JP6925580B2 - Hair cosmetics - Google Patents

Description

The present invention relates to a novel alkyloxylan derivative that can be effectively used in hair cosmetics and the like.

Generally, an alkyloxylan derivative is synthesized by anionic polymerization using an alkali metal hydroxide such as potassium hydroxide and ring-opening addition of alkyloxylans such as oxylan, methyloxylan and ethyloxylan to an initiator having active hydrogen such as alcohol. Will be done. In particular, when methyloxylan is used in this anionic polymerization to synthesize a methyloxylan derivative, unsaturated monool is produced as a by-product, and the amount produced increases as the molecular weight of the methyloxylan derivative increases. Therefore, there is a problem that the increase in the molecular weight of the methyloxylan derivative is hindered and the proportion of low molecular weight bodies increases in the molecular weight distribution.

In order to solve this problem, compounds having a P = N bond such as phosphazene compounds, complex metal cyanide complex catalysts and the like are used. By using these catalysts, the formation of unsaturated monool can be suppressed and a high molecular weight methyloxylane derivative can be synthesized. Among these catalysts, the composite metal cyanide complex catalyst has higher catalytic activity than the former catalyst and is a useful polymerization catalyst for the production of methyloxylane derivatives (Non-Patent Document 1).

It has also been reported that the high molecular weight methyloxylane derivative synthesized using this composite metal cyanide complex catalyst not only has a low unsaturated monool content but also has a narrow molecular weight distribution. It is said that a methyloxylan derivative having a narrower molecular weight distribution has a lower viscosity and is easier to handle, and is very useful as a raw material for polyurethane. A method for producing a methyloxylan derivative having a narrower molecular weight distribution has been reported (Patent Documents 1 and 1). A few).

However, there is a problem that the viscosity is not sufficient in applications such as lubricating oil. Further, most of the number of hydroxy groups (number of functional groups) in the molecule of these high molecular weight methyloxylan derivatives is bifunctional or more, and it is particularly difficult to synthesize a monofunctional high molecular weight methyloxylan derivative.

By the way, the alkyloxylan derivative is also used as a raw material for cosmetics. For example, Patent Document 4 describes a cosmetic for hair containing polyoxypropylene butyl ether, which is said to be easy to wash off during rinsing and to give a smooth finish to hair. However, when using such hair cosmetics, while rinsing with a large amount of water, the water loosens the hair and makes it easy for fingers to pass through, but after rinsing, when draining the hair, there is a squeak. There was a problem in that it occurred and that the hair remained stiff and sticky.

ACS Symposium Series, Vol. 6, pp 20-37 (1975)

Japanese Patent Application Laid-Open No. 10-007787 JP-A-2004-2697776 WO2011 / 034030 JP 2013-189423

An object of the present invention is that even a high molecular weight alkyloxylan derivative does not remain sticky or stiff when blended in hair cosmetics or the like, and further, after rinsing, it becomes slippery when draining water from the hair. It is to provide an excellent novel alkyloxylane derivative.

As a result of diligent studies in view of the above matters, the present inventors have obtained an alkyloxylan derivative in which the molecular weight pattern obtained by gel permeation chromatography measurement is asymmetrical and the molecular weight distribution is biased toward the high molecular weight side. Was found to be solved, for example, when it was added to a cosmetic for hair.

That is, the present invention is as follows.
[1] represented by Formula (1), and characterized in that it comprises an alkyl oxirane derivative that satisfies the relationship of M _H and M _L Togashiki calculated from the chromatogram obtained by the gel permeation chromatography measurement (2) Hair cosmetics .

Z- [O- (AO) n-H] x ... (1)

(In equation (1),
Z represents a residue having 1 to 22 carbon atoms and having 1 to 6 hydroxyl groups excluding all hydroxyl groups.
x represents a number from 1 to 6
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more. )

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(The elution time of the two points on the chromatogram where the length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L and the refractive index intensity is L / 2 When the earlier point is the point O, the slower elution time is the point Q, and the intersection of the straight line G connecting the points O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is P, the point O _{Let MH} be the distance between the point Q and the intersection P, and let _ML be the distance between the point Q and the intersection P.)

