JP7202524B2 - Alkylene oxide derivatives, lubricants, antifoaming agents, base materials for cosmetics and cosmetics containing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to novel alkylene oxide derivatives, lubricants, antifoaming agents, cosmetic bases and cosmetic compositions containing the same, which can be effectively used in various applications.

Alkylene oxide derivatives are generally produced by ring-opening addition polymerization of oxyethylene (EO), oxypropylene (PO), and the like. It is possible to control the hydrophilic/lipophilic balance and molecular weight by controlling the number of moles of EO and PO added, as well as the form of addition. in use. Random adducts of EO and PO are used for water-based antifoaming agents, lubricants, base materials for cosmetics, etc., because their water-dispersibility and water-solubility can be adjusted by the number of moles of EO and PO added.

Water-based antifoaming agents are used in a wide variety of fields, such as the paper pulp manufacturing industry, the paint manufacturing industry, the cement manufacturing industry, the fiber processing industry, the fermentation industry, and waste water. For this reason, defoaming agents that can be used in a wide range of temperatures are required, for example, outside air from summer to winter for cement applications, around 40°C for fermentation applications, and 50°C or higher for textile processing applications. Known antifoaming agents include oil-in-water emulsions containing silicone oils and higher alcohols as main components. However, emulsion antifoaming agents are prone to sedimentation and uneven distribution during long-term use. There was a problem of contamination of On the other hand, polyalkylene glycol-based antifoaming agents are used as antifoaming agents with good water dispersibility. Therefore, emulsion antifoams with improved stability have been developed.

For example, Patent Document 1 discloses that an oil-in-water emulsion antifoaming agent containing a nonionic surfactant obtained by adding ethylene oxide to a secondary higher alcohol exhibits an excellent antifoaming effect and is excellent in stability. has been reported.

In addition, in the field of lubricants, alkylene oxide is widely used as a water-based lubricating oil with excellent cooling efficiency because it is nonflammable and highly stable at high temperatures, and there is no concern about separation or decomposition. there is For example, Patent Literature 2 reports an alkylene oxide adduct of a diol as a lubricating base oil having excellent water solubility and lubricating properties. However, when a surfactant such as an alkylene oxide is used, foam generation is significant, which may cause problems such as poor lubrication and reduced workability.

For this reason, Patent Document 3, for example, discloses a metal working oil composition containing a reverse block polyether obtained by adding oxypropylene to polyethylene glycol as a lubricant having defoaming properties.

In addition, nonionic surfactants are generally widely used as base materials for cosmetics, for example, emulsifiers for cosmetics, in emulsified cosmetics such as creams, milky lotions, and foundations in order to increase the stability of emulsions. Among these, polyoxyethylene-polyoxypropylene alkyl block copolymers are particularly known as emulsifiers that are resistant to hydrolysis and have excellent emulsifying performance.

Patent Document 4 describes that a polyoxyethylene polypropylene alkyl ether obtained by block addition of propylene oxide and ethylene oxide to a long-chain alcohol has a relatively low melting point, is easy to handle, and forms a stable emulsion over a long period of time. Further, Patent Document 5 describes that an O/W emulsified composition using a polyoxyethylene-polyoxypropylene block copolymer as an emulsifier is excellent in emulsification stability and feel during use.

JP 2001-62204 JP 2012-131982 Japanese Patent Application Laid-Open No. 08-231977 Japanese Patent Laid-Open No. 11-349438 JP 2010-132647

However, with the antifoaming agent described in Patent Document 1, the antifoaming effect depends on temperature, and the antifoaming agent to be used has to be changed depending on the application, process, and season in some cases. Furthermore, there were problems such as separation and increase in viscosity during long-term storage exceeding 30 days.

In addition, in the lubricant described in Patent Document 3, when the lubricant is heated by processing heat during use and reaches a high temperature of 50 ° C. or higher, the lubricant foams, and it is possible to achieve both lubricity and antifoaming properties. was difficult. Furthermore, there was a problem with long-term stability.

In addition, emulsified compositions using emulsifiers such as those described in Patent Documents 4 and 5 may become unstable when the temperature changes sharply, and are not sufficiently stable in terms of stability. In order to ensure stability in the presence of severe temperature changes, it is necessary to add a polymer or the like to increase the viscosity of the system, or adsorb a polymer or the like to the surface of the emulsion particles to create a steric repulsion between the emulsions. However, in that case, there is a problem that the feeling of touch is deteriorated, such as stickiness derived from the polymer.

