JP5675688B2 - Alkylene oxide adduct and process for producing the same - Google Patents

Description

  The present invention relates to an alkylene oxide adduct having excellent fluidity and storage stability at low temperatures and excellent emulsifying power and thickening performance, and a method for producing the same.

Ethylene oxide adducts obtained by adding ethylene oxide to higher alcohols are useful and widely used in various industrial applications such as detergents, emulsifiers, dispersants, oil phase component modifiers, penetrants, and polymer raw materials. Higher alcohol ethylene oxide adducts are excellent in emulsification and dispersion performance. However, there are drawbacks such as a high freezing point and poor low-temperature stability.
In order to remedy these disadvantages, ethylene oxide / propylene oxide copolymer adducts of higher alcohols have been proposed. Generally, when a propylene oxide structural unit is introduced into a polyoxyethylene chain, fluidity and stability at low temperatures are improved, and merits such as low foaming properties are produced. However, on the other hand, the introduction of a propylene oxide structural unit in the polyoxyethylene chain also causes a demerit that the emulsifying power and the thickening performance are reduced as compared with a simple ethylene oxide adduct.

In order to optimize the performance of this higher alcohol ethylene oxide / propylene oxide copolymer adduct, various structural designs have been studied.
For example, Patent Document 1 has a random adduct of ethylene oxide and propylene oxide; Patent Document 2 has a block adduct of ethylene oxide and then propylene oxide; Patent Document 3 has a block adduct of propylene oxide and then ethylene oxide; Reference 4 includes random addition of ethylene oxide and propylene oxide, followed by block addition of ethylene oxide; Patent Document 5 includes random addition of ethylene oxide and propylene oxide, followed by addition of ethylene oxide, and block addition of propylene oxide. Patent Document 6 discloses ethylene oxide, then propylene oxide, then block adduct of ethylene oxide, and the like. However, these ethylene oxide / propylene oxide copolymer adducts do not sufficiently satisfy any required properties such as low foaming property, emulsifying power, dispersing power, and thickening. In addition, the adducts of Patent Documents 5 and 6 have a problem in production such that the reaction process is complicated and multistage, and thus the production time is long.

Patent Document 7 proposes a higher alcohol-based alkylene oxide adduct intermediate composition having water and a solvent and having excellent uniform transparency and good fluidity, but water or solvents that do not directly contribute to performance. Is not preferable because it is mixed.
As described above, the alkylene oxide adducts of Patent Documents 1 to 7 have problems, but the current situation is that the conventional alkylene oxide adducts must be used while having these problems.

JP-A-7-303825 JP-A 63-12192 JP-A-53-58505 Japanese Patent Laid-Open No. 10-461189 JP-A-10-130690 JP-A-10-195499 Japanese Patent Laid-Open No. 51-13394

  An object of the present invention is to provide an alkylene oxide adduct having good low-temperature fluidity and excellent emulsifying power and thickening performance, and a method for producing the same.

  In order to solve the above-mentioned problems, the present inventors have conducted intensive studies. As a result, when alcohol is reacted with ethylene oxide and propylene oxide, the weight ratio of ethylene oxide and propylene oxide is controlled within a certain range. As a result, the knowledge that an alkylene oxide adduct that solves the above problems can be obtained was obtained, and the present invention was completed.

The method for producing an alkylene oxide adduct of the present invention has the following general formula (A):
ROH (A)
(R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure.)
A process for producing an alkylene oxide adduct comprising a step of simultaneously supplying ethylene oxide and propylene oxide to an alcohol represented by
The start of supply of ethylene oxide and propylene oxide is T0, the end of supply of ethylene oxide and propylene oxide is T100, and the times T1 and T2 between T0 and T100 are T0 <T1 <T2 <T100 and (T2-T1 ) /T100=0.01

The weight ratio of ethylene oxide to propylene oxide supplied at each time point of T0, T100, T1, and T2 is determined by [EO / PO] _T0 , [EO / PO] _T100 , [EO / PO] _T1 and [EO / PO] _T2 is a production method that simultaneously satisfies the following mathematical formulas (B) to (D).
0 <[EO / PO] _T0 <1 (B)
1 <[EO / PO] _T100 <100 (C)
0.8 <[EO / PO] _T2 / [EO / PO] _T1 < 1.2 (D)

In this production method, it is preferable that at least one of the following (1) to (4) is satisfied.
(1) The following mathematical formulas (B-1) and (C-1) are further satisfied.
0.1 <[EO / PO] _T0 <0.5 (B-1)
2 <[EO / PO] _T100 <20 (C-1)
(2) The following numerical formula (D-1) is further satisfied.
0.9 <[EO / PO] _T2 / [EO / PO] _T1 <1.2 (D-1)

(3) After the said process, it further includes the process of supplying 1 type of the alkylene oxide chosen from ethylene oxide and a propylene oxide, and carrying out an addition reaction.
(4) The alkylene oxide is ethylene oxide.

The alkylene oxide adduct of the present invention has the following general formula (1):
RO-[(PO) p / (EO) q] -H (1)
(However, R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO represents an oxypropylene group, and EO represents an oxyethylene group. P and q denote the average number of moles added, respectively, where p = 1 to 20 and q = 1 to 50. [(PO) p / (EO) q] is p moles of PO and q moles. This is a polyoxyalkylene group formed by random addition of EO.)
An alkylene oxide adduct represented by the formula:

Based on the charts obtained by measuring the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the alkylene oxide adduct, N _PO-PO , N _PO2 , N _EO-R , N _R , N _EO- defined below respectively. reading _{OH, N PO-OH,} the _{N 1OH} and _{N 2OH,}
N _PO-PO : Sum of integral values of ¹³ C-NMR spectrum attributed to primary carbon of PO-PO bonded PO N _PO2 : Integrated value of ¹³ C-NMR spectrum attributed to secondary carbon of PO Sum N _EO-R : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly ether-bonded to R group N _R : Integral of ¹³ C-NMR spectrum attributed to α-position carbon of R group Sum of values N _EO-OH : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly bonded to terminal hydroxyl group N _PO-OH : To carbon of PO directly bonded to terminal hydroxyl group sum _{N 1 OH} of the integrated value of the ¹³ C-NMR spectrum attributed: primary sum _{N 2OH} of ¹ H-NMR integral value of the spectrum attributable to protons bound methylene group of the hydroxyl group: coupling a secondary hydroxyl group Of integrated values of ¹ H-NMR spectrum assigned to proton of methine group

Then, the obtained reading values are respectively calculated by the following formulas (I) to (IV):
_Er (%) = 100 * _NPO-PO / ( _NPO-PO + _NPO2 ) (I)
E _EO-R (%) = 100 × N _EO-R / N _R (II)
E _EO-OH (%) = 100 × N _EO-OH / (N _EO-OH + N _PO—OH ) (III)
_{E OH (%) = 100 ×} N 2OH / (N 1OH + N 2OH) (IV)
Randomized exponent E _r obtained by _{substituting,} the percentage E _EO-R oxyethylene groups connected directly to the R _group, oxyethylene group terminal hydroxyl groups are directly connected percent E _EO-OH, and the terminal hydroxyl group 2 quaternizing rate _{E OH} parameters are to satisfy the following formula (I-a) ~ a (IV-a), respectively, an alkylene oxide adduct.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 49 (II-A)
51 ≦ E _EO-OH ≦ 99 (III-A)
1 ≦ E _OH ≦ 49 (IV-A)

The alkylene oxide adduct preferably satisfies at least one of the following 1) to 5).
1) p = 1-10 and q = 1-30.
2) Carbon number of said R is 8-20.
3) The weight average molecular weight is 200-5000.
4) The cloud point measured by the butyl diglycol method (BDG method) is 0-95 degreeC.
5) The following mathematical formulas (IB) to (IV-B) are further satisfied.
10 ≦ E _r ≦ 35 (IB)
10 ≦ E _EO-R ≦ 40 (II-B)
65 ≦ E _EO-OH ≦ 95 (III-B)
10 ≦ E _OH ≦ 40 (IV-B)

Another alkylene oxide adduct of the present invention is an alkylene oxide adduct obtained by adding one kind of alkylene oxide selected from ethylene oxide and propylene oxide to the above alkylene oxide adduct and subjecting it to an addition reaction. ,
The following general formula (2):
RO-[(PO) p / (EO) q]-(AO) r-H (2)
(However, R represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO is an oxypropylene group, EO is an oxyethylene group, AO Represents one kind of oxyalkylene group selected from an oxyethylene group and an oxypropylene group, p, q and r represent the average number of moles added, p = 1 to 20 , q = 1 to 50 and r = 1 to 50. [(PO) p / (EO) q] is a polyoxyalkylene group formed by random addition of p mol of PO and q mol of EO.)
It is the alkylene oxide adduct represented by these. Here, the AO is preferably an oxyethylene group.

The emulsifier of the present invention contains the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component.
The dispersant of the present invention contains the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component.
The cleaning agent of the present invention contains the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component.

The method for producing an alkylene oxide adduct of the present invention can efficiently produce an alkylene oxide adduct having good low-temperature fluidity and excellent emulsifying power and thickening performance.
The alkylene oxide adduct of the present invention has good low-temperature fluidity and excellent emulsifying power and thickening performance.

The emulsifier of the present invention has an emulsifying power because it contains an alkylene oxide adduct as an essential component.
Since the dispersant of the present invention contains an alkylene oxide adduct as an essential component, it has excellent dispersion power.
Since the cleaning agent of the present invention contains an alkylene oxide adduct as an essential component, it has excellent cleaning power.

It is a graph which shows a time-dependent change from the supply start time to the end of supply about the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Example 1. It is a graph which shows a time-dependent change from the supply start time to the supply end time about the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Example 6. It is a graph which shows a time-dependent change from the supply start time to the supply end time about the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Comparative Example 1. 2 is a chart showing the results of measuring the ¹³ C-NMR spectrum of the alkylene oxide adduct obtained in Example 1. FIG. 2 is a chart showing the results of measuring the ¹ H-NMR spectrum of the alkylene oxide adduct obtained in Example 1. FIG.

[Production method of alkylene oxide adduct]
The method for producing an alkylene oxide adduct of the present invention has the following general formula (A):
ROH (A)
(R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure.)
Is a production method including a step of simultaneously adding ethylene oxide and propylene oxide to the alcohol represented by the formula (hereinafter, this step may be referred to as “addition reaction step 1”). Hereinafter, for the sake of simplicity, “ethylene oxide and propylene oxide” may be referred to as “alkylene oxide A”.

Further, after the addition reaction step 1, a step of supplying one type of alkylene oxide selected from ethylene oxide and propylene oxide to cause an addition reaction (hereinafter, this step may be referred to as “addition reaction step 2”). .).
R in the alcohol represented by the general formula (A) is an alkyl group or an alkenyl group. R may be composed of either a linear or branched structure.