[ 2 ] The hair cosmetic according to [1], wherein the alkyloxylan derivative is represented by the following formula (5).

R ¹ O- (AO) n-H ... (5)

(In equation (5),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms.
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more. )

The alkyloxylan derivative exhibiting a specific molecular weight distribution according to the present invention, when blended in, for example, hair cosmetics, does not leave stickiness or stiffness, and is particularly excellent in slipperiness when draining water after rinsing.

FIG. 1 is a model chromatogram diagram for explaining _ML and _MH defined in the present invention. FIG. 2 is a model chromatogram diagram for explaining _{W 1/2} and W _5% as defined in the present invention. FIG. 3 is a chromatogram diagram of Synthesis Example 1. FIG. 4 is a chromatogram diagram of Comparative Synthesis Example 1.

The alkyloxylane derivative of the present invention is a compound represented by the formula (1).

Z- [O- (AO) n-H] x ... (1)

In the formula (1), Z represents a residue having 1 to 22 carbon atoms and having 1 to 6 hydroxyl groups excluding all hydroxyl groups, x represents a number of 1 to 6, and AO represents carbon. It is an oxyalkylene group of number 3. n is the average number of moles of oxyalkylene group AO added, which is 25 or more.

In the formula (1), Z is a residue obtained by removing all the hydroxyl groups (OH) from the compound Z (OH) x having 1 to 22 carbon atoms and having 1 to 6 hydroxyl groups. x is the number of hydroxyl groups of this compound. Z is a residue having 1 to 22 carbon atoms, preferably 1 to 14 carbon atoms, more preferably 1 to 6 carbon atoms, and having 1 to 6 hydroxyl groups minus all hydroxyl groups. x is the number of hydroxyl groups of the compound of Z, which is 1 to 6. Examples of the compound having 1 to 6 hydroxyl groups include methanol, ethanol and butanol when x = 1, ethylene glycol, propylene glycol and hexylene glycol when x = 2, and glycerin and tri when x = 3. Examples thereof include methylolpropane, erythritol, pentaerythritol, sorbitol, diglycerin, and alkylglycoside when x = 4, xylitol when x = 5, dipentaerythritol, sorbitol, and inositol when x = 6. Further, a mixture thereof may be used as the compound having 1 to 6 hydroxyl groups. x is preferably 1 to 3, and x = 1 is most preferable.

In formula (1), Z may be R ¹ O, and in this case x = 1. In this case, R ¹ is a hydrocarbon group having 1 to 22 carbon atoms.

Hydrocarbon group of 1 to 22 carbon atoms represented by R ¹ is a functional group composed of carbon and hydrogen, an alkyl group, an alkenyl group, a one selected from a cycloalkyl group, an aryl group or an aralkyl group, It is preferably an alkyl group or an alkenyl group, more preferably an alkyl group or an alkenyl group having 1 to 14 carbon atoms, further preferably an alkyl group or an alkenyl group having 1 to 6 carbon atoms, and most preferably an alkyl group having 1 to 6 carbon atoms. preferable. The alkyl group having 1 to 6 carbon atoms may be linear or branched, but a linear alkyl group is more preferable. Examples of the linear alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group. Hydrocarbon group of 1 to 22 carbon atoms represented by R ¹ in only one kind, or two or more kinds.

AO is an oxyalkylene group having 3 carbon atoms. Further, n is the average number of moles of oxyalkylene group AO added, which is 25 or more. When n is less than 25, the viscosity is low, and there is a possibility that the slipperiness when draining the water of the hair after rinsing when blended in the hair cosmetics is insufficient. From this point of view, n is 25 or more, but 50 or more is more preferable.

In addition, the viscosity increases as n increases. From the viewpoint of ease of blending in cosmetics, n is preferably 150 or less, and more preferably 120 or less.