An object of the present invention is to provide an alkylene oxide derivative containing a high molecular weight material, which is suitable for various uses such as lubricants, antifoaming agents, base materials for cosmetics, and cosmetic compositions containing the same. It is to be.

Another object of the present invention is to provide an antifoaming agent that can obtain sufficient antifoaming performance irrespective of temperature and has long-term stability by using an alkylene oxide derivative containing a high molecular weight substance.

Another object of the present invention is to provide a lubricant having both sufficient lubricating properties, defoaming properties and stability by using an alkylene oxide derivative containing a high molecular weight substance.

Another object of the present invention is to provide an emulsified cosmetic that secures long-term emulsification stability under severe temperature changes by using an alkylene oxide derivative containing a high molecular weight substance.

As a result of intensive studies in view of the above matters, the present inventors have found that the molecular weight pattern obtained by gel permeation chromatography measurement is left-right asymmetric, and the molecular weight distribution is biased toward the high molecular weight side, and is suitable for various applications. We have found that oxide derivatives can solve the above problems.

That is, the present invention is as follows.
(1)
The ratio Mz/Mw between the weight-average molecular weight (Mw) and the z-average molecular weight (Mz) represented by the formula (1) and calculated from the chromatogram obtained by gel permeation chromatography measurement satisfies the relationship of the formula (2). An alkylene oxide derivative with improved temperature change stability , characterized by:

Z-[O-[(PO)a-(EO)b]-H]n (1)

(In formula (1),
Z represents a residue obtained by removing all the hydroxyl groups from a compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups,
n represents a number from 1 to 6,
PO represents an oxypropylene group,
EO represents an oxyethylene group,

a and b represent the number of added moles of the oxypropylene group PO and the oxyethylene group EO, respectively, a is a number of 1 to 200, b is a number of 1 to 200,
(PO)a-(EO)b indicates that the oxypropylene group PO and the oxyethylene group EO are block-added,
a+b≧10 and a/b=1/5 to 5/1. )

20 ≦Mz/Mw≦ 50 (2)

(2) The alkylene oxide derivative of (1), wherein the tailing factor (TF) calculated from the chromatogram satisfies the relationships of formulas (3) and (4).

TF= _W0.05L /2a (3)
1.5≤TF≤5.0 (4)

(Among the two points where the refractive index intensity is L/20 on the chromatogram, point R is the earlier elution time, point S is the later elution time, and a straight line H connecting point R and point S And when the intersection of the perpendicular drawn from the maximum point K to the baseline B at which the refractive index intensity on the chromatogram is maximum is T, the distance between the point S and the intersection T is a, and the point R and the point Let the distance of S be W _0.05L .)

(3)
A lubricant comprising the alkylene oxide derivative of (1) or (2).

(4)
An antifoaming agent comprising the alkylene oxide derivative of (1) or (2).

(5)
A cosmetic base material comprising the alkylene oxide derivative of (1) or (2).

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel alkyl oxide derivative whose molecular weight distribution is biased toward the high molecular weight side, whose temperature change stability is improved, and which is suitable for various uses.

Moreover, according to the antifoaming agent comprising the alkylene oxide derivative of the present invention, sufficient antifoaming performance can be obtained regardless of the temperature.

Further, according to the lubricant comprising the alkylene oxide derivative of the present invention,
It is possible to provide lubricants with sufficient lubricity, defoaming properties and stability.

Further, according to the emulsified cosmetic composition comprising the alkylene oxide derivative of the present invention, long-term emulsification stability is ensured in the presence of temperature changes, and when the emulsion is applied, it is non-sticky and spreadable. A rich emulsified cosmetic can be provided.

FIG. 1 is a model chromatogram diagram for explaining Mz/Mw defined in the present invention. FIG. 2 is a model chromatogram diagram for explaining the TF defined in the present invention.

In this specification, the numerical range defined using the symbol "-" includes the numerical values at both ends (upper limit and lower limit) of "-". For example, "2 to 5" represents 2 or more and 5 or less.