The carbon number of R is usually 1 to 30, preferably 1 to 25, more preferably 1 to 22, particularly preferably 6 to 20, and most preferably 8 to 20. When the carbon number of R exceeds 30, the hydrophobicity of the resulting alkylene oxide adduct increases.
The alcohol is not particularly limited. For example, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonaol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, , Straight chain alkanols such as heptadecanol, octadecanol, nonadecanol, eicosanol, heneicosanol, docosanol, tricosanol, tetracosanol, pentacosanol, hexacosanol, heptacosanol, octacosanol, nonacosanol and triacosanol; to 2-ethyl Xanol, 2-propylheptanol, 2-butyloctanol, 1-methylheptadecanol, 2-hexylocta Branched alkanols such as hexol, 1-hexylheptanol, isodecanol, isotridecanol, 3,5,5-trimethylhexanol; hexenol, heptenol, octenol, nonenol, decenol, undecenol, dodecenol, tridecenol, tetradecenol, pentadecenol, Linear alkenols such as xadecenol, pentadecenol, hexadecenol, heptadecenol, octadecenol, nonadecenol, eisenol, docosenol, tetracosenol, pentacosenol, hexacosenol, heptacosenol, heptacosenol, octacosenol, nonacosenol and triaconsenol; isohexenol, isohexenol, ethyl Tridecenol, 1-methylheptadecenol, - hexyl Cheb tenor, branched alkenol such as isotriazole dec Nord and iso-octadecenyl Knoll and the like. These alcohols may be used alone or in combination of two or more. Specific examples of higher alcohol products are not particularly limited. For example, higher alcohols derived from natural fats and oils such as palm alcohol and palm alcohol, the Calcoal series (made by Kao), the Conol series (made by Shin Nippon Rika) Oxocol series (manufactured by Kyowa Hakko Chemical), neodol series (manufactured by Shell Chemical), ALFOL series (manufactured by Sasol), EXXAL series (manufactured by Exxon Mobil) and the like. These higher alcohol products may be used alone or in combination of two or more.

The production method of the present invention may be performed in the presence of a catalyst. The catalyst is not particularly limited. For example, alkali (earth) metal hydroxides such as sodium hydroxide, potassium hydroxide, cesium hydroxide, calcium hydroxide, barium hydroxide, strontium hydroxide; potassium oxide Alkali (earth) metal oxides such as sodium oxide, calcium oxide, barium oxide, magnesium oxide, strontium oxide; alkali metals such as metal potassium and metal sodium; metal hydrides such as sodium hydride and potassium hydride ; Carbonates of alkali (earth) metals such as sodium carbonate, sodium bicarbonate and potassium carbonate; sulfates of alkali (earth) metals such as sodium sulfate and magnesium sulfate; organics such as methanesulfonic acid and trifluoromethanesulfonic acid Sulfonic acid; sodium paratoluenesulfonate, patorue Aromatic sulfonates such as pyridinium sulfonate; amine compounds such as monoethanolamine, diethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, and triethylamine; iron powder, aluminum powder, antimony powder, aluminum (III) chloride, Aluminum bromide (III), iron (III) chloride, iron (III) bromide, cobalt (III) chloride, antimony (III) chloride, antimony (V) chloride, antimony (III) bromide, tin tetrachloride, four Lewis acids such as titanium chloride, boron trifluoride and boron trifluoride diethyl ether; proton acids such as sulfuric acid and perchloric acid; potassium perchlorate, sodium perchlorate, calcium perchlorate, magnesium perchlorate, etc. Alkali (earth) metal perchlorate; calcium metho Alkali (earth) metal alkoxides such as sid, sodium ethoxide and lithium ethoxide; Alkali (earth) metal phenoxides such as potassium phenoxide and calcium phenoxide; Sodium silicate, potassium silicate, sodium aluminosilicate, potassium aluminosilicate, Silicates such as sodium metasilicate, orthosilicate sodium, zeolite; Al-Mg complex oxides such as calcined aluminum hydroxide and magnesium, metal ion-added magnesium oxide, calcined hydrotalcite, or surface modified products thereof, lanthanoids A complex etc. are mentioned. These catalysts may be used alone or in combination of two or more.
Although there is no limitation in particular about the usage-amount of a catalyst, Preferably it is 0.001-10 weight part with respect to 100 weight part of alcohol, More preferably, it is 0.001-8 weight part, More preferably, it is 0.01-6. Part by weight, particularly preferably 0.05 to 5 parts by weight, most preferably 0.05 to 3 parts by weight. If the amount of the catalyst used is less than 0.001 part by weight, the addition reaction may not proceed sufficiently. On the other hand, when the amount of the catalyst used exceeds 10 parts by weight, the alkylene oxide adduct may be easily colored.

In the production method of the present invention, it is preferable that raw materials such as alcohol and catalyst are charged into a reaction vessel, and the reaction vessel is subjected to degassing treatment or dehydration treatment. The degassing process is performed by, for example, a vacuum degassing system, a vacuum degassing system, or the like. Further, the dehydration process is performed by, for example, a heat dehydration method, a vacuum dehydration method, a vacuum dehydration method, or the like.
In the production method of the present invention, the production form is not particularly limited, and may be a continuous type or a batch type. Although there is no limitation in particular about reaction container, For example, the tank-type reaction container provided with the stirring blade, the micro reactor, etc. can be mentioned. Although there is no limitation in particular as a stirring blade, A max blend blade, a tornado blade, a full zone blade, etc. can be mentioned.

In the production method of the present invention, the addition reaction may be started from a reduced pressure state, may be started from an atmospheric pressure state, or may be started from a pressurized state. When starting from an atmospheric pressure state or a pressurized state, it is preferably carried out in an inert gas atmosphere. When the addition reaction is carried out in an inert gas atmosphere, it is possible to sufficiently remove impurities generated due to side reactions between alkylene oxides such as ethylene oxide and propylene oxide and oxygen, and safety. From the viewpoint of this, it is preferable because it is useful. The inert gas is not particularly limited, and examples thereof include nitrogen gas, argon gas, and carbon dioxide gas. These inert gases may be used alone or in combination of two or more. The oxygen concentration in the reaction vessel under an inert gas atmosphere is not particularly limited, but is preferably 10% by volume or less, more preferably 5% by volume or less, still more preferably 3% by volume or less, and particularly preferably 1% by volume. % Or less, and most preferably 0.5% by volume or less. If the oxygen concentration in the reaction vessel exceeds 10% by volume, impurities may not be sufficiently removed, and it may not be preferable from the viewpoint of safety.
The initial pressure in the reaction vessel is not particularly limited. For example, the gauge pressure is preferably 0 to 0.50 MPa, more preferably 0 to 0.45 MPa, still more preferably 0 to 0.4 MPa, and particularly preferably 0. ~ 0.35 MPa, most preferably 0-0.3 MPa. If the initial pressure in the reaction vessel is less than 0 MPa, the amount of impurities generated may increase. On the other hand, when the initial pressure in the reaction vessel is more than 0.50 MPa, the reaction rate may be slow.

When alkylene oxide A is supplied to the alcohol, an addition reaction occurs. Here, since ethylene oxide and propylene oxide are supplied at the same time, the polyoxyalkylene group formed in the resulting alkylene oxide adduct is likely to be generated by random addition, which is preferable.
There is no particular limitation on the method of supplying the alkylene oxide A at the same time, but 1) a method of supplying ethylene oxide and propylene oxide to alcohol simultaneously from different supply lines, and 2) ethylene oxide and propylene oxide. And a continuous supply of alcohol mixed with in-line from a different line, or 3) a mixture of parts of ethylene oxide and propylene oxide in advance. And then a method in which the remaining ethylene oxide and the remaining propylene oxide are continuously supplied to the alcohol simultaneously from different supply lines, and 4) mixing in which ethylene oxide and propylene oxide are mixed in advance. Prepare some method sequentially supplies like the alcohol separates these mixtures in several stages and the like.

In addition reaction process 1, it is preferable to supply, changing the weight ratio of ethylene oxide and propylene oxide supplied.
In addition reaction step 1, it is more preferable that the weight ratio of ethylene oxide and propylene oxide to be supplied is controlled so that the weight ratio of propylene oxide is large at the start of supply and the weight ratio of ethylene oxide is large at the end of the supply. .

Here, the supply start time of ethylene oxide and propylene oxide (alkylene oxide A) is T0, the supply end time of alkylene oxide A is T100, and the times T1 and T2 between T0 and T100 are T0 <T1 <T2 < When T100 and (T2−T1) /T100=0.01 are set, the weight ratio of ethylene oxide to propylene oxide supplied at each time point of T0, T100, T1, and T2 is determined as [EO / PO] _T0 , [EO / PO] _T100 , [EO / PO] _T1 and [EO / PO] _T2 may satisfy the following formulas (B) to (D) simultaneously.
0 <[EO / PO] _T0 <1 (B)
1 <[EO / PO] _T100 <100 (C)
0.8 <[EO / PO] _T2 / [EO / PO] _T1 <10 (D)

The numerical formula (B) is preferably 0.02 <[EO / PO] _T0 <0.9, more preferably 0.05 <[EO / PO] _T0 <0.8, and particularly preferably 0.08 <[EO. / _PO] T0 <0.7, most preferably _{0.1 <[EO / PO] T0} <0.5. [EO / PO] When _T0 is 0, the resulting alkylene oxide adduct may have low emulsifying power and thickening performance. On the other hand, when [EO / PO] _T0 is 1 or more, the resulting alkylene oxide adduct may have low emulsifiability.
The numerical formula (C) is preferably 1.2 <[EO / PO] _T100 <80, more preferably 1.5 <[EO / PO] _T100 <60, and particularly preferably 1.8 <[EO / PO] _T100. <40, most preferably 2 <[EO / PO] _T100 <20. [EO / PO] If _T100 is 1 or less, the resulting alkylene oxide adduct may have low emulsifiability. On the other hand, when [EO / PO] _T100 is 100 or more, it may be difficult to control the supply of ethylene oxide and propylene oxide.

The numerical formula (D) is preferably 0.8 <[EO / PO] _T2 / [EO / PO] _T1 <5.0, more preferably 0.8 <[EO / PO] _T2 / [EO / PO] _T1. <2.0, particularly preferably 0.9 <[EO / PO] _T2 / [EO / PO] _T1 <1.2, most preferably 1.0 ≦ [EO / PO] _T2 / [EO / PO] _T1 <1.2. When [EO / PO] _T2 / [EO / PO] _T1 is 0.8 or less, the resulting alkylene oxide adduct may have low emulsifiability. When [EO / PO] _T2 / [EO / PO] _T1 is 10 or more, the low temperature fluidity of the resulting alkylene oxide adduct may not be excellent.
Roughly speaking, the expressions (B) to (D) mean that the weight ratio of ethylene oxide is gradually increased from the start of supply of ethylene oxide and propylene oxide to the end of supply. It is. However, in a minute time range that satisfies the relationship of (T2−T1) /T100=0.01 (for example, T2−T1), the weight ratio of ethylene oxide may be temporarily decreased. .

The supply rate of the alkylene oxide A may be adjusted so as to satisfy the formulas (B) to (D) at the same time, and is not particularly limited. For example, 1) The supply rate of the alkylene oxide A at the start of supply is Fast and gradually slow the supply rate (a large amount of alkylene oxide A is supplied at the start of supply, and decrease at the end of the supply), 2) The supply rate of alkylene oxide A at the start of supply is slow and the supply is gradually A method of increasing the speed (a small amount is supplied at the start of supply of alkylene oxide A, and increasing the amount at the end of supply), and 3) the supply rate of ethylene oxide is slow at the start of supply, and gradually the supply rate is gradually increased over time. On the other hand, the supply rate of propylene oxide is increased at the start of supply, and gradually decreased with the passage of time (ethylene oxide). A small amount is supplied at the start of supply of the side, and the amount is increased at the end of supply, while a large amount of propylene oxide is supplied at the start of supply, and the amount is reduced at the end of supply), and 4) the supply rate of propylene oxide is constant. Keep the supply rate of ethylene oxide at the start of supply slow and gradually increase the supply rate over time, or 5) keep the supply rate of ethylene oxide constant and increase the supply rate of propylene oxide at the start of supply. For example, a method of slowing the supply speed gradually with the passage of time can be used.
The pressure in the reaction vessel during the addition reaction is affected by the supply rate of alkylene oxide A, the reaction temperature, the amount of catalyst, and the like. The pressure in the reaction vessel during the addition reaction is not particularly limited, but is preferably 0 to 5.0 MPa, more preferably 0 to 4.0 MPa, further preferably 0 to 3.0 MPa, and particularly preferably 0 to 0 in terms of gauge pressure. 2.0 MPa, most preferably 0.1-1.0 MPa. When the pressure in the reaction vessel during the addition reaction is less than 0 MPa, the reaction rate may be slow. On the other hand, if the pressure in the reaction vessel during the addition reaction is more than 5.0 MPa, the production may be difficult.