The alkyloxylane 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 the refractive index intensity and the elution time. In the alkyloxylan derivative of the present invention, the chromatogram is asymmetrical and satisfies the relationship of the formula (2). The _{closer the ML} / _MH is to 1, the more symmetrical the shape of the chromatogram is.

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

Here, FIG. 1 is a model diagram of a chromatogram obtained by gel permeation chromatography of an alkyloxylan derivative, in which the horizontal axis represents the elution time and the vertical axis represents the refractive index intensity obtained by using a differential refractometer. show.

When the sample solution is injected into the gel permeation chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve increases as the refractive index intensity increases. After that, when the maximum point K at which the refractive index intensity becomes maximum is passed, the elution curve descends.

Further, in the gel permeation chromatography of the alkyloxylan derivative of the present invention, when there are a plurality of maximum points of the refractive index intensity of the chromatogram, the point having the highest refractive index intensity is defined as the maximum point K. Further, when there are a plurality of maximum points having the same refractive index intensity, the one with the slower elution time is designated as the maximum point K of the refractive index intensity. At this time, peaks caused by the developing solvent used for gel permeation chromatography and pseudo peaks caused by baseline fluctuations caused by the columns and devices used are excluded.

M _L / M _H, respectively, calculated from the chromatogram in the following manner.
(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and the length of the perpendicular line is L.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 2, the one with the earlier elution time is designated as point O, and the one with the slower elution time is designated as point Q.
(3) Let P be the intersection of the straight line G connecting the points O and Q and the perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) point O and the intersection point P distance _{M H} of the distance of an intersection P and the point Q and _{M L.}

Alkyl oxiranes of the present invention _is M L / _{M H} satisfies _{0.35 ≦ M L / M H ≦} 0.75. When M _L / M _H is greater than 0.75, resulting a decrease in the viscosity of the alkyl oxirane derivative, when it was formulated in the hair cosmetic, sufficient, after finishing rinse, slipperiness when cutting the hair of water Does not express sex. In this _respect, the M L / _{M H} is 0.75 or less, more preferably be 0.62 or less.

Also, as M _L / M _H is reduced, the bias of the high molecular weight side is increased in the molecular weight distribution, and increase in viscosity derived therefrom seen. When M _L / M _H is less than 0.35, too high viscosity, hardly formulated, for example, cosmetics. From this point of view
Although the M _L / M _H 0.35 or higher and more preferably be 0.36 or more.

In a preferred embodiment, in gel permeation chromatography, the chromatogram represented by the refractive index intensity and the elution time obtained by using a differential refractometer is asymmetrical, and the chromatograph obtained as shown below is obtained. The asymmetric value As of the peak of the gram satisfies the following equations (3) and (4).
As = W _1/2 / W _5% ... (3)
0.30 ≤ As ≤ 0.70 ... (4)

The method of calculating As will be further described with reference to the model diagram of the chromatogram of FIG. The horizontal axis shows the elution time, and the vertical axis shows the refractive index intensity obtained by using a differential refractometer.
When the sample solution is injected into the gel permeation chromatograph and developed, elution starts from the molecule with the highest molecular weight, and the elution curve increases as the refractive index intensity increases. After that, the elution curve goes down after passing the maximum point where the refractive index intensity becomes maximum.

(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 thereof.
(2) Of the two points on the chromatogram having a refractive index intensity of L / 20, the one with the earlier elution time is designated as the point R, and the one with the slower elution time is designated as the point S.
(3) Let T be the intersection of the straight line H connecting the points R and S and the perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B.
(4) The distance between the point R and the intersection T is W _1/2 , and the distance between the point R and the point S is W _5% .

In a preferred embodiment, As satisfies 0.30 ≦ As ≦ 0.70. By setting As to 0.70 or less, the viscosity is improved, and when an alkyloxylane derivative is added to, for example, a hair cosmetic, it promotes sufficient slipperiness when draining the hair after rinsing. Tend. From this point of view, it is more preferable that As is 0.65 or less.