(Alkylene oxide derivative)
The alkyloxirane derivative of the present invention is a compound represented by formula (1).
Z-[O-[(PO)a-(EO)b]-H]n (1)

Z is a residue obtained by removing all hydroxyl groups from a compound having 1 to 24 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and having 1 to 6 hydroxyl groups, n is the number of hydroxyl groups in the compound (Z(OH)n) and is 1 to 6; The compound (Z(OH)n) having 1 to 6 hydroxyl groups includes methanol, ethanol, butanol when n=1, ethylene glycol, propylene glycol, hexylene glycol when n=2, and n= If 3, glycerin, trimethylolpropane; if n=4, erythritol, pentaerythritol, sorbitan, diglycerin, alkyl glycoside; if n=5, xylitol; if n=6, dipentaerythritol, sorbitol, inositol. etc. A mixture of these may also be used as the compound having 1 to 6 hydroxyl groups. In antifoaming agents, n is preferably 2 to 6, more preferably n=3 to 6, and even more preferably n=3. In lubricants and emulsified cosmetics, n is preferably 1 to 4, more preferably 1 to 3, and still more preferably 1.

In formula (1), Z may be R ¹ where n=1 and R ¹ is a hydrocarbon group of 1-24 carbon atoms.

The hydrocarbon group having 1 to 24 carbon atoms represented by R ¹ is a functional group consisting of carbon and hydrogen, and is one selected from an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, or an aralkyl group, An alkyl group or alkenyl group is preferable, an alkyl group or alkenyl group having 1 to 12 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is most preferable. The alkyl group having 1 to 6 carbon atoms may be linear or branched, and more preferably linear. Examples of linear alkyl groups having 1 to 6 carbon atoms include methyl group, ethyl group, propyl group, butyl group and hexyl group. The hydrocarbon group having 1 to 24 carbon atoms represented by R ¹ may be of one type or two or more types.

PO is an oxypropylene group, EO is an oxyethylene group, a and b indicate the number of added moles of PO and EO, respectively, a is a number from 1 to 200, b is a number from 1 to 200, and a+b≧10. (PO) _b -(EO) _c represents a polyoxyalkylene group formed by block addition of PO and EO, and the molar ratio (a/b) of PO and EO is 1/5 to 5/1.

If a+b is less than 10, the temperature versatility of the antifoaming agent, the lubricity of the lubricant, and the emulsifiability of the emulsified cosmetic may be insufficient. From this point of view, a+b is preferably 10 or more, more preferably 13 or more. Also, the viscosity increases as a+b increases. From the viewpoint of ease of dispersion and blending, a+b is preferably 120 or less, more preferably 100 or less.
Further, the total number of added moles of PO and EO, n×(a+b), is preferably 50 or more, more preferably 60 or more, and even more preferably 70 or more. Also, it is more preferably 100 or less, and even more preferably 80 or less.

If a/b is less than 1/5, the temperature versatility of the antifoaming agent and the lubricity of the lubricant may deteriorate, and the emulsified cosmetic may become sticky and have a poor feel. If it exceeds 5/1, water dispersibility and water solubility may deteriorate. Therefore, a/b is set to 1/5 to 5/1, but 1/2.5 to
4/1 is even more preferable, and 1/1.25 to 1/1 is even more preferable.

(GPC Characteristics of Alkyloxirane Derivatives)
The alkyl oxirane derivatives of the present invention are defined by molecular weights obtained by chromatograms 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.

In the alkyloxirane derivative of the present invention, the ratio Mz/Mw between the weight average molecular weight (Mw) and the z average molecular weight (Mz) obtained from the chromatogram is 20 ≦Mz/Mw≦ 50 .

Here, Mw and Mz are obtained from GPC by the following formulas.

where N is the number of polymer molecules, M is the molecular weight, and C is the sample concentration. Mw is a weighted average using the molecular weight as a weight, and Mz is a weighted average using the square of the molecular weight as a weight. Mw is affected by the presence of high molecular weights, and Mz is even more affected by the presence of high molecular weights than Mw. Therefore, the alkylene oxide derivative of the present invention has Mw and Mz like the chromatogram shown in FIG.

If Mz/Mw is less than 20 , the temperature versatility of the antifoaming agent, the lubricity of the lubricant, and the emulsion stability of the emulsified cosmetic may become insufficient. From this point of view, Mz/Mw is more preferably 20 or more, more preferably 40 or more. When Mz/Mw is more than 50 , the molecular weight distribution is more biased toward the high molecular weight side, resulting in an increase in viscosity and the like, making it difficult to disperse and blend in each formulation. From this point of view, Mz/Mw is more preferably 50 or less.

