Synthesis Example 3 was used instead of the silicone modifier Z-1. to obtain polyether-modified silicone A-2 of Example 2 having a kinematic viscosity of 110 Pa·s at 100°C.

(Synthesis Example 8: Synthesis of polyether-modified silicone A-3)
The procedure was carried out in the same manner as in Synthesis Example 6, except that the silicone modifier Z-3 (223 parts by mass, unsaturated equivalent: 0.44 meq/g) synthesized in Synthesis Example 4 was used instead of the silicone modifier Z-1. to obtain a polyether-modified silicone A-3 of Example 3 having a kinematic viscosity of 301 Pa·s at 100°C.

(Synthesis Example 9: Synthesis of polyether-modified silicone A'-1)
In the same manner as in Synthesis Example 6, except that the silicone modifier Z′-1 (154 parts by mass, unsaturated equivalent: 0.64 meq/g) synthesized in Synthesis Example 5 was used instead of the silicone modifier Z-1. A polyether-modified silicone A'-1 of Comparative Example 1 having a kinematic viscosity of 102 Pa·s at 100° C. was obtained.

(Preparation of Oil Agent Base: Examples 1-3, Comparative Examples 1-3)
Massage oils shown in Table 3 were prepared by the following preparation method.
Specifically, under room temperature conditions, various modified silicones of Examples and Comparative Examples and olive oil (manufactured by Kanto Kagaku Co., Ltd.) were stirred until uniform.

(Evaluation of dripping)
Using a dynamic viscoelasticity device (Paar Physica MCR-300, manufactured by Anton Paar), the shear viscosity at a temperature of 20 ° C. and a shear rate of 0.1 and 1.0 (1 / s) was measured, and the shear rate Based on the value of the ratio, the difficulty of dripping when spreading the massage oil was evaluated based on the following criteria. For the evaluation, the massage oil added with 1 wt % of the water used for the sensory evaluation was used. A blank test was performed once in order to allow the evaluation sample to adapt to the instrument, and the main test was performed 1 minute after the end of the test.

Judgment criteria “◎”: Ratio of 1.4 or more “○”: Ratio of 1.3 or more and less than 1.4 “△”: Ratio of 1.1 or more and less than 1.3 “×”: Ratio of 1.4 or more less than 1

(Sensory evaluation of massage oil)
After washing with bar soap and rinsing with running water, both hands were thoroughly dried using a hair dryer. After about 0.2 mL of the evaluation sample was dropped on the back of the left hand, the feeling was evaluated when the sample was spread over the entire back of the hand with the pads of the fingers of the right hand. Assuming that the massage oil was used when the skin surface was wet, 1 wt% of water was added to each massage oil and mixed uniformly, and the massage oil was applied. After spreading, the feeling of use when blended with the skin was evaluated according to the following evaluation criteria, and the sum of the scores was evaluated in the following 4 grades from "A" to "X".

Evaluation criteria 2 points: Feeling of oil film and moderately heavy feeling of use 1 point: Feeling of oil film but slightly light feeling of use 0 point: Light feeling of use without feeling of oil film

Judgment criteria “◎”: Total score is 18 points or more “○”: Total score is 15 points or more and 17 points or less “△”: Total score is 10 points or more and 14 points or less “×”: Total score is 9 points or less

Regarding the sensory evaluation of the massage oil, when comparing Examples 1 to 3 with Comparative Examples 1 to 3, Examples 1 to 3 do not drip when spread and have an oily film feeling when blended on the skin. It was moderately heavy and had excellent usability. In Comparative Examples 1 to 3, dripping occurred when spreading, and a sufficient oil film was not obtained when blended on the skin, and a good feeling of use was not obtained.

Claims (4)

An alkenyl group-containing polyoxyalkylene derivative represented by formula (1), wherein _MH and _ML calculated from a chromatogram obtained by gel permeation chromatography satisfy the relationship of formula (2) ,
In the presence of a composite metal cyanide catalyst, the alkenyl group-containing polyoxyalkylene derivative has a water content of 0.5 wt% or less with respect to an initiator having an alkenyl group having 2 to 8 carbon atoms and one hydroxyl group. An alkylene oxide having 3 to 4 carbon atoms in an amount of 0.01 wt% or less is subjected to ring-opening addition polymerization at 50 ° C. to 150 ° C.,
V ₁ is the supply rate during the supply of 5 to 20 wt% of the total supply amount of the alkylene oxide, V ₂ is the supply rate during the supply of 20 to 50 wt% of the total supply amount of the alkylene oxide, V ₁ /V ₂ = 1.1 to 2.0, V ₂ /V ₃ = 1.1 to 1.5, where V ₃ is the supply rate while supplying 50 to 100 wt% of the total supply amount. An alkenyl group-containing polyoxyalkylene derivative characterized by:

R ¹ O—(AO ¹ ) _a —[(AO ² ) _b /(EO) _c ]—R ² (1)

(In formula (1),
R ¹ represents an alkenyl group having 2 to 8 carbon atoms,
AO ¹ and AO ² represent an oxyalkylene group having 3 to 4 carbon atoms,
EO represents an oxyethylene group,
The average added mole number a of AO ¹ satisfies a>0,
The average added mole number b of AO ² and the average added mole number c of EO satisfy b ≥ 0 and c ≥ 0,
the sum of a, b and c is 10 to 100;
When the average added mole number b of AO ² and the average added mole number c of EO are greater than 0, (AO ² ) _b /(EO) _c is the oxyalkylene group having 3 to 4 carbon atoms AO ² and the oxyethylene indicating that the group EO is randomly added,
R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. )

0.20≦ _ML / _MH ≦0.60 (2)

(In formula (2), the length of the perpendicular from the maximum point K on the chromatogram to the baseline B is L, and the refractive index intensity is L / 20 on the chromatogram. Of the points, the earlier elution time is point O, the later elution time is point Q, and the intersection of a straight line G connecting point O and point Q and a perpendicular line drawn from the maximum point K to the baseline B is the point. P, the distance between point O and intersection P is _MH , and the distance between point Q and intersection P is _ML .)
A silicone modifier comprising the alkenyl group-containing polyoxyalkylene derivative according to claim 1 .
3. A polyoxyalkylene-modified silicone comprising a reaction product of the silicone modifier according to claim 2 and a hydrogen organopolysiloxane represented by formula (3).

(In formula (3),
d is 1 to 200, e is 0 to 100, e/d is 0 to 1,
R ³ is a hydrocarbon group having 1 to 8 carbon atoms,
R ⁴ and R ⁵ are each independently a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and when e=0, at least one of R ⁴ and R ⁵ is a hydrogen atom. )
A cosmetic oil modifier comprising the polyoxyalkylene-modified silicone according to claim 3 .

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