Further, as As becomes smaller, the bias on both sides of the polymer in the molecular weight distribution becomes larger, and the resulting increase in viscosity can be seen. By setting As to 0.30 or more, it is possible to prevent the viscosity from becoming too high and to easily incorporate it into cosmetics. From this point of view, As
It is more preferably 0.57 or more.

In the present _invention, M L, _M gel permeation chromatography to determine the _H and As (GPC) is, SHODEX KF SHODEX as a system (R) GPC101GPC dedicated system, SHODEX RI-71s as a differential refractometer, as a guard column -G, 3 HODEX KF804L as a column were continuously mounted, the column temperature was 40 ° C., tetrahydrofuran was flown as a developing solvent at a flow rate of 1 ml / min, and 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product was injected. Then, a BORWIN GPC calculation program is used to obtain a chromatogram represented by the refractive refractometer intensity and the elution time.

When producing the alkyloxylane derivative of the present invention, preferably, in the presence of a composite metal cyanide catalyst (hereinafter abbreviated as DMC catalyst) as an initiator, an alkylene oxide having 3 carbon atoms, that is, methyloxylane is used. Ring-opening is added. Initiator having at least one hydroxyl group in the molecule and a DMC catalyst are added to the reaction vessel, and methyloxylane is continuously or intermittently added under stirring in an inert gas atmosphere for addition polymerization. Methyloxylane may be added under pressure or may be added under atmospheric pressure.

At this time, the average supply rate of methyloxylan is not limited, but it is desirable to change it depending on the amount of methyloxylan charged. Specifically, the rate between supplying 5 to 20 wt% of the total supply of methyloxylan (supply amount per unit time) is V ₁ , and the rate while supplying 20 to 50 wt% of the total supply of methyloxylan. When V ₂ and 50 to 100 wt% of the total supply of methyloxylan are supplied as V ₃ , V ₁ / V ₂ = 1.1 to 2.0, V ₂ / V ₃ = 1. It is preferable to control the average supply rate of methyloxylane so as to be 1 to 1.5.

The reaction temperature is preferably 50 ° C. to 150 ° C., more preferably 70 ° C. to 110 ° 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 is slow and the productivity is poor.

As the initiator in the present invention, in the formula (1), a compound having Z having 1 to 22 carbon atoms and having a hydroxyl group number x of 1 to 6 or a compound obtained by adding methyloxylane to those compounds can be used. Examples of the initiator include butanol, butylpropylene glycol, polyoxypropylene glycol, polyoxypropylene glyceryl ether and the like. When Z is R ^{1 O, a monohydric alcohol (R 1} OH) having a hydrocarbon group having 1 to 22 carbon atoms represented by ^{R 1} in the formula (5) is used as the initiator. Can be done.

The amount of water contained in the initiator and methyloxylan is not particularly limited, but it is desirable that the amount of water contained in the initiator is 0.5 wt% or less and that of methyloxylan 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% with respect to the alkyloxylane derivative to be produced. The DMC catalyst may be introduced into the reaction system all at once at the beginning, or may be introduced in a sequential manner. After completion of the polymerization reaction, the composite metal complex catalyst is removed. The catalyst can be removed by a known method such as filtration, centrifugation, or treatment with a synthetic adsorbent.

A known DMC catalyst can be used in the present invention, and can be represented by, for example, the formula (6).

Ma [M'x (CN) y] b (H ₂ O) c · (R) d ... (6)

In formula (6), M and M'are metals, R is an organic ligand, a, b, x and y are positive integers that vary depending on the valence and coordination number of the metal, and c and d are metals. It is a positive integer that changes depending on the coordination number of.

Examples of the metal M include Zn (II), Fe (II), Fe (III), Co (II), Ni (II), Al (III), Sr (II), Mn (II), Cr (III), Examples thereof include Cu (II), Sn (II), Pb (II), Mo (IV), Mo (VI), W (IV), W (VI), and Zn (II) is preferably used.