In a preferred embodiment, in gel permeation chromatography, the chromatogram represented by the refractive index intensity and elution time obtained using a differential refractometer is left-right asymmetric, and the chromatogram obtained as shown below Gram's tailing factor (TF) satisfies 1.50≤TF≤5.0.

The method for calculating TF will be further described with reference to the model diagram of the chromatogram in FIG. The horizontal axis indicates the elution time, and the vertical axis indicates the refractive index intensity obtained using a differential refractometer. 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.

In addition, in the gel permeation chromatography of the alkylene oxide derivative of the present invention, when there are a plurality of maximum points of refractive index intensity in the chromatogram, the maximum point K is the point with the highest refractive index intensity. 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.

(1) A perpendicular line is drawn from the maximum point K of the refractive index intensity on the chromatogram to the baseline B, and its length is L. (2) Of the two points on the chromatogram where the refractive index intensity is L/20, point R is the earlier elution time, and point S is the later elution time. (3) Let T be the point of intersection between a straight line H connecting the points R and S and a perpendicular line drawn from the maximum point K of the refractive index intensity to the baseline B. (4) Let the distance between point S and intersection T be a, and the distance between point R and point S be W _0.05L .
TF= _W0.05L /2a (3)
1.5≤TF≤5.0 (4)

In a preferred embodiment, TF satisfies 1.5≤TF≤5.0. A TF of 1.5 or more tends to improve the temperature versatility of the antifoaming agent, the lubricity of the lubricant, and the stability of the hair cosmetic composition. From this point of view, TF is more preferably 2.0 or more, most preferably 3.0 or more.

In addition, as the TF increases, the molecular weight distribution becomes more biased on both sides of the polymer, resulting in an increase in viscosity and the like. If the TF is greater than 5.0, the molecular weight distribution is more biased toward the high molecular weight side, resulting in an increase in viscosity and the like, making it difficult to disperse and blend in each formulation. From this point of view, TF is more preferably 4.5 or less, most preferably 4.0 or less.

In the present invention, gel permeation chromatography (GPC) for determining Mz/Mw and TF is performed using SHODEX (registered trademark) GPC101 GPC dedicated system as a system and SHODEX as a differential refractometer.
RI-71s, SHODEX KF-G 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. 0.1 ml of wt % tetrahydrofuran solution is injected and a chromatogram expressed as refractive index intensity and elution time is obtained using the BORWIN GPC calculation program.

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

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

As the initiator in the present invention, in Formula (1), compounds in which Z has 1 to 24 carbon atoms and the number of hydroxyl groups x is 1 to 6, or those compounds to which oxypropylene is added can be used. Examples of initiators include butanol, butylpropylene glycol, polyoxypropylene glycol, polyoxypropylene glyceryl ether, and the like. When Z is R ¹ , the initiator may be a monohydric alcohol (R ¹ OH) having a hydrocarbon group of 1 to 24 carbon atoms represented by R ¹ in formula (5). can.

Although there are no particular restrictions on the amount of water contained in the initiator and oxypropylene, it is desirable that the amount of water contained in the initiator is 0.5 wt% or less, and that of oxypropylene 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 alkylene oxide derivative 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 (6).
Md[M'y(CN)z]e(HO)f.(R)g (6)

In formula (6), M and M' are metals, R is an organic ligand, d, e, y and z are positive integers that vary depending on the valence and coordination number of the metal, and f and g are metal is a positive integer that varies depending on the coordination number of

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 R, alcohols, ethers, ketones, esters and the like 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.

(Antifoaming Agent) The alkylene oxide derivative of the present invention can be used as an antifoaming agent. The antifoaming agent of the present invention can be used as a single alkylene oxide derivative represented by formula (1), or as a formulation in which an alkylene oxide derivative is dissolved in an aqueous component to improve water dispersibility when used in an aqueous system. . Aqueous components include water, lower alcohols such as ethyl alcohol and propyl alcohol, and mixtures of water and lower alcohols. Although there is no particular limitation on the mixing ratio of water, the concentration of the alkylene oxide derivative is preferably 0.1 to 99 wt%. If the concentration of the alkylene oxide derivative is less than 0.1 wt%, the defoaming power may be lowered. On the other hand, when the concentration of the alkylene oxide derivative is 99 wt % or more, the handleability may be poor.

The antifoaming agent of the present invention may further contain known antifoaming agents such as organic solvents, mineral oils, animal and vegetable oils, and other ingredients such as stabilizers, thickeners and preservatives, if necessary.