The reaction temperature for the addition reaction of alkylene oxide A is not particularly limited, but is preferably 70 to 240 ° C, more preferably 80 to 220 ° C, still more preferably 90 to 200 ° C, particularly preferably 100 to 190 ° C, and most preferably. Is 110-180 ° C. If the reaction temperature is less than 70 ° C., the addition reaction may not proceed sufficiently. On the other hand, when the reaction temperature exceeds 240 ° C., coloring of the resulting alkylene oxide adduct and decomposition of the polyoxyalkylene group in the alkylene oxide adduct may be promoted.
The time required for the addition reaction (reaction time) is not particularly limited, but is preferably 0.1 to 100 hours, more preferably 0.1 to 80 hours, still more preferably 0.1 to 60 hours, and particularly preferably. 0.1 to 40 hours, most preferably 0.5 to 30 hours. If the reaction time is less than 0.1 hour, the addition reaction may not proceed sufficiently. On the other hand, when the reaction time exceeds 100 hours, the production efficiency may deteriorate.

When the supply of the alkylene oxide A is completed, the internal pressure in the reaction vessel gradually decreases as the alkylene oxide A is consumed. The addition reaction of alkylene oxide A is preferably continued until no change in internal pressure is observed. The addition reaction of alkylene oxide A ends when no change in internal pressure is observed over a certain period of time. An unreacted alkylene oxide A may be recovered by performing a heating and decompression operation or the like as necessary.
In the addition reaction of alkylene oxide A, an inert solvent can be used as necessary. For example, when a solid alcohol such as triaconsenol is used as the alcohol, it is preferable to use it by dissolving it in an inert solvent in advance before the reaction, thereby improving the reactivity more sufficiently, and handling properties. high. In addition, if an inert solvent is used, a heat removal effect can be expected.

There are no particular limitations on the inert solvent, but examples include ethers such as diethyl ether, ethylene glycol dimethyl ether, dioxane, and tetrahydrofuran; esters such as diethylene glycol methyl ether acetate and propylene glycol methyl ether acetate; acetone, methyl isobutyl ketone, and methyl ethyl ketone. Ketones such as sulfolane, sulfones such as sulfolane and dimethylsulfonoxide, halogenated hydrocarbons such as dichloromethane and chloroform, aromatic hydrocarbons such as benzene, toluene and xylene, and the like such as pentane, hexane, cyclopentane and cyclohexane. Aliphatic hydrocarbons etc. are mentioned, You may use together 1 type (s) or 2 or more types. Of these, aromatic hydrocarbons are preferable, and toluene is more preferable.
The amount of the inert solvent used is not particularly limited, but when used to dissolve alcohol, it is preferably 10 to 1000 parts by weight, more preferably 10 to 500 parts by weight with respect to 100 parts by weight of alcohol. Parts, more preferably 10 to 400 parts by weight, particularly preferably 10 to 300 parts by weight, and most preferably 10 to 200 parts by weight. If the amount of the inert solvent is more than 1000 parts by weight with respect to 100 parts by weight of the alcohol, the addition reaction may not proceed sufficiently. On the other hand, if the amount of the inert solvent is less than 10 parts by weight, the alcohol may not be sufficiently dissolved. When an inert solvent is used, it is preferably removed after the addition reaction. By removing the inert solvent, the generation of impurities due to the remaining inert solvent can be sufficiently prevented, and an alkylene oxide adduct having excellent physical properties can be obtained. The solvent removal step is as described later.

After completion of the addition reaction of alkylene oxide A, it is preferable to neutralize and / or remove the catalyst or remove the inert solvent as necessary.
The neutralization of the catalyst is limited to the case where the catalyst is mainly an alkali catalyst, and may be performed by an ordinary method. For example, hydrochloric acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, acrylic acid, methacrylic acid It is preferable to carry out by adding an acid such as.

The neutralization of the catalyst is preferably carried out in an inert gas atmosphere. Although there is no limitation in particular as an inert gas, For example, nitrogen gas, argon gas, a carbon dioxide gas etc. are mentioned, You may use 1 type (s) or 2 or more types together.
The temperature during neutralization of the catalyst is not particularly limited, but is preferably 50 to 200 ° C, more preferably 50 to 190 ° C, still more preferably 60 to 180 ° C, particularly preferably 60 to 170 ° C, and most preferably. 60-160 ° C. If the temperature during neutralization of the catalyst is less than 50 ° C., the time required for neutralization may become long. On the other hand, when the temperature during neutralization of the catalyst is higher than 200 ° C., coloring of the resulting alkylene oxide adduct and decomposition of the polyoxyalkylene group in the alkylene oxide adduct may be promoted.

By the neutralization of the catalyst, the pH of the reaction product obtained by the above addition reaction is preferably adjusted to 4 to 10, more preferably 5 to 8, particularly preferably 6 to 8. Moreover, antioxidants, such as quinones and phenols, can also be used together as necessary during catalyst neutralization.
The neutralized salt produced by neutralization may be further subjected to solid-liquid separation. Examples of the method for solid-liquid separation of the neutralized salt produced by neutralization include filtration and centrifugation. For filtration, for example, a filter paper, a filter cloth, a cartridge filter, a two-layer filter of cellulose and polyester, a metal mesh filter, a sintered metal filter, etc., under reduced pressure or pressurized conditions of 20 to 140 ° C. It is good to do. Centrifugation may be performed, for example, using a centrifuge such as a decanter or a centrifugal clarifier. Moreover, about 1-30 weight part of water can also be added with respect to 100 weight part of liquids before solid-liquid separation as needed. As the solid-liquid separation, particularly when filtration is performed, it is preferable to use a filter aid because the filtration rate is improved.

The filter aid is not particularly limited. For example, each series of Celite, High Flow Supercell, and Cell Pure (manufactured by Advanced Minerals Corporation), silica # 645, silica # 600H, silica # 600S, silica # 300S, silica # 100F Diatomaceous earth such as Daikalite (manufactured by Chuo Silica), diatomite such as Daikalite (manufactured by Grefco); Perlite such as RocaHelp (manufactured by Mitsui Mining & Smelting), Topco (manufactured by Showa Kagaku); Cellulose-based filter aids such as Advanced Minerals Corporation); silica gels such as silopute (Fuji Silysia Chemical Co., Ltd.) and the like. These filter aids may be used alone or in combination of two or more.
For the filter aid, a precoat method for forming a filter aid layer on the filter surface such as filter paper in advance may be used, or a body feed method for directly adding to the filtrate may be used, or both of these may be used in combination. Good. The amount of the filter aid used is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1.5 parts by weight with respect to 100 parts by weight of the liquid before solid-liquid separation. The filtration rate depends on the size of the filter surface, the degree of vacuum or pressurization, the treatment humidity, etc., but is preferably 100 kg / m ² · hr or more, more preferably 300 kg / m ² · hr or more. More preferably 500 kg / m ² · hr or more.

The removal of the alkali catalyst is not particularly limited, but for example, a method of solid-liquid separation after adsorbing the alkali catalyst to the adsorbent is preferable.
Examples of the adsorbent include silicates such as aluminum silicate and magnesium silicate, activated clay, acid clay, silica gel, ion exchange resin and the like. Examples of commercially available adsorbents include KYOWARD 600, 700 (manufactured by Kyowa Chemical Co., Ltd.), Mizuka Life P-1, P-1S, P-1G, F-1G (manufactured by Mizusawa Chemical Co., Ltd.), Tomita-AD600, 700. Silicates (Tomita Pharmaceutical Co., Ltd.), etc .; Amberlist (Rohm and Haas), Amberlite (Rohm and Haas), Diaion (Mitsubishi Chemical), Dowex (Dow Chemical) And the like, and the like. These adsorbents may be used alone or in combination of two or more.

The amount of the adsorbent used is, for example, preferably 100 to 5000 parts by weight, more preferably 300 to 3000 parts by weight with respect to 100 parts by weight of the alkali catalyst.
The conditions for removing the alkali catalyst are not particularly limited. For example, the adsorbent is stirred and mixed at a temperature of 20 to 140 ° C. for 5 to 120 minutes under any one of reduced pressure, normal pressure, and pressurized conditions, A method of separating the adsorbent on which the alkali catalyst is adsorbed by the above-mentioned solid-liquid separation method, or a column or the like is previously filled with the adsorbent, and the reaction mixture is passed at a temperature of 20 ° C to 140 ° C to adsorb the alkali catalyst. And a method of removing the alkali catalyst. At this time, if necessary, 1 to 20 parts by weight of a water-soluble solvent such as water or lower alcohol represented by ethanol may be added to 100 parts by weight of the reaction mixture.

The residual amount after removal of the alkali catalyst is not particularly limited, but is preferably 300 ppm or less, more preferably 200 ppm or less, still more preferably 100 ppm or less, particularly preferably 50 ppm or less, and most preferably 20 ppm or less.
The removal of the inert solvent is preferably performed by distillation, for example.
In addition, when performing neutralization and / or removal of a catalyst and removal of an inert solvent, the order of each step is not particularly limited. For example, after neutralization and / or removal of a catalyst, The removal is preferable because the resulting alkylene oxide adduct is excellent in purification efficiency.

In the production method of the present invention, the content of unreacted remaining alcohol is not particularly limited, but is preferably 1 part by weight or less, more preferably 0.8 parts per 100 parts by weight of the resulting alkylene oxide adduct. 01 parts by weight or less, more preferably 0.001 parts by weight or less, particularly preferably 0.0001 parts by weight or less, and most preferably 0.00001 parts by weight or less. If the content of the unreacted alcohol remaining is more than 1 part by weight with respect to 100 parts by weight of the alkylene oxide adduct, odor may be generated.
Next, when the addition reaction step 2 is performed, after the addition reaction step 1, one type of alkylene oxide selected from ethylene oxide and propylene oxide is supplied to cause addition reaction. In addition reaction step 2, one of ethylene oxide and propylene oxide is subjected to an addition reaction with respect to the terminal hydroxyl group of the alkylene oxide adduct obtained in addition reaction step 1.

The alkylene oxide used in the addition reaction step 2 may be any one of ethylene oxide and propylene oxide, but ethylene oxide is preferable because of excellent emulsifying power and thickening performance.
In addition reaction step 2, 1) one of ethylene oxide and propylene oxide may be supplied to the reaction mixture obtained in addition reaction step 1 as it is, and the addition reaction may be carried out. 2) addition reaction step As described above, the reaction mixture obtained in 1 is subjected to neutralization and / or removal of the catalyst or removal of the inert solvent, and after the treatment, the ethylene oxide and the propylene oxide are used. One type may be supplied to carry out the addition reaction.

[Alkylene oxide adduct]
The alkylene oxide adduct of the present invention has the following general formula (1):
RO-[(PO) p / (EO) q] -H (1)
(However, R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO represents an oxypropylene group, and EO represents an oxyethylene group. P and q denote the average number of moles added respectively, where p = 1-30 and q = 1-50, [(PO) p / (EO) q] is expressed in p moles of PO and q moles. This is a polyoxyalkylene group formed by random addition of EO.)
It is the alkylene oxide adduct represented by these.