Examples of the metal M'are Fe (II), Fe (III), Co (II), Co (III), Cr (II), Cr (III), Mn (II), Mn (III), Ni (II). , V (IV), V (V) and the like, and among them, Fe (II), Fe (III), Co (II) and Co (III) are preferably used.

As the organic ligand R, alcohol, ether, ketone, ester and the like can be used, and alcohol is more preferable. Preferred organic ligands are water-soluble, and specific examples thereof include tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, N, N-dimethylacetamide, ethylene glycol dimethyl ether (glyme), and diethylene glycol dimethyl ether ( Diglyme) and the like. Particularly preferably, it is Zn ₃ [Co (CN) ₆ ] ₂ coordinated with tert-butyl alcohol.

The alkyloxylan derivative of the present invention can be used in cosmetics by blending it as a raw material in cosmetics.

Especially when blended in hair cosmetics, especially in treatments, it has excellent slipperiness when rinsing the treatment, slipperiness when draining hair after rinsing, and smoothness of hair after drying. It is useful in that it does not leave a sticky feeling.

The alkyloxylan derivative of the present invention is used as an oil agent in cosmetics, and its concentration is preferably 0.001 to 5 wt%. When the concentration of the alkyloxylan derivative is lower than 0.001 wt%, the effect cannot be sufficiently exerted. Further, if the concentration is higher than 5 wt%, it will have a sticky feel when dried, which is not preferable as a cosmetic.

In addition, the cosmetics of the present invention include liquid fats and oils, higher fatty acids, higher alcohols, silicon, esters, anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric tensides, if necessary. Other ingredients such as activators, moisturizers, preservatives, pearling agents, pH adjusters, UV absorbers, hydrotopes, fragrances and the like may be added.

Hereinafter, the present invention will be described in detail with reference to examples.
(Reference synthesis example: Synthesis of complex metal cyanide complex catalyst)
_{A 15 ml aqueous solution containing 0.84 g of potassium hexacyanocobaltate K 3} Co (CN) ₆ was added dropwise to a 2.0 ml aqueous solution containing 2.1 g of zinc chloride over 15 minutes with stirring at 40 ° C. After completion of the 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. To this solid, 14 ml of water and 8.0 g of tert-butyl alcohol were added, and the mixture was stirred for 30 minutes and then filtered (second filtration) to obtain a solid.

Further, once 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. Then, 0.7 g of a composite metal cyanide complex catalyst was obtained.

(Synthesis Example 1)
Reference synthesis with 200 g of n-butanol in a stainless steel 5 liter (internal volume 4,890 ml) pressure resistant tank equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. 0.2 g of the composite metal cyanide complex catalyst of the example was charged. After the nitrogen substitution, the temperature was raised to 110 ° C., and 243 g of methyloxylan (LOT.151211D, manufactured by Sumitomo Chemical Co., Ltd.) was charged from a nitrogen gas blowing tube under the condition of 0.3 MPa or less over 16 hours. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured.

After 16 hours, the pressure in the reaction vessel dropped sharply. Then, while keeping the inside of the reaction vessel at 110 ° C., methyloxylane was gradually added from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and a total of 3,270 g of methyloxylan was continuously added under stirring. Pressure added. At this time, the time until 987 g of methyloxylane was introduced was 60 minutes, the time until 2,470 g was introduced was 180 minutes, and the time until 3,270 g was introduced was 270 minutes.

After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour. 2220 g was extracted from the reaction vessel, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 1,110 g of methyloxylane was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 2 hours. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour. Again, 1,044 g was withdrawn from the reaction vessel, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 312 g of methyloxylane was added from a nitrogen gas blowing tube over 40 minutes under the condition of 0.6 MPa or less. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 1) was measured by gel permeation chromatography.