Applications of the antifoaming agent of the present invention are not particularly limited. It can be used in dyeing industry, rubber industry, synthetic resin industry, ink industry, paint industry, textile industry and the like.

When using the antifoaming agent of the present invention, there is no particular limitation on the mixing ratio in the aqueous medium that needs to be defoamed. 0.0001 to 5 wt%, more preferably 0.001 to 5 wt%.

(Lubricant) The alkylene oxide derivative of the present invention can be used as a lubricant. The antifoaming agent of the present invention can be used as a single alkylene oxide derivative represented by formula (1), or as a formulation in which an alkylene oxide derivative is dissolved in an aqueous component to improve water dispersibility when used in an aqueous system. . Aqueous components include water, lower alcohols such as ethyl alcohol and propyl alcohol, and mixtures of water and lower alcohols.

The lubricant of the present invention is water-soluble and has excellent lubricating properties and defoaming properties. It can be used as a metal processing oil used for processing such as polishing and cutting of silicon wafers, and as a base oil for water-based lubricating oil such as water-glycol hydraulic oil.

In addition, the lubricant of the present invention may optionally contain a detergent-dispersant, an antioxidant, an oiliness agent, an emulsifier, an extreme pressure agent, a metal deactivator, a rust inhibitor, a viscosity index improver and a pour point depressant. Other components commonly used in lubricants, such as, may be added.

(Base material for cosmetics)
The alkylene oxide derivative of the present invention can be used in cosmetics by blending it into cosmetics as a raw material.
In particular, when blended as an emulsifier in an emulsified cosmetic, it is possible to prepare an emulsified cosmetic that ensures long-term emulsification stability even under temperature changes.

The alkylene oxide derivative of the present invention is used as an emulsifier in cosmetics, and its concentration is preferably 0.1 to 10 wt % or more. When the concentration of the alkylene oxide derivative is lower than 0.1 wt%, the effect cannot be sufficiently exhibited.

In addition, the cosmetic of the present invention may optionally contain liquid fats and oils, higher fatty acids, higher alcohols, silicones, esters, surfactants, moisturizing agents, preservatives, pearlizing agents, pH adjusters, and ultraviolet absorbers. Other ingredients commonly used in cosmetics, such as agents, hydrotopes, perfumes, etc., may be added.

EXAMPLES The present invention will be described in detail below with reference to examples and comparative examples.
(Synthesis of double metal cyanide complex 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 a double metal cyanide complex catalyst.

(Synthesis Example 1: Synthesis of Example Compound 1)
A 5 L autoclave equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas inlet tube, a stirrer, an evacuation tube, a cooling coil, and a steam jacket was charged with 100 g of butylpropylene glycol and 0.04 g of a double metal cyanide complex catalyst. After the replacement, the temperature was raised to 110° C., and 132 g of oxypropylene was added dropwise from a nitrogen gas blowing pipe under the condition of 0.3 MPa or less, and the change in pressure and temperature in the reaction vessel over time was measured. After that, the pressure in the reactor dropped sharply. After that, while maintaining the inside of the reactor at 110° C., 1494 g of oxypropylene was gradually added dropwise from a nitrogen gas blowing pipe under a condition of 0.5 MPa or less. After the addition was completed, the mixture was allowed to react at 110°C for 3 hours, and then 1258 g of oxyethylene was added dropwise at 110°C. After completion of the addition, the mixture was reacted at 110° C. for 1 hour, treated under reduced pressure at 75 to 85° C. for 1 hour, and filtered. The resulting compound 1 was measured by gel permeation chromatography.
However, the butyl propylene glycol used was manufactured by Nippon Emulsion, the oxypropylene manufactured by Sumitomo Chemical, and the oxyethylene manufactured by Nippon Shokubai.

(Synthesis Examples 2 to 7: Synthesis of Example Compounds 2 to 6 and Comparative Example Compound 1)
A compound was synthesized in the same manner as in Synthesis Example 1 except for the starting material, the number of moles of oxypropylene and oxyethylene added, and the type of alkylene oxide. The obtained Example Compounds 2 to 6 and Comparative Example Compound 1 were measured by gel permeation chromatography.