Based on the chart in which the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the alkylene oxide adduct were measured, N _PO-PO , N _PO2 , N _EO-R , N _R , and N _EO-OH defined below respectively. , _NPO-OH , _N1OH and _N2OH ,
N _PO-PO : Sum of integral values of ¹³ C-NMR spectrum attributed to primary carbon of PO-PO bonded PO N _PO2 : Integrated value of ¹³ C-NMR spectrum attributed to secondary carbon of PO Sum N _EO-R : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly ether-bonded to R group N _R : Integral of ¹³ C-NMR spectrum attributed to α-position carbon of R group Sum of values N _EO-OH : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly bonded to terminal hydroxyl group N _PO-OH : To carbon of PO directly bonded to terminal hydroxyl group sum _{N 1 OH} of the integrated value of the ¹³ C-NMR spectrum attributed: primary sum _{N 2OH} of ¹ H-NMR integral value of the spectrum attributable to protons bound methylene group of the hydroxyl group: coupling a secondary hydroxyl group Of integrated values of ¹ H-NMR spectrum assigned to proton of methine group

Then, the obtained reading values are respectively calculated by the following formulas (I) to (IV):
_Er (%) = 100 * _NPO-PO / ( _NPO-PO + _NPO2 ) (I)
E _EO-R (%) = 100 × N _EO-R / N _R (II)
E _EO-OH (%) = 100 × N _EO-OH / (N _EO-OH + N _PO—OH ) (III)
_{E OH (%) = 100 ×} N 2OH / (N 1OH + N 2OH) (IV)
Randomized exponent E _r obtained by _{substituting,} the percentage E _EO-R oxyethylene groups connected directly to the R _group, oxyethylene group terminal hydroxyl groups are directly connected percent E _EO-OH, and the terminal hydroxyl group 2 quaternizing rate _{E OH} parameters are to satisfy the following formula (I-a) ~ a (IV-a), respectively.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 49 (II-A)
51 ≦ E _EO-OH ≦ 99 (III-A)
1 ≦ E _OH ≦ 49 (IV-A)

R is a group derived from the alcohol described in the above production method, and the description thereof is also as described above.
PO is an oxypropylene group, and p represents the average number of moles added of the oxypropylene group. The average added mole number p of the oxypropylene group is not particularly limited, but is usually 1 to 30, preferably 1 to 25, more preferably 1 to 20, still more preferably 1 to 15, particularly preferably 1 to 12, Most preferably, it is 1-10. When the average added mole number of the oxypropylene group is less than 1, hydrophobicity and compatibility with the substrate may not be sufficient. On the other hand, if the average number of moles added of the oxypropylene group is more than 30, hydrophobicity may become too strong.

EO represents an oxyethylene group, and q represents the average number of moles added of the oxyethylene group. The average addition mole number q of the oxyethylene group is not particularly limited, but is usually 1 to 50, preferably 1 to 45, more preferably 1 to 40, still more preferably 1 to 30, particularly preferably 1 to 25, Most preferably, it is 1-20. When the average added mole number of the oxyethylene group is less than 1, hydrophilicity or compatibility with the substrate may not be sufficient. On the other hand, when the average number of added moles of oxyethylene groups is more than 50, hydrophilicity may become too strong.
[(PO) p / (EO) q] is a polyoxyalkylene group formed by randomly adding p mol of oxypropylene group and q mol of oxyethylene group. One end of the polyoxyalkylene group is bonded to the R group via an ether bond, and the other end is a hydroxyl group (hereinafter, this hydroxyl group may be referred to as a terminal hydroxyl group). Random addition in the present invention means an addition state in which oxypropylene groups and oxyethylene groups are randomly copolymerized and arranged.

When normal random addition is performed, the ratio of ethylene oxide and propylene oxide to be supplied is not changed as the addition reaction proceeds, and a substantially constant value is maintained. The oxypropylene group can be located at any position of the polyoxyalkylene group such as the R group side of the polyoxyalkylene group, the terminal hydroxyl group side of the polyoxyalkylene group, the R group side of the polyoxyalkylene group and the midpoint of the terminal hydroxyl group side. The molar ratio of oxyethylene groups is almost the same value.
On the other hand, in the polyoxyalkylene group of the alkylene oxide adduct of the present invention, the above molar ratio is greatly characterized. That is, the alkylene oxide adduct of the present invention is formed with the progress of the addition reaction by changing the weight ratio of the supplied ethylene oxide and propylene oxide over time, as described in the above production method. The molar ratio of ethylene oxide and propylene oxide varies depending on the position in the polyoxyalkylene group. And the gradient of the molar ratio depending on the position in a polyoxyalkylene group comes to arise. In the alkylene oxide adduct of the present invention, specifically, 1) on the R group side of the polyoxyalkylene group of the alkylene oxide adduct, the molar ratio of the oxypropylene group is large, and 2) on the R group side of the polyoxyalkylene group. The molar ratio of the polyoxyethylene group gradually increases as it approaches the terminal hydroxyl group side of the polyoxyalkylene group, and 3) the molar ratio of the oxyethylene group increases on the terminal hydroxyl group side of the polyoxyalkylene group. .

In the alkylene oxide adduct of the present invention, when a gradient occurs in the molar ratio of the oxypropylene group and the oxyethylene group depending on the position in the polyoxyalkylene group, the randomization index E _r and R group described above Percentage of EO groups directly bonded E _EO-R , percentage of EO groups directly bonded to terminal hydroxyl groups E _EO-OH , and secondary hydroxylation of terminal hydroxyl groups calculated from the peak area of ¹ H-NMR spectrum The rate E _OH satisfies the above formulas (IA) to (IV-A), respectively.
The randomization index E _r (%) is usually 1 ≦ E _r ≦ 45, preferably 1 ≦ E _r ≦ 40, more preferably 1 ≦ E _r ≦ 35, particularly preferably 5 ≦ E _r ≦ 35, most preferably Preferably, 10 ≦ E _r ≦ 35. The smaller the value of _Er, the higher the randomization rate in the polyoxyalkylene group. If _Er is less than 1%, the reaction may be difficult. On the other hand, if _Er is more than 45%, it cannot be said that random addition but block addition.

N _PO-PO is the sum of all integral values attributed to the primary carbon of PO-PO bonded _PO in the ¹³ C-NMR spectrum, and all the values confirmed in the range of 74.3 to 76.0 ppm It is the sum of integral values.
N _PO2 is the sum of all integral values attributed to the secondary carbon of PO in the ¹³ C-NMR spectrum, and is the sum of all integral values confirmed in the range of 72.2 to 73.8 ppm.

The percentage E _EO-R (%) of oxyethylene groups directly bonded to the R group is usually 1 ≦ E _EO-R ≦ 49, preferably 1 ≦ E _EO-R ≦ 45, more preferably 1 ≦ E _{EO -R≤40} , particularly preferably _5≤EEO- R≤40, most preferably _{10≤EEO-R≤40} . When _EO-R is less than 1%, it cannot be said that random addition, and is very close to the structure of block addition. On the other hand, if _EO-R is more than 49%, the emulsifying power may not be excellent.
N _R is the sum of all integral values attributed to the α-position carbon of the R group in the ¹³ C-NMR spectrum, and is the sum of all integral values confirmed in the range of 71.2 to 72.0 ppm. .

N _EO-R is the sum of all integral values attributed to the oxyethylene group directly ether-bonded to the R group in the ¹³ C-NMR spectrum, and is found in the range of 69.7 to 70.3 ppm. It is the sum of integral values.
The percentage E _EO-OH (%) of EO directly bonded to the terminal hydroxyl group is usually 51 ≦ E _EO-OH ≦ 99, preferably 55 ≦ E _EO-OH ≦ 99, more preferably 60 ≦ E _EO-OH. ≦ 99, particularly preferably 65 ≦ E _EO-OH ≦ 99, most preferably 65 ≦ E _EO-OH ≦ 95. If _EO-OH is less than 51%, the emulsifying power may not be excellent. On the other hand, if E _EO-OH is more than 99%, it cannot be said that random addition, and is very close to the structure of block addition.

N _EO-OH is the sum of all integral values attributed to carbon of EO directly bonded to the terminal hydroxyl group in the ¹³ C-NMR spectrum, and is all confirmed in the range of 61.0 to 63.0 ppm. Is the sum of the integral values of.
N _PO—OH is the sum of all integral values attributed to the carbon of PO directly bonded to the terminal hydroxyl group in the ¹³ C-NMR spectrum, and is all confirmed in the range of 65.0 to 67.5 ppm. Is the sum of the integral values of.

The terminal hydroxyl group secondaryization rate E _OH (%) is usually 1 ≦ E _OH ≦ 49, preferably 1 ≦ E _OH ≦ 45, more preferably 1 ≦ E _OH ≦ 40, and particularly preferably 5 ≦ E _OH ≦ 40. Most preferably, 10 ≦ E _OH ≦ 40. When _EOH is less than 1%, the structure of the block compound is extremely close. On the other hand, if the _EOH exceeds 49%, the emulsifying power may not be excellent. In the ^{1 H-NMR} spectrum measurement for determining the E _OH, using trifluoroacetic acetylated samples alkylene oxide adduct with trifluoroacetic anhydride.
N _2OH ^is the sum of all integral values attributed to the proton of methine groups bonded to the secondary hydroxyl group in the 1 H-NMR spectrum, all of the integration to be confirmed in a range of normal 5.1~5.5ppm It is the sum of values.

N _1OH is the sum of all integral values attributed to the protons of the methylene group to which the primary hydroxyl group is bonded in the ¹ H-NMR spectrum, and all integrals usually confirmed in the range of 4.3 to 4.7 ppm. It is the sum of values.
The weight average molecular weight of the alkylene oxide adduct of the present invention is not particularly limited, but is preferably 200 to 5000, more preferably 200 to 4000, still more preferably 200 to 3000, particularly preferably 200 to 2000, and most preferably. 200-1500. When the weight average molecular weight is less than 200, the emulsifiability of the alkylene oxide adduct may be low. When the weight average molecular weight is more than 5000, handling properties may be low. The measurement method of a weight average molecular weight is demonstrated in detail in an Example.

In the present invention, as a method for measuring the cloud point of the alkylene oxide adduct, the following measurement method is selected according to the cloud point range of the alkylene oxide adduct to be measured.
The clouding point of the alkylene oxide adduct of the present invention is usually a method in which a 1% by weight aqueous solution of an alkylene oxide adduct is prepared and heated to turbidize the solution once, and then gradually cooled to eliminate the turbidity. Use to measure. As said cloud point, Preferably it is 0-95 degreeC, More preferably, it is 0-90 degreeC, More preferably, it is 0-85 degreeC, Especially preferably, it is 0-80 degreeC, Most preferably, it is the range of 0-75 degreeC. If the cloud point is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point is higher than 95 ° C., the handling property of the alkylene oxide adduct may be low.

In the present invention, when the cloud point is less than 40 ° C. or more than 80 ° C., the cloud point may not be measurable or the measurement value may be unreliable even if it can be measured. A measurement method shown below, which is different from the cloud point measurement method, is selected, and the value obtained by the measurement method is defined as the cloud point.
When the cloud point is lower than 40 ° C., a 1% by weight aqueous solution of an alkylene oxide adduct may already be cloudy at room temperature and may not be measured. Therefore, when the said cloud point is less than 40 degreeC, let the cloud point of an alkylene oxide adduct be the value measured by the butyl diglycol method (BDG method) demonstrated in detail in a following example. The cloud point of the alkylene oxide adduct measured by the BDG method is preferably 0 to 95 ° C, more preferably 20 to 95 ° C, still more preferably 20 to 90 ° C, particularly preferably 20 to 85 ° C, and most preferably 20 to 80 ° C. If the cloud point measured by the BDG method is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point measured by the BDG method exceeds 95 ° C., the handling property of the alkylene oxide adduct may be low.