For gel permeation chromatography, a system dedicated to SHODEX GPC101GPC, a differential refractometer SHODEX RI-71S, a guard column HOLDEX KF-GS, and three HODEX KF804L columns were continuously mounted, and the column temperature was 40 ° C. and the developing solvent was used. Tetrahydrofuran was flowed at a flow rate of 1 ml / min, 0.1 ml of a 0.1 wt% tetrahydrofuran solution of the obtained reaction product was injected, and a chromatograph represented by a refractive refractometer intensity and an elution time was used using a BORWIN GPC calculation program. Got a gram. FIG. 3 is the obtained chromatogram. _{When ML} / _MH was calculated from this chromatogram, it was 0.52 and As was 0.58.

(Synthesis Examples 2 to 6)
Reference with 200 g of butyl propylene glycol for a stainless steel 5 liter (internal volume 4,890 ml) pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. 0.2 g of the composite metal cyanide complex catalyst of the synthesis example was charged. After nitrogen substitution, the temperature was raised to 110 ° C., and 210 g of methyloxylan was charged from a nitrogen gas blowing tube under the condition of 0.3 MPa or less over 4 hours. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured.

After 4 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 110 ° C., methyloxylane was gradually added from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 3,287 g of methyloxylan was continuously pressurized and added under stirring. bottom. At this time, the time until 840 g of methyloxylan was added was 60 minutes, the time until 2,100 g was added was 108 minutes, and the time until 3,287 g was added was 132 minutes.

After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour, and then 1,680 g was withdrawn from the reaction vessel. The temperature of the residue in the reaction vessel was raised to 110 ° C., and 696 g of methyloxylane was added over 77 minutes from a nitrogen gas blowing tube under the condition of 0.6 MPa or less. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 1,188 g was taken out from the reaction vessel again, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed.

The obtained reaction product (Synthesis Example 2) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.62, As was 0.65.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and while keeping the inside of the reaction vessel at 110 ° C., 291 g of methyloxylane was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 35 minutes. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 752 g was withdrawn from the reaction vessel again, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 3) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.58, As was 0.63.

Further, the residue of the reaction vessel was heated to 110 ° C., and while keeping the inside of the reaction vessel at 110 ° C., 174 g of methyloxylane was added over 20 minutes from a nitrogen gas blowing tube under the condition of 0.6 MPa or less. .. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 619 g was withdrawn from the reaction vessel again, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 4) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.52, As was 0.61.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and while keeping the inside of the reaction vessel at 110 ° C., 121 g of methyloxylane was added over 30 minutes from a nitrogen gas blowing tube under the condition of 0.6 MPa or less. After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 370 g was taken out from the reaction vessel again, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 5) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.42, As was 0.59.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 122 g of methyloxylane was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 30 minutes while keeping the inside of the reaction vessel at 110 ° C. After reacting at 110 ° C. for 1 hour, the mixture was subjected to decompression treatment at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas, and then filtered. The obtained reaction product (Synthesis Example 6) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.36, As was 0.57.

(Synthesis Examples 7-8)
A stainless steel 5 liter (internal volume 4,890 ml) pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, steam jacket, propylene glycol and methyloxylan 200 g of polyoxypropylene glycol having a molecular weight of 700 and 0.1 g of a composite metal cyanide complex catalyst of the reference synthesis example were charged. After nitrogen substitution, the temperature was raised to 110 ° C., and 145 g of methyloxylane was charged from a nitrogen gas blowing tube under the condition of 0.3 MPa or less over 3 hours. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured.

After 3 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 110 ° C., methyloxylan was gradually added from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 1,230 g of methyloxylan was continuously pressurized and added under stirring. bottom. At this time, the time to add 130 g of methyloxylan was 10 minutes, the time to add 540 g was 55 minutes, and the time to add 1230 g was 60 minutes.

After completion of the addition, the reaction was carried out at 110 ° C. for 1 hour, and then 550 g was withdrawn from the reaction vessel, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 7) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.65, As was 0.65.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and while keeping the inside of the reaction vessel at 110 ° C., 870 g of methyloxylan was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 80 minutes. After reacting at 110 ° C. for 1 hour, the mixture was subjected to decompression treatment at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas, and then filtered. The obtained reaction product (Synthesis Example 8) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.6, As was 0.6.