(Synthesis Example 8: Synthesis of Comparative Example Compound 2)
A 5 L autoclave equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas inlet tube, a stirrer, an evacuation tube, a cooling coil, and a steam jacket was charged with 100 g of butylpropylene glycol and 6.0 g of potassium hydroxide as a catalyst. After the replacement, the temperature was raised to 110° C., and 1626 g of oxypropylene was gradually added dropwise from a nitrogen gas blowing pipe under the condition of 0.5 MPa or less. After reacting at 110°C for 3 hours, 1258 g of oxyethylene was added dropwise at 110°C. After completion of the addition, react at 110° C. for 1 hour, treat under reduced pressure at 75-85° C. for 1 hour, transfer the reactant to a 5 L round-bottomed flask, quickly neutralize with 1N hydrochloric acid, dehydrate under a nitrogen gas atmosphere, and filter. did

Table 1 shows the Mz/Mw and TF values obtained from the chromatograms of Synthesis Examples 1 to 8 and the properties of the compounds. However, the hydroxyl value was measured according to JIS K-1557-1, and the molecular weight was calculated from the hydroxyl value.

(Antifoam performance)
In order to evaluate the stability and antifoaming properties of the antifoaming agents containing the alkylene oxide derivatives of Synthesis Examples 1-8, antifoaming agents were prepared using Synthesis Examples 1-8.
8 parts by weight of stearyl alcohol, 9 parts by weight of arachidyl alcohol, and 8 parts by weight of behenyl alcohol were added to 1 part by weight of the alkylene oxide derivatives of Synthesis Examples 1 to 8. After uniformly mixing at 70°C, 73 parts by weight of water at 70°C was added while stirring. The mixture was cooled to 25°C while stirring to obtain an antifoaming agent.

The obtained antifoaming agent was allowed to stand in a 6-hour cycle test chamber at -5°C to 60°C for 3 months, and the state after 3 months was observed and visually measured according to the following criteria.

○:
Stable state △:
Slightly uneven state x:
Separated State The results are shown in Table 2.

Furthermore, an antifoaming test was conducted to evaluate the antifoaming properties of the obtained antifoaming agent. A 0.04% saponin aqueous solution was prepared by diluting saponin with tap water, and an alkylene oxide derivative was added to 125 ppm. 200 mL of the prepared sample was placed in a 1000 mL graduated cylinder, and the aqueous solution was air-bubbled at 100 mL/min for 10 minutes while maintaining the aqueous solution at 20°C. The volume from the bottom of the graduated cylinder to the highest point of the foam was defined as the volume of the sample, and the volume increase rate of the sample after air bubbling was calculated. The volume increase rate is calculated by the following formula, and the smaller the value of the volume increase rate, the better the defoaming property.

Volume increase rate (%) =
(Sample volume after air bubbling−Sample volume before air bubbling) (ml)/Sample volume before air bubbling (ml)×100

◎:
The volume increase rate is less than 110% and the defoaming property is excellent.
The volume increase rate is 110% or more and less than 200%, and the antifoaming property is excellent △:
The volume increase rate is 200% or more and less than 300%, and the defoaming property is poor.
The volume increase rate is 300% or more, and the antifoaming property is inferior. Similar experiments were conducted at 40°C and 60°C. Table 2 shows the results.

(lubricant performance)
In order to evaluate the lubricity of the alkylene oxide derivatives of Synthesis Examples 1-8, lubricants were prepared using the alkylene oxide derivatives of Synthesis Examples 1-8. The lubricant is a mixture of 30 parts by weight of an alkylene oxide derivative, 5 parts by weight of caprylic acid, 2 parts by weight of sebacic acid, 25 parts by weight of triethanolamine, 0.1 part by weight of benzotriazole, and 37.9 parts by weight of water. dissolved to obtain a lubricant.

The obtained lubricant was allowed to stand in a 6-hour cycle test chamber at -5°C to 60°C for 3 months.

○:
Stable state △:
Slightly uneven state x:
Separated state The results are shown in Table 3.

Furthermore, the coefficient of friction was measured in order to evaluate the lubricity of the obtained lubricant.
A lubricity test was performed using an SRV Lubricant and material test system (manufactured by Optimal). The test was performed with a ball/disk, and SUJ-2 was used for each test piece. The test conditions were a temperature of 50° C., a load of 40 N, an amplitude of 1 mm, and a frequency of 50 Hz. Lubricity was evaluated according to the following criteria. Table 3 shows the results.