On the other hand, when the cloud point of a 1% by weight aqueous solution of an alkylene oxide adduct is higher than 80 ° C., the cloud point of the alkylene oxide adduct is determined by a method using a potassium sulfate aqueous solution as described in detail in the following examples (potassium sulfate). Method). The cloud point of the alkylene oxide adduct measured by the potassium sulfate method is preferably 0 to 95 ° C, more preferably 20 to 95 ° C, still more preferably 20 to 90 ° C, particularly preferably 20 to 85 ° C, and most preferably 20 ~ 80 ° C. When the cloud point measured by the potassium sulfate method is less than 0 ° C., the emulsifiability of the alkylene oxide adduct may be low. On the other hand, when the cloud point measured by the potassium sulfate method is more than 95 ° C., the handling property of the alkylene oxide adduct may be low.
Another alkylene oxide adduct of the present invention (hereinafter sometimes referred to as an alkylene oxide adduct B) is an alkylene oxide adduct described above (hereinafter referred to as an alkylene oxide adduct B). Oxide adduct A.) is an alkylene oxide adduct obtained by supplying one kind of alkylene oxide selected from ethylene oxide and propylene oxide to the addition reaction.

The alkylene oxide adduct B is
The following general formula (2):
RO-[(PO) p / (EO) q]-(AO) r-H (2)
(However, R represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO is an oxypropylene group, EO is an oxyethylene group, AO Represents one kind of oxyalkylene group selected from an oxyethylene group and an oxypropylene group, p, q and r represent the average number of moles added, p = 1 to 30, q = 1 to 50 and r = 1 to 50. [(PO) p / (EO) q] is a polyoxyalkylene group formed by random addition of p mol of PO and q mol of EO.) It is.

The difference in structure between the alkylene oxide adduct A and the alkylene oxide adduct B is that, in the alkylene oxide adduct A, the polyoxyalkylene group formed by random addition is terminated, whereas the alkylene oxide addition is terminated. In the product B, after the polyoxyalkylene group formed by random addition, a (poly) oxyalkylene group in which one oxyalkylene group selected from oxyethylene group and oxypropylene group is added at an average addition mole number r is added. It is a point that has become a structure. This (poly) oxyalkylene group is obtained by addition reaction of alkylene oxide selected from ethylene oxide and propylene oxide.
The alkylene oxide that undergoes an addition reaction with respect to the alkylene oxide adduct A may be any one of ethylene oxide and propylene oxide, but ethylene oxide is preferred because of its excellent emulsifying power and thickening performance. Therefore, oxyethylene group is preferable as AO in the general formula (2).

The average addition mole number r of AO is 1-50 normally, Preferably it is 1-40, More preferably, it is 1-30, More preferably, it is 1-25, Most preferably, it is 1-20, Most preferably, it is 1-15. If the average added mole number of AO is less than 1, the emulsifying power may not be sufficient. On the other hand, when the average added mole number of AO is more than 50, handling properties may be low.
Also in the alkylene oxide adduct B, the randomization index E _r , the percentage E _EO-R of the oxyethylene group directly bonded to the R group, the percentage of the oxyethylene group directly bonded to the terminal hydroxyl group E _EO-OH , The terminal hydroxyl group secondaryization ratio E _{OH and the} like are preferably in a specific range, similar to the alkylene oxide adduct A described above.

The randomization index E _r (%) of the alkylene oxide adduct B and the percentage E _EO-R (%) of the EO group directly bonded to the R group are preferably in the same range as the alkylene oxide adduct A.
The range of the percentage E _EO-OH (%) of the EO group directly bonded to the terminal hydroxyl group of the alkylene oxide adduct B depends on whether AO is an oxyethylene group or an oxypropylene group.

When AO is an oxyethylene group, E _{EO- OH} (%) is usually 70 ≦ E _EO-OH ≦ 100, preferably 75 ≦ E _EO-OH ≦ 100, more preferably 80 ≦ E _EO-OH ≦. 100, particularly preferably 85 ≦ E _EO-OH ≦ 100, most preferably 90 ≦ E _EO-OH ≦ 100. If _EO-OH is less than 70%, the emulsifying power may not be excellent.
When AO is an oxypropylene group, E _{EO- OH} (%) is usually 0 ≦ E _EO-OH ≦ 30, preferably 0 ≦ E _EO-OH ≦ 25, more preferably 0 ≦ E _{EO—. OH} ≦ 20, particularly preferably 0 ≦ E _EO—OH ≦ 15, most preferably 0 ≦ E _EO—OH ≦ 10. If _EO-OH is more than 30%, the emulsifying power may not be excellent.

The degree of secondaryization E _OH (%) of the terminal hydroxyl group of the alkylene oxide adduct B differs depending on whether AO is an oxyethylene group or an oxypropylene group.
When AO is an oxyethylene group, E _OH (%) is usually 0 ≦ E _OH ≦ 30, preferably 0 ≦ E _OH ≦ 25, more preferably 0 ≦ E _OH ≦ 20, particularly preferably 0 ≦ E. _OH ≦ 15, most preferably 0 ≦ E _OH ≦ 10. If E _OH (%) is more than 30%, fluidity at low temperatures may not be excellent.

When AO is an oxypropylene group, E _OH (%) is usually 70 ≦ E _EO-OH ≦ 100, preferably 75 ≦ E _EO-OH ≦ 100, more preferably 80 ≦ E _EO-OH ≦. 100, particularly preferably 85 ≦ E _EO-OH ≦ 100, most preferably 90 ≦ E _EO-OH ≦ 100. If E _OH (%) is 70% or less, fluidity at low temperatures may not be excellent.
The weight average molecular weight of the alkylene oxide adduct B is not particularly limited. For example, it is preferably 200 to 8000, more preferably 200 to 6000, still more preferably 200 to 4000, particularly preferably 200 to 3000, and most preferably. 200-2000. When the weight average molecular weight of the alkylene oxide adduct B is less than 200, the emulsifying power of the alkylene oxide adduct B may be low. On the other hand, when the weight average molecular weight of the alkylene oxide adduct B is more than 8000, handling properties may be inferior.
The cloud point of the alkylene oxide adduct B is the same as that described for the cloud point of the alkylene oxide adduct A.

[Uses of alkylene oxide adducts]
The alkylene oxide adduct obtained by the production method of the present invention and / or the alkylene oxide adduct of the present invention is, for example, a liquid or powder detergent for clothing, household detergent, kitchen detergent, solid detergent, shampoo, machine / Detergents such as metal detergents, antifoaming agents, antifoaming agents, lubricants, textile oil agents, paper agents, deresinating agents, deinking agents, degreasing agents, water reducing agents, flocculants, dispersants, emulsion polymerization agents, In various uses such as an emulsifier, a solubilizer, a suspending agent, a thickener, a gelling agent, an antistatic agent, and a surface treatment agent, it can be used as an essential component.
Hereinafter, the case where the use is an emulsifier, a dispersant, and a cleaning agent will be described in detail.

(emulsifier)
The emulsifier of the present invention comprises the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component. The emulsifier of the present invention exhibits an emulsifying action in which one of liquids that are not mixed with each other is made into fine particles and dispersed in the other, and generally also functions as a solubilizer. An emulsion is obtained by this emulsifying action and can be used for emulsion polymerization and the like.
Examples of the combination of liquids that do not mix with each other include a combination of water and a liquid organic material such as an oily material. In this case, the emulsion obtained using the emulsifier may be O / W type or W / O type.

The liquid organic substance may be naturally derived, synthetically derived or a mixture thereof, and may be either hydrophilic or lipophilic.
The lipophilic liquid organic substance is not particularly limited, and examples thereof include orange oil, pine root oil, brackish oil, eucalyptus oil, lemon oil, butterfly leaf oil, bergamot oil, rosemary oil, patchouli oil, rose oil, Perfumes such as menthol oil, peppermint oil, lavender oil, pinene, limonene, myrcene, heptanal, octanal, cyclamenaldehyde, isobutyl acetate, anisole, menthone; dimethyl silicone, amino silicone, epoxy silicone, carboxyl silicone, methyl hydrogen silicone, etc. Silicone; mineral oil such as asphalt, kerosene, petroleum jelly, mineral turpentine, spindle oil, gasoline, fluid paffin, machine oil, naphthenic oil, naphtha; beef tallow, lard, corn oil, soybean oil, rapeseed oil, olive Animal and vegetable oils such as castor oil, palm oil and coconut oil; higher alcohols such as lauryl alcohol, stearyl alcohol and oleyl alcohol; organic solvents such as toluene, xylene, benzene, carbon tetrachloride, cyclohexane and trichlorofluoroethane; butyl stearate And esters such as isopropyl palmitate; fatty acids such as stearic acid and oleic acid, and the like may be used alone or in combination of two or more.

The emulsifier of this invention may contain other surfactant other than the alkylene oxide adduct demonstrated above. The other surfactants may be any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. More than one species may be used in combination. Specific examples of such other surfactants are shown in the following description of the cleaning agent.
The emulsifier of the present invention includes water-soluble polymers such as polyethylene glycol, polyethylene oxide, cellulose ether, polyvinyl alcohol, polyvinyl pyrrolidone, gum arabic, guar gum and xanthan gum; hydrotropes such as ethanol and ethylene glycol; phosphoric acid, acetic acid and lactic acid Further, it may further contain an acid such as citric acid, succinic acid, hydrochloric acid or sulfuric acid.

The blending ratio of the alkylene oxide adduct described above contained in the emulsifier of the present invention is not particularly limited, but is preferably 5 to 100% by weight of the total emulsifier, more preferably 20 to 100% by weight, and still more preferably. It is 30 to 100% by weight, particularly preferably 40 to 100% by weight, and most preferably 40 to 95% by weight. If the blending ratio of the alkylene oxide adduct contained in the emulsifier is less than 5% by weight, the emulsifying action may not be sufficiently exhibited.
The blending ratio of the emulsifier of the present invention in the emulsion obtained by blending the emulsifier of the present invention is not particularly limited, but is preferably 1 to 50% by weight of the whole emulsion, more preferably 1 to 40% by weight, and further It is preferably 1 to 30% by weight, particularly preferably 5 to 30% by weight, and most preferably 5 to 20% by weight. When the blending ratio of the emulsifier of the present invention is less than 1% by weight, the emulsifying effect may not be obtained because the emulsifier is too little. On the other hand, if the blending ratio of the emulsifier of the present invention is more than 50% by weight, an emulsifying effect corresponding to a large blending amount cannot be obtained, which may be economically disadvantageous.

The use of the emulsifier of the present invention is not particularly limited, but for example, emulsion polymerization use; fragrance use used in rooms, toilets, cars, etc .; cosmetic use such as shampoo, rinse, permanent, etc .; car wax, car wash machine Polishing for wax, tire / leather wax, coating agent, bumper wax, etc .; for mold release between tire bladder and inner liner, for aluminum die-casting, sandals, men's shoes, women's shoes, sports shoe urethane Mold release application for soles, food packaging plastics, etc .; lubricant application; coating agent application; synthetic resin application; rubber industry application; detergent industry application; metal processing application; antifoaming agent application; Used as a usage.
Various monomers used when the emulsifier of the present invention is used for emulsion polymerization are not particularly limited. Monomers: carboxyl group-containing monomers such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid; vinylidene chloride; vinyl acetate; methyl (meth) acrylate, ethyl (meth) acrylate, n (Meth) acrylic such as -butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, β-carboxyethyl acrylate, etc. Acid ester monomer; , Styrene monomers such as α-methylstyrene and chlorostyrene; acrylamide monomers such as acrylamide, substituted acrylamide, methacrylamide and substituted methacrylamide; N-phenylmaleimide, N- (2-chlorophenyl) maleimide, N -Maleimide monomers such as cyclohexylmaleimide and N-laurylmaleimide, and the like may be used, or one or more may be used in combination.