(Synthesis Examples 9 to 11)
Methyloxylan in glycerin in a stainless steel 5 liter (internal volume 4,890 ml) pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. 100 g of polyoxypropylene glycol glyceryl ether having a molecular weight of 510 obtained by the reaction and 0.05 g of the composite metal cyanide complex catalyst of the reference synthesis example were charged. After nitrogen substitution, the temperature was raised to 110 ° C., and 50 g of methyloxylane was charged from a nitrogen gas blowing tube under the condition of 0.3 MPa or less over 5 hours. At this time, the changes over time in the pressure and temperature in the reaction vessel were measured.

After 5 hours, the pressure in the reaction vessel decreased sharply. Then, while keeping the inside of the reaction vessel at 110 ° C., methyloxylan was gradually added from the nitrogen gas blowing tube under the condition of 0.6 MPa or less, and 690 g of methyloxylan was continuously pressurized and added under stirring. At this time, the time until 150 g of methyloxylan was added was 20 minutes, the time until 370 g was added was 15 minutes, and the time until 690 g was added was 30 minutes.

After completion of the addition, the mixture was reacted at 110 ° C. for 1 hour, 480 g was withdrawn from the reaction vessel, and while blowing nitrogen gas, the pressure was reduced at 75 to 85 ° C. and 50 to 100 Torr for 1 hour, and then filtration was performed. The obtained reaction product (Synthesis Example 9) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.65, As was 0.66.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 180 g of methyloxylane was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 20 minutes while keeping the inside of the reaction vessel at 110 ° C. After reacting at 110 ° C. for 1 hour, depressurize at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas, then withdraw 200 g from the reaction vessel again and blow in nitrogen gas at 75 to 85 ° C. After decompression treatment at 50 to 100 Torr for 1 hour, filtration was performed. The obtained reaction product (Synthesis Example 10) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.64, As was 0.64.

Further, the temperature of the residue in the reaction vessel was raised to 110 ° C., and 140 g of methyloxylane was added from a nitrogen gas blowing tube under the condition of 0.6 MPa or less over 20 minutes while keeping the inside of the reaction vessel at 110 ° C. After reacting at 110 ° C. for 1 hour, the mixture was subjected to decompression treatment at 75 to 85 ° C. and 50 to 100 Torr for 1 hour while blowing nitrogen gas, and then filtered. The obtained reaction product (Synthesis Example 11) was measured by gel permeation chromatography. As a _{result, M} L / M _H is 0.62, As was 0.61.

(Comparative Synthesis Example 1)
A stainless steel 5 liter (internal volume 4,890 ml) pressure resistant reactor equipped with a thermometer, pressure gauge, safety valve, nitrogen gas blow pipe, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket is reacted with methyloxylan. 250 g of the obtained polyoxypropylene butyl ether having a molecular weight of 1,290 and 5.4 g of potassium hydroxide were charged. React 2322 g of methyloxylan at 100 ° C. to remove residual methyloxylan under reduced pressure at 0 ° C. for 30 minutes, transfer the reaction to a 5 L eggplant flask, quickly neutralize with 1N hydrochloric acid, and under a nitrogen gas atmosphere. After dehydration, filtration was performed.

The obtained reaction product (Comparative Synthesis Example 1) was measured by gel permeation chromatography. FIG. 4 is the obtained chromatogram.

Synthesis Examples 1 to 11 and Comparative Synthesis Examples 1 and Table 2 PREMINOL S1004F (manufactured by Asahi Glass Co., Ltd., high molecular weight / low by-product polyether polyol, number of functional groups 1), PREMINOL S4013F (manufactured by Asahi Glass Co., Ltd., high molecular weight) Tables 1 and 2 show the values of _ML / _MH and As obtained from the chromatogram of the low by-product polyether polyol and the number of functional groups 2), and the characteristics of the compounds.