◎:
A coefficient of friction (μ) of 0.11 or less:
A coefficient of friction (μ) greater than 0.11 and less than or equal to 0.12 Δ:
Friction coefficient (μ) is greater than 0.12 and 0.14 or less ×:
Friction coefficient (μ) is greater than 0.14

Defoaming properties when used as a lubricant were evaluated.
50 ml of a lubricant diluted with a 5% aqueous solution was placed in a 100 ml cylinder, shaken for 10 seconds, and then the time until bubbles disappeared was measured. Defoaming properties were evaluated according to the following criteria. Table 3 shows the results.

◎:
Defoams within 15 seconds and has excellent antifoaming ○:
Defoaming within 30 seconds longer than 15 seconds, excellent defoaming △:
Defoaming within 60 seconds longer than 30 seconds, poor antifoaming x:
Defoaming takes longer than 60 seconds and has poor defoaming properties.

(Emulsification performance)
Emulsions were prepared in order to evaluate the emulsifying performance of the alkylene oxide derivatives of Synthesis Examples 1-8.
Using the alkylene oxide derivatives of Synthesis Examples 1 to 8, emulsions were prepared with the compositions shown in Table 4. The adjustment method is as follows.
(1)
The oil phase is heated to 80°C and dissolved uniformly.
(2)
After uniformly dissolving the aqueous phase at 25°C, the solution is heated to 80°C.
(3)
Add the water phase while stirring the oil phase at 80°C.

Immediately after emulsification, the prepared emulsified composition was allowed to stand in a 6-hour cycle test tank at -5°C to 60°C for 3 months, and the state after 3 months was observed, and the emulsified state was visually measured according to the following criteria. went.

◎:
A state in which the emulsion is fine and stable ○:
Stable state △:
Slightly uneven state x:
Slightly separated state XX:
creaming or separating

As is clear from Table 2, the antifoaming agents using Synthesis Examples 1 to 6 were excellent in stability, and all were excellent in antifoaming properties at 20, 40 and 60°C.

As is clear from Table 3, the lubricants using Synthesis Examples 1 to 6 were all excellent in stability, lubricity and antifoaming properties.

As is clear from Table 5, all of Compounds 1 to 6 used in Examples maintained long-term emulsification stability under severe temperature changes.

On the other hand, as is clear from Tables 2, 3, and 5, Comparative Example Compounds 1 and 2, which do not correspond to the alkylene oxide derivatives of the present invention, have defoaming properties, lubricity, and long-term stability under severe temperature changes. Emulsion stability, none satisfies all.

Claims (5)

The ratio Mz/Mw between the weight-average molecular weight (Mw) and the z-average molecular weight (Mz) represented by the formula (1) and calculated from the chromatogram obtained by gel permeation chromatography measurement satisfies the relationship of the formula (2). An alkylene oxide derivative with improved temperature change stability , characterized by:

Z-[O-[(PO)a-(EO)b]-H]n (1)

(In formula (1),
Z represents a residue obtained by removing all the hydroxyl groups from a compound having 1 to 24 carbon atoms and 1 to 6 hydroxyl groups,
n represents a number from 1 to 6,
PO represents an oxypropylene group,
EO represents an oxyethylene group,

a and b represent the number of added moles of the oxypropylene group PO and the oxyethylene group EO, respectively, a is a number of 1 to 200, b is a number of 1 to 200,
(PO)a-(EO)b indicates that the oxypropylene group PO and the oxyethylene group EO are block-added,
a+b≧10 and a/b=1/5 to 5/1. )

20 ≦Mz/Mw≦ 50 (2)
2. The alkylene oxide derivative according to claim 1, wherein the tailing factor (TF) calculated from the chromatogram satisfies the relationships of formulas (3) and (4).

TF= _W0.05L /2a (3)
1.5≤TF≤5.0 (4)

(Among the two points where the refractive index intensity is L/20 on the chromatogram, point R is the earlier elution time, point S is the later elution time, and a straight line H connecting point R and point S And when the intersection of the perpendicular drawn from the maximum point K to the baseline B at which the refractive index intensity on the chromatogram is maximum is T, the distance between the point S and the intersection T is a, and the point R and the point Let the distance of S be W _0.05L .)
A lubricant comprising the alkylene oxide derivative according to claim 1 or 2.
An antifoaming agent comprising the alkylene oxide derivative according to claim 1 or 2.
A base material for cosmetics, comprising the alkylene oxide derivative according to claim 1 or 2.

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