(Dispersant)
The dispersant of the present invention contains the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component. The dispersant of the present invention is mixed with various powders to enhance its dispersibility.
The various powders may be any powder composed of any one of an inorganic compound, an organic compound, and a mixture of an inorganic compound / organic compound, and is not particularly limited. For example, carbon black; montmorillonite, beidellite, nontronite , Saponite, hectorite, sauconite, stevensite, etc .; divermiculite, trivermiculite, etc. vermiculite; halloysite, kaolinite, enderite, dickite, nacrite, chrysotile, etc. kaolin; Pyrosilicates such as light, clintonite, muscovite, biotite, phlogopite, synthetic mica, fluorine mica, paragolite, phlogopite, lepidrite, tetrasilic mica, teniolite; antigolite, etc. Jamite; Chlorite such as donpasite, sudstone, kukkaite, clinochlore, chamosite, chlorite, and nanthite; Piolite-palygoskite such as sepiolite and palygorskite; , Sulfates such as barium sulfate; metal oxides such as silica, alumina, magnesium oxide, antimony trioxide, titanium oxide, white carbon, and iron oxide; metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and iron hydroxide Carbon black; Graphite; Potassium oleate, sodium oleate, potassium dodecanoate, sodium dodecanoate, beef tallow fatty acid sodium, beef tallow fatty acid potassium, coconut oil fatty acid sodium, coconut oil fatty acid potassium, etc. Fatty acid soap, magnesium laurate, calcium laurate, zinc laurate, magnesium myristate, calcium myristate, zinc myristate, magnesium palmitate, calcium palmitate, zinc palmitate, magnesium stearate, calcium stearate, zinc stearate, tri Metal soap such as aluminum octadecanoate, aluminum dioctadecanoate, aluminum monooctadecanoate, calcium octadecanoate, zinc octadecanoate, magnesium octadecanoate, barium octadecanoate; paraffin wax, microcristan wax, candelilla wax, carnauba wax, rice wax , Fischer-Tropsch wax, polyethylene wax, montan wax, honey Wax such as lauric acid amide, stearic acid amide, oleic acid amide, hydrogenated castor oil, 12-hydroxystearic acid, etc .; Sumithion; parathion; methyl methacrylate resin, butyl methacrylate resin, ethyl acrylate resin, butyl acrylate resin, Modified acrylic resins (for example, silicone-modified acrylic resins, vinyl chloride resin-modified acrylic resins, acrylic-urethane resins, etc.), acrylic resins such as ethylene-ethyl acrylate copolymers; polycarbonate resins; fluorinated resins (ETFE, PVDF); polystyrene Resin, chloropolystyrene resin, poly-α-methylstyrene resin, styrene-butadiene copolymer, styrene-vinyl chloride copolymer, styrene-vinyl acetate copolymer, styrene-maleic acid copolymer, styrene-acrylic Acid ester copolymers (for example, styrene-methyl acrylate copolymer, styrene-ethyl acrylate copolymer, styrene-butyl acrylate copolymer, styrene-octyl acrylate copolymer, styrene-phenyl acrylate copolymer) Polymer), styrene-methacrylic acid ester copolymer (for example, styrene-methyl methacrylate copolymer, styrene-ethyl methacrylate copolymer, styrene-phenyl methacrylate copolymer, etc.), styrene-α-chloro. Styrenic resins such as methyl acrylate copolymer and styrene-acrylonitrile-acrylic acid ester copolymer (monopolymer or copolymer containing styrene or styrene substitution product); vinyl chloride resin; polyvinylidene chloride resin; rosin modification Maleic resin; phenolic resin; epoxy resin; Resin; Polyolefin resin such as polyethylene resin and polypropylene resin; Polybutadiene; Ionomer resin, Polyurethane resin; Silicone resin; Ketone resin; Xylene resin; Polyvinyl butyral resin; Polyamide resin; Modified polyphenylene oxide resin, etc. You may use together 1 type, or 2 or more types.

The average particle size of various powders is not particularly limited, but is preferably 0.1 to 200 μm, more preferably 0.1 to 100 μm, still more preferably 0.1 to 50 μm, particularly preferably 0.1 to 40 μm, Most preferably, it is 0.1-30 micrometers. If the average particle size of the various powders exceeds 200 μm, the dispersion effect may not be excellent.
The specific gravity of various powders is not particularly limited, but is preferably 0.5 to 5, more preferably 0.5 to 4.5, still more preferably 0.5 to 4, and particularly preferably 0.6 to 3. 5, most preferably 0.7-3. If the specific gravity of various powders is less than 0.5, the dispersion effect may not be excellent. On the other hand, when the specific gravity of various powders exceeds 5, the dispersion effect may not be excellent.

  The blending ratio of the dispersant of the present invention is not particularly limited. For example, it is preferably 1 to 70 parts by weight, more preferably 1 to 60 parts by weight, and still more preferably 5 to 100 parts by weight of various powders. 60 parts by weight, particularly preferably 5 to 50 parts by weight, further particularly preferably 5 to 40 parts by weight, and most preferably 5 to 30 parts by weight. When the blending ratio of the dispersing agent is less than 1 part by weight, the dispersing effect may not be obtained because the dispersing agent is too small. On the other hand, if the blending ratio of the dispersant is more than 70 parts by weight, a dispersing effect corresponding to a large blending amount cannot be obtained, which may be economically disadvantageous.

(Washing soap)
The cleaning agent of the present invention comprises the alkylene oxide adduct obtained by the above production method and / or the alkylene oxide adduct as an essential component.
The cleaning agent of the present invention may further contain water because of its good water dispersibility when used in an aqueous system. The mixing ratio of water is not particularly limited, but is preferably 1 to 10000 parts by weight, more preferably 10 to 1000 parts by weight, and still more preferably 20 to 1000 parts by weight with respect to 100 parts by weight of the alkylene oxide adduct. Especially preferably, it is 30-1000 weight part, Most preferably, it is 60-1000 weight part. If the blending ratio of water is less than 1 part by weight, the detergency may be reduced. On the other hand, when the blending ratio of water is more than 10,000 parts by weight, handling properties may be inferior.

The cleaning agent of the present invention may contain other surfactants other than the alkylene oxide adduct described above. The other surfactants may be any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants. More than one species may be used in combination.
Examples of such other surfactants that are nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene cetyl ether and polyoxyethylene lauryl ether; polyoxyethylene nonylphenyl ether, polyoxyethylene Polyoxyalkylene alkyl phenyl ethers such as octylphenyl ether; polyoxyalkylene fatty acid esters such as polyoxyethylene monolaurate and polyoxyethylene monooleate; sorbitan fatty acid esters such as sorbitan monopalmitate and sorbitan monooleate; polyoxy Polyoxyalkylene sorbitan fatty acid esters such as ethylene sorbitan monostearate and polyoxyethylene sorbitan monooleate; glycerol monostearate Glycerol fatty acid esters such as glycerol monopalmitate, glycerol monolaurate; polyoxyalkylene hydrogenated castor oil; polyoxyalkylene sorbitol fatty acid ester; polyglycerol fatty acid ester; alkyl glycerol ether; Sucrose fatty acid ester; polyoxyalkylene alkylamine; oxyethylene-oxypropylene block polymer; ethylene oxide adduct of 5,8-dimethyl-6-dodecyne-5,8-diol (addition mole number: 37 to 43), 2, 5,8,11-Tetramethyl-6-dodecin-5,8-diol ethylene oxide (addition mole number 7-13) / propylene oxide (addition mole number 37-43) with block type 2,5,8,11-tetramethyl-6-dodecin-5,8-diol ethylene oxide (addition mole number 17-23) / propylene oxide (addition mole number 17-23) random type adduct, etc. Polyoxyalkylene acetylenic diol ether is mentioned, You may use 1 type (s) or 2 or more types together.

Examples of such other anionic surfactants include fatty acid salts such as sodium oleate, potassium palmitate, triethanolamine oleate; sodium lauryl sulfate, ammonium lauryl sulfate, sodium stearyl sulfate, Alkyl sulfate salts such as sodium cetyl sulfate; polyoxyalkylene alkyl ether acetates such as polyoxyethylene tridecyl ether sodium acetate; alkyl benzene sulfonates such as sodium dodecylbenzene sulfonate; polyoxyalkylene alkyl ether sulfates; stearoyl methyl Higher fatty acid amide sulfonates such as taurine Na, lauroylmethyl taurine Na, myristoyl methyl taurine Na, palmitoyl methyl taurine Na; lauroyl N-acyl sarcosine salts such as sodium lucocin; alkyl phosphates such as sodium monostearyl phosphate; polyoxyalkylene alkyl ether phosphates such as sodium polyoxyethylene oleyl ether and sodium polyoxyethylene stearyl ether phosphate Salts; long-chain sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate and sodium dioctylsulfosuccinate; long-chain N-acyl glutamates such as sodium monosodium N-lauroylglutamate and disodium N-stearoyl-L-glutamate; Polyacrylic acid, polymethacrylic acid, polymaleic acid, polymaleic anhydride, copolymer of maleic acid and isobutylene, copolymer of maleic anhydride and isobutylene, maleic acid and Copolymer of isobutylene, copolymer of maleic anhydride and diisobutylene, copolymer of acrylic acid and itaconic acid, copolymer of methacrylic acid and itaconic acid, copolymer of maleic acid and styrene , Copolymer of maleic anhydride and styrene, copolymer of acrylic acid and methacrylic acid, copolymer of acrylic acid and methyl acrylate, copolymer of acrylic acid and vinyl acetate, acrylic Copolymers of acids and maleic acids, alkali metal salts (lithium salts, sodium salts, potassium salts, etc.) and alkaline earth metal salts (magnesium salts, calcium salts, etc.) of copolymers of acrylic acid and maleic anhydride , Polycarboxylates such as ammonium salts and amine salts; naphthalene sulfonic acid, alkyl naphthalene sulfonic acid, formalin of naphthalene sulfonic acid Condensates, formalin condensates of alkylnaphthalene sulfonic acids, and alkali metal salts (lithium salts, sodium salts, potassium salts, etc.), alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts and amine salts thereof Naphthalene sulfonates such as melamine sulfonic acid, alkyl melamine sulfonic acid, formalin condensate of melamine sulfonic acid, formalin condensate of alkyl melamine sulfonic acid, and alkali metal salts thereof (lithium salt, sodium salt, potassium salt, etc.) ), Alkaline earth metal salts (magnesium salts, calcium salts, etc.), ammonium salts, melamine sulfonates such as amine salts, etc .; lignin sulfonic acid, and alkali metal salts thereof (lithium salts, sodium salts, potassium salts, etc.) ), Alkaline earth metals (Magnesium salt, calcium salt, etc.), lignin sulfonic acid salts such as ammonium salts and amine salts and the like, may be alone or in combination of two or more.
Examples of such other cationic surfactants include alkyltrimethylammonium salts such as stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, and cetyltrimethylammonium bromide; dialkyldimethylammonium salts; trialkyls A methyl ammonium salt, an alkylamine salt, etc. are mentioned, You may use 1 type (s) or 2 or more types together.

Examples of such other surfactants that are amphoteric surfactants include 2-undecyl-N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide. Imidazoline-based amphoteric surfactants such as -1-carboxyethyloxy disodium salt; 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine, sulfobetaine, etc. Betaine amphoteric surfactants of the above; amino acid-type amphoteric surfactants such as N-laurylglycine, N-lauryl β-alanine, N-stearyl β-alanine, etc. Good.
The cleaning agent of the present invention includes chelating agents such as nitrilotriacetate, citrate and polyacrylate; inorganic builders such as carbonate and silicate; alkaline compounds such as sodium hydroxide and potassium hydroxide; Alkanolamines such as monoethanolamine and diethanolamine; Hydrotropes such as ethanol and ethylene glycol; Enzymes; Fluorescent agents; Dyes; Fragrances; Disinfectants; Preservatives; Moisturizers; Good. When other components are blended, it is preferable that the cleaning agent is a liquid cleaning agent because the compatibility of each component constituting the cleaning agent is good and the cleaning power may be improved.