Regarding Comparative Synthesis Example 1, PREMINOL S1004F, and PREMINOL S4013F, since the chromatogram has more than one maximum refractive index and is not a monomodal peak, M at the peak having the maximum refractive index intensity is M. _{The values of L} / _MH and As are shown.

In Tables 1 and 2, the hydroxyl value was measured according to JIS K-1557-1, the kinematic viscosity was measured according to JIS K-2283, the degree of unsaturation was measured according to JIS K-1557, and the molecular weight was calculated from the hydroxyl value. It is a thing.

(Examples 1 to 11, Comparative Examples 1 to 3)
Hair treatments are prepared according to the formulations shown in Tables 3 and 4 and the following manufacturing methods, and "slipperiness during rinsing", "slipperiness when draining hair after rinsing", and "after drying". The "smoothness of hair" and "non-sticky feeling" were evaluated and judged according to the following criteria, and the results are also shown in Tables 3 and 4. In Tables 3 and 4, NAA-48 (manufactured by NOF Corporation) was used as the cetearyl alcohol, and cation VB-M flakes (manufactured by NOF Corporation) were used as the behentrimonium chloride.

(Production method)
[1]: Ingredients (1) and (2) were heated to 80 ° C. and uniformly mixed.
[2]: [1] was added to the component (3) and emulsified and mixed. Then, while stirring, the mixture was cooled to 30 ° C. or lower.
[3]: For [2], any of the components (4) to (12) was added and stirred until uniform to obtain a hair treatment.

(Evaluation method)
A specialized panel consisting of 10 women aged 25 to 55 years old, "slipperiness during rinsing", "slipperiness when draining hair after rinsing", "smoothness of hair after drying" And "No stickiness" were evaluated on a 5-point scale according to the following criteria. Furthermore, it was totaled and judged.

(standard)
Evaluation points: 5 points: very good, 4 points: good, 3 points: normal, 2 points: slightly defective, 1 point: defective.

The hair cosmetic containing an alkyloxylan derivative having a specific molecular weight distribution of the present invention does not leave stickiness or stiffness, and also has slipperiness during rinsing and slipperiness when draining hair after rinsing. It was excellent.

In Comparative Example 1, an alkyloxylan derivative having a wide molecular weight distribution was blended on the low molecular weight side, but after rinsing, the slipperiness when draining the water of the hair decreased, and there was a sticky feeling.
In Comparative Examples 2 and 3, an alkyloxylan derivative having a very narrow molecular weight distribution was blended, but the slipperiness at the time of rinsing and the slipperiness at the time of draining the hair after rinsing were lowered, and there was a sticky feeling. rice field.

Claims (2)

It is represented by the formula (1), and characterized in that it comprises an alkyl oxirane derivative that satisfies the relationship of M _H and M _L Togashiki calculated from the chromatogram obtained by the gel permeation chromatography measurement (2), Hair cosmetics .

Z- [O- (AO) n-H] x ... (1)

(In equation (1),
Z represents a residue having 1 to 22 carbon atoms and having 1 to 6 hydroxyl groups excluding all hydroxyl groups.
x represents a number from 1 to 6
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more. )

_{0.35 ≦ M L / M H ≦} 0.75 ···· (2)

(The elution time of the two points on the chromatogram where the length of the perpendicular line from the maximum point K where the refractive index intensity on the chromatogram is maximum to the baseline B is L and the refractive index intensity is L / 2 When the earlier point is the point O, the slower elution time is the point Q, and the intersection of the straight line G connecting the points O and the point Q and the perpendicular line drawn from the maximum point K to the baseline is P, the point O _{Let MH} be the distance between the point Q and the intersection P, and let _ML be the distance between the point Q and the intersection P.)
The hair cosmetic according to claim 1, wherein the alkyloxylan derivative is represented by the following formula (5).

R ¹ O- (AO) n-H ... (5)

(In equation (5),
R ¹ represents a hydrocarbon group having 1 to 22 carbon atoms.
AO represents an oxyalkylene group having 3 carbon atoms.
n represents a number of 25 or more. )

Images