  The cleaning agent of the present invention can be used for cleaning various objects depending on purposes. The object to be cleaned is not particularly limited. For example, a cleaning agent for clothing that cleans clothes, etc .; a cleaning agent for hair or skin, nails, hair that cleans eyes, or a body cleaner; dishes, cooking utensils, vegetables, etc. Kitchen cleaners; residential cleaners that clean walls, floors, tatami mats, furniture, ceilings, roofs, etc .; hard surface cleaners that clean toilets, bathtubs, bathrooms, ventilation fans, microwave ovens, sinks, etc .; automatic dishwashing Machine cleaners; textile cleaners; industrial cleaners for cleaning automobiles, aircraft, vehicles, machine parts, and the like.

Below, the Example of this invention is described concretely with the comparative example. The present invention is not limited to these examples.
[ ^13C -NMR method]
About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, about 0.5 ml of deuterated chloroform is added as a deuterated solvent and dissolved, and then a ¹³ C-NMR measuring apparatus (AVANCE400, 100 MHz manufactured by BRUKER) is used. Measured with

^[1 H-NMR method and 2 quaternizing rate calculation method]
About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated chloroform is added and dissolved as a deuterated solvent. Thereafter, about 0.1 ml of trifluoroacetic anhydride was added to prepare an analytical sample, which was measured with a ¹ H-NMR measuring apparatus (AVANCE400, 400 MHz manufactured by BRUKER).

(Weight average molecular weight)
The alkylene oxide adduct was dissolved in tetrahydrofuran so that the nonvolatile content concentration was about 0.2% by mass, and then gel permeation chromatography (GPC) was measured under the following measurement conditions. Subsequently, a calibration curve was prepared from the GPC measurement result of polyethylene glycol having a known molecular weight, and the weight average molecular weight was calculated.
(Measurement condition)
Device name: HLC-8220 (manufactured by Tosoh Corporation)
Column: KF-G, KF-402HQ, KF-403HQ each connected in series (all manufactured by Shodex)
Eluent: Tetrahydrofuran Injection volume: 10 μl
Eluent flow rate: 0.3 ml / min Temperature: 40 ° C

[Measurement of cloud point]
A 1% by weight aqueous solution of an alkylene oxide adduct was prepared, heated to make the solution turbid, and gradually cooled to measure the temperature T at which the turbidity disappeared. Here, when it was in the range of T = 40 to 80 ° C., it was regarded as the cloud point of the alkylene oxide adduct.
In the alkylene oxide adducts of Examples 7 and 9 and Comparative Examples 8 and 10, since the above temperature range was satisfied, the temperature T at which the turbidity disappeared upon cooling was directly used as the cloud point.
In the alkylene oxide adducts of Examples 1 to 6 and Comparative Examples 1 to 7, T was less than 40 ° C., so the value measured by the following butyl diglycol method (BDG method) is taken as the cloud point. In Example 8 and Comparative Example 9, since T was higher than 80 ° C., the value measured by the following method (potassium sulfate method) using an aqueous potassium sulfate solution as a solvent was defined as the cloud point.

(BDG method)
A cloud point test solution was prepared by adding an alkylene oxide adduct to a 25% by weight aqueous solution of n-butyl diglycol (also known as 2- (2-butoxyethoxy) ethanol, diethylene glycol mono-n-butyl ether). In that case, it adjusted so that the density | concentration of the alkylene oxide adduct in a cloud point test liquid might be 10 weight%. Subsequently, the cloud point test solution was once clouded by heating, and the temperature at which the cloud point disappeared gradually after cooling was defined as the cloud point.

(Potassium sulfate method)
A cloud point test solution was prepared by adding an alkylene oxide adduct to a 5 wt% aqueous solution of potassium sulfate. At that time, the concentration of the alkylene oxide adduct in the cloud point test solution was adjusted to 1% by weight. Subsequently, the cloud point test solution was once clouded by heating, and the temperature at which the cloud point disappeared gradually after cooling was defined as the cloud point.

[Example 1]
Into a 1 L autoclave connected with ethylene oxide and propylene oxide supply lines, 100 g of lauryl alcohol (molecular weight 186) and 0.3 g of potassium hydroxide were charged, and then the inside of the autoclave was purged with nitrogen and stirred. Vacuum dehydration was performed at 80 ° C.
Subsequently, after raising the temperature to 130 ° C., ethylene oxide and propylene oxide were simultaneously fed while maintaining the reaction temperature of 145 ± 5 ° C. and the reaction pressure of 3.5 ± 0.5 kg / cm ² . With ethylene oxide, the supply was started from a supply rate of 10 g / h, and the supply amount was gradually increased to complete the supply at a final supply rate of 70 g / h, and a total amount of 118 g was supplied in about 170 minutes. In addition, with propylene oxide, the supply was started at a supply rate of 70 g / h, the supply amount was gradually decreased, and the supply was completed at a final supply rate of 10 g / h, and a total amount of 110 g was supplied in about 170 minutes.

The weight ratio [EO / PO] _T0 of ethylene oxide and propylene oxide supplied at the start of supply was 0.39. The weight ratio [EO / PO] _T100 of ethylene oxide and propylene oxide supplied at the end of the supply was 6.2. The supply of ethylene oxide and propylene oxide satisfied the condition of 0.9 <[EO / PO] _T2 / [EO / PO] _T1 <1.2. FIG. 1 shows a schematic diagram showing the change over time from the start of supply to the end of supply for the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Example 1. FIG. FIG. 1 shows that the supply time and the weight ratio [EO / PO] have a linear function relationship.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.

Propylene oxide addition mole number (q) of the obtained alkylene oxide adduct was 3, and ethylene oxide addition mole number (p) was 7.
The integrated values of ¹³ C-NMR spectrum (FIG. 4) and ¹ H-NMR spectrum (FIG. 5) of the resulting alkylene oxide adduct were read, and N _{PO-PO 4} , N _{PO 2} , N _EO-R , N _R , N _{EO-OH, N PO-OH} , N 1OH, N 2OH , each 2.59,7.36,0.50,1.46,1.00,0.22,4.19,1.00 met It was. E _r , E _EO-R , E _EO-OH , and E _OH calculated from these integral values were 26.0, 34.2, 82.0, and 19.3, respectively. The obtained alkylene oxide adduct had a weight average molecular weight of 680. Regarding the cloud point, first, an aqueous solution containing 1% by weight of an alkylene oxide adduct was prepared, but it was already cloudy at room temperature, so that the cloud point was 58 ° C. as measured by the BDG method.

[Examples 2 to 5]
In Examples 2 to 5, an alkylene oxide adduct was obtained in the same manner as in Example 1 except that the raw materials were changed as shown in Table 1 in Example 1, and the physical properties and the like were the same as in Example 1. evaluated. The results are shown in Table 1.

Example 6
After charging 100 g of lauryl alcohol (molecular weight 186) and 0.3 g of potassium hydroxide in a 1 L autoclave connected to a 0.5 L mixing tank, the inside of the autoclave was purged with nitrogen and stirred at 80 ° C. Vacuum dehydration was performed.
Next, after raising the temperature to 130 ° C., while maintaining the reaction temperature of 145 ± 5 ° C. and the reaction pressure of 3.5 ± 0.5 kg / cm ² , the mixed solution of ethylene oxide and propylene oxide was divided into three times in the mixing tank Prepared and supplied. First, in the first time, a liquid in which 18 g of ethylene oxide and 68 g of propylene oxide were mixed was supplied over 60 minutes. Next, in the second time, a solution in which 35 g of ethylene oxide and 30 g of propylene oxide were mixed was supplied in 40 minutes, and in the last third time, a solution in which 65 g of ethylene oxide and 12 g of propylene oxide were mixed was supplied in 55 minutes. . The total amount of ethylene oxide supplied was 118 g, and the total amount of propylene oxide supplied was 110 g. The total time required for supplying ethylene oxide and propylene oxide was 155 minutes.

The weight ratio [EO / PO] _T0 of ethylene oxide and propylene oxide supplied at the start of supply was 0.27. The weight ratio [EO / PO] _T100 of ethylene oxide and propylene oxide supplied at the end of the supply was 5.3. The supply of ethylene oxide and propylene oxide satisfied the condition of 0.8 <[EO / PO] _T2 / [EO / PO] _T1 <10. FIG. 2 shows a schematic diagram showing the change over time from the start of supply to the end of supply for the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Example 6. FIG. 2 shows that the supply time and the weight ratio [EO / PO] have a step function relationship.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.

The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 7, and a propylene oxide addition mole number (q) of 3.
E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct are 27.1 and 31. 31, respectively. 2, 82.1 and 20.8. The resulting alkylene oxide adduct had a weight average molecular weight of 682. As for the cloud point, first, a 1% by weight aqueous solution of an alkylene oxide adduct was prepared. Since it was already cloudy at room temperature, the cloud point was 57 ° C. as measured by the BDG method.

Example 7
After charging 300 g of the alkylene oxide adduct obtained in Example 1 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 99 g of ethylene oxide was supplied in about 40 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 7, a propylene oxide addition mole number (q) of 3, and an ethylene oxide addition mole number (r) of 3.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct are 26.1 and 34. respectively. 2, 98.2, and 3.5. The resulting alkylene oxide adduct had a weight average molecular weight of 755. The cloud point was 79 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

Example 8
After charging 300 g of the alkylene oxide adduct obtained in Example 1 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 189 g of ethylene oxide was supplied in about 80 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 7, a propylene oxide addition mole number (q) of 3, and an ethylene oxide addition mole number (r) of 7.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct are 26.1 and 34. respectively. It was 8, 99.1, 1.9. The resulting alkylene oxide adduct had a weight average molecular weight of 978. The cloud point was first measured by preparing a 1% concentration aqueous solution of an alkylene oxide adduct, but it did not become cloudy even when the temperature exceeded 80 ° C., so the cloud point was 68 ° C. as measured by the potassium sulfate method.

Example 9
After charging 300 g of the alkylene oxide adduct obtained in Example 3 and 1.0 g of potassium hydroxide in a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 130 g of ethylene oxide was supplied in about 60 minutes while maintaining the reaction temperature of 145 ± 5 ° C. and the reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 3, a propylene oxide addition mole number (q) of 2, and an ethylene oxide addition mole number (r) of 4.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 20.4 and 26. 3, 98.1 and 2.1. The resulting alkylene oxide adduct had a weight average molecular weight of 584. The cloud point was 74 ° C. as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 1]
After charging 100 g of lauryl alcohol (molecular weight 186) and 0.3 g of potassium hydroxide in a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., ethylene oxide and propylene oxide were simultaneously fed while maintaining the reaction temperature of 145 ± 5 ° C. and the reaction pressure of 3.5 ± 0.5 kg / cm ² . Ethylene oxide was supplied while maintaining a supply rate of 41 g / h, and a total amount of 118 g was supplied in about 170 minutes. Propylene oxide was supplied while maintaining a supply rate of 39 g / h, and a total amount of 110 g was supplied in about 170 minutes.

The weight ratio [EO / PO] _T0 of ethylene oxide and propylene oxide supplied at the start of supply was 1.1. The weight ratio [EO / PO] _T100 of ethylene oxide to propylene oxide supplied at the end of the supply was 1.1. FIG. 3 shows a schematic diagram showing the change over time from the start of supply to the end of supply for the weight ratio [EO / PO] of ethylene oxide and propylene oxide supplied in Comparative Example 1. FIG. 3 shows that the weight ratio [EO / PO] is at a constant value regardless of the supply time.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.

The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 3, and a propylene oxide addition mole number (q) of 7.
E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 20.1, 53. 5, 44.3 and 55.3. The resulting alkylene oxide adduct had a weight average molecular weight of 68.1. As for the cloud point, first, an aqueous solution containing 1% by weight of an alkylene oxide adduct was prepared. Since it was already cloudy at room temperature, the cloud point was 55 ° C. as measured by the BDG method.

[Comparative Examples 2 to 5]
In Comparative Examples 2 to 5, the alkylene oxide adducts were obtained in the same manner as in Comparative Example 1 except that the raw materials were changed as shown in Table 2 in Comparative Example 1, and the physical properties and the like were the same as in Comparative Example 1. evaluated. The results are shown in Table 2.

[Comparative Example 6]
After charging 100 g of lauryl alcohol (molecular weight 186) and 0.3 g of potassium hydroxide in a 1 L autoclave, the inside of the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., 110 g of propylene oxide was supplied in about 150 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . After aging until the internal pressure decreased and became constant, 118 g of ethylene oxide was supplied in about 150 minutes.

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct was a block adduct of PO and EO, the ethylene oxide addition mole number (p) was 7, and the propylene oxide addition mole number (q) was 3.

E _r , E _EO-R , E _EO-OH , E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 50.3, 0, 100.0 and 9.3. The resulting alkylene oxide adduct had a weight average molecular weight of 678. As for the cloud point, first, an aqueous solution containing 1% by weight of an alkylene oxide adduct was prepared. Since it was already cloudy at room temperature, the cloud point was 56 ° C. as measured by the BDG method.

[Comparative Example 7]
A 1 L autoclave was charged with 100 g of decanol (molecular weight 159) and 0.3 g of potassium hydroxide, and the autoclave was purged with nitrogen, followed by dehydration under reduced pressure at 80 ° C. with stirring.
Subsequently, after raising the temperature to 130 ° C., 109 g of propylene oxide was supplied in about 150 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . After aging until the internal pressure decreased and became constant, 138 g of ethylene oxide was supplied in about 150 minutes.

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 3 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture, and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The obtained alkylene oxide adduct was a block adduct of PO and EO, the ethylene oxide addition mole number (p) was 3, and the propylene oxide addition mole number (q) was 2.

E _r , E _EO-R , E _EO-OH , E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 50.1, 0, 100.0 and 9.3. The resulting alkylene oxide adduct had a weight average molecular weight of 415. Regarding the cloud point, first, an aqueous solution containing 1% by weight of an alkylene oxide adduct was prepared. Since it was already cloudy at room temperature, the cloud point was 51 ° C. as measured by the BDG method.

[Comparative Example 8]
After charging 300 g of the alkylene oxide adduct obtained in Comparative Example 1 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen and then dehydrated at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 99 g of ethylene oxide was supplied in about 40 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 7, a propylene oxide addition mole number (q) of 3, and an ethylene oxide addition mole number (r) of 3.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 20.2, 53. 5, 97.1, 4.1. The resulting alkylene oxide adduct had a weight average molecular weight of 753. The cloud point was 78 ° C as measured with a 1% strength aqueous solution of an alkylene oxide adduct.

[Comparative Example 9]
After charging 300 g of the alkylene oxide adduct obtained in Comparative Example 1 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen and then dehydrated at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 189 g of ethylene oxide was supplied in about 80 minutes while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 7, a propylene oxide addition mole number (q) of 3, and an ethylene oxide addition mole number (r) of 7.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 20.2, 53. 3, 98.3 and 2.7. The resulting alkylene oxide adduct had a weight average molecular weight of 980. The cloud point was first measured by preparing a 1% concentration aqueous solution of an alkylene oxide adduct, but it did not become cloudy even when the temperature exceeded 80 ° C., so the cloud point was 68 ° C. as measured by the potassium sulfate method.

[Comparative Example 10]
After charging 300 g of the alkylene oxide adduct obtained in Comparative Example 3 and 1.0 g of potassium hydroxide into a 1 L autoclave, the inside of the autoclave was purged with nitrogen and then dehydrated at 80 ° C. with stirring. It was.
Subsequently, after raising the temperature to 130 ° C., 130 g of ethylene oxide was supplied in about 60 minutes while maintaining the reaction temperature of 145 ± 5 ° C. and the reaction pressure of 3.5 ± 0.5 kg / cm ² .

After the supply of ethylene oxide was completed, while maintaining the reaction temperature, the mixture was aged until the internal pressure decreased and became constant, and cooled to 80 ° C. As a post-treatment, 9 g of a synthetic adsorbent (KYOWARD 700, Kyowa Chemical Industry Co., Ltd.) was added to the resulting reaction mixture and the mixture was stirred at 90 ° C. for 1 hour in a nitrogen stream, and then the catalyst was removed by filtration. Thus, an alkylene oxide adduct was obtained.
The resulting alkylene oxide adduct had an ethylene oxide addition mole number (p) of 3, a propylene oxide addition mole number (q) of 2, and an ethylene oxide addition mole number (r) of 4.

E _r , E _EO-R , E _EO-OH , and E _OH calculated from the integrated values of the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct were 19.3 and 58. respectively. It was 9, 97.5, 3.9. The resulting alkylene oxide adduct had a weight average molecular weight of 588. The cloud point was 75 ° C as measured with a 1% strength aqueous solution of an alkylene oxide adduct.
Using the alkylene oxide adducts of the present invention obtained in Examples 1 to 9 and the alkylene oxide adducts obtained in Comparative Examples 1 to 10, respectively, the following method was used to perform low temperature pour point (low temperature fluidity), emulsification Force and aqueous solution viscosity (thickening) were evaluated.

[Measurement of low temperature pour point (low temperature fluidity)]
It measured using the method based on the method of JISK2269. That is, 45 ml of alkylene oxide adduct taken in a test tube was heated to 45 ° C. and then cooled in a cooling bath using a cryogen. Each time the temperature dropped by 2.5 ° C., the test tube was removed from the cooling bath, and the temperature at which the alkylene oxide adduct stopped moving at all for 5 seconds was read. The smaller the value of the low temperature pour point, the better the low temperature fluidity.

(Measurement of emulsifying power)
4 g of alkylene oxide adduct was added to 40 g of xylene and 56 g of water, and the mixture was emulsified with stirring at 4500 rpm for 5 minutes using a TK homomixer (manufactured by Tokushu Kika Kogyo Co., Ltd.) at room temperature. The emulsified performance was evaluated by measuring the emulsified layer and the water separating layer after leaving the prepared emulsion in a 50 ° C. atmosphere for 1 hour. The emulsifying power is calculated by the following formula. The larger the emulsifying power, the better the emulsifying power.
Emulsifying power (%) = (amount of charged water-amount of water separation) (ml) / amount of charged water (ml) x 100

[Measurement of viscosity of aqueous solution (thickening)]
A 50 wt% alkylene oxide adduct was prepared and measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd .: BL type) in an atmosphere at 25 ° C. The greater the value of the aqueous solution viscosity, the better the thickening.

[Evaluation of emulsion stability]
A perfume emulsion composition was obtained by mixing 20 g of the polyalkylene oxide adduct, 100 g of lavender oil, and 400 g of ion-exchanged water. The appearance of the fragrance emulsion composition was confirmed after 30 ml of the fragrance emulsion composition taken in the screw tube was heated and stored in a thermostat at 50 ° C. for 168 hours. The evaluation criteria for emulsion stability are as follows.
A: The appearance after heating is the same as that at room temperature, and the emulsion stability is excellent.
X: Turbidity and separation occur in the appearance after cooling, and the emulsion stability is poor.

[Evaluation of dispersion stability]
10 g of the polyalkylene oxide adduct, 20 g of calcium carbonate (average particle size 5.0 μm), and 70 g of ion-exchanged water were mixed to obtain an aqueous dispersion of calcium carbonate. The appearance of the aqueous dispersion of calcium carbonate was confirmed after the aqueous dispersion of calcium carbonate was stored in a constant temperature bath at 50 ° C. for 24 hours for a 100 ml centrifuge tube. The evaluation criteria for dispersion stability are as follows.
O: The sediment of calcium carbonate is less than 10 ml.
X: The sediment of calcium carbonate is 10 ml or more.

[Evaluation of cleaning power]
A cleaning agent was prepared by mixing 0.03 g of an alkylene oxide adduct, 0.6 g of sodium metasilicate, and 299.37 water. Separately, a 100 mesh wire net with mineral oil adhered thereto was prepared, immersed in a cleaning agent, and washed for 2 minutes. The washed 100 mesh wire net was immersed in distilled water for 1 minute to perform rinsing, and the washing rate was calculated from the amount of oil removed before and after washing to evaluate the washing power. The detergency is calculated by the following formula. The greater the detergency value, the better the detergency.
Detergency (%) = (Amount of mineral oil adhering to 100 mesh wire mesh before washing−Amount of mineral oil adhering to 100 mesh wire mesh after washing) (g) / Amount of mineral oil adhering to 100 mesh wire mesh before washing (g) × 100
A: Detergency is 60% or more.
X: Detergency is less than 60%.
The evaluation results are shown in Table 3. The alkylene oxide adducts of Examples 1 and 6 correspond in basic structure to those of Comparative Examples 1 and 6. The alkylene oxide adduct of Example 2 corresponds to Comparative Examples 2 and 7, and Examples 3 to 5 correspond to Comparative Examples 3 to 5, respectively.

From the above evaluation results, Examples 1 and 6 are superior to Comparative Example 1 in emulsifying power and viscosity, and are superior in Comparative Example 6 to low-temperature fluidity. In Example 2, the emulsifying power and viscosity increase are superior to Comparative Example 2, and the low temperature fluidity is superior to Comparative Example 7. In Examples 3 to 5, the emulsifying power and the thickening are superior to the corresponding Comparative Examples 3 to 5, respectively. In Examples 7-9, the emulsifying power and the thickening are superior to the corresponding Comparative Examples 8-10.
Moreover, in Examples 1-9, it was excellent in emulsification stability, dispersion stability, and a detergency, and was excellent as an emulsifier, a dispersing agent, and a cleaning agent. On the other hand, Comparative Examples 1 to 10 were not excellent in emulsion stability, dispersion stability and detergency.

Claims (16)

The following general formula (A):
ROH (A)
(R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of either a linear or branched structure.)
A process for producing an alkylene oxide adduct comprising a step of simultaneously supplying ethylene oxide and propylene oxide to an alcohol represented by
The start of supply of ethylene oxide and propylene oxide is T0, the end of supply of ethylene oxide and propylene oxide is T100, and the times T1 and T2 between T0 and T100 are T0 <T1 <T2 <T100 and (T2-T1 ) /T100=0.01
The weight ratio of ethylene oxide to propylene oxide supplied at each time point of T0, T100, T1, and T2 is set to [EO / PO] _T0 , [EO / PO] _T100 , [EO / PO] _T1 and [EO / PO] A method for producing an alkylene oxide adduct that simultaneously satisfies the following formulas (B) to (D) as _T2 .
0 <[EO / PO] _T0 <1 (B)
1 <[EO / PO] _T100 <100 (C)
0.8 <[EO / PO] _T2 / [EO / PO] _T1 < 1.2 (D) The manufacturing method of the alkylene oxide adduct of Claim 1 which further satisfies the following numerical formula (B-1) and (C-1).
0.1 <[EO / PO] _T0 <0.5 (B-1)
2 <[EO / PO] _T100 <20 (C-1) The manufacturing method of the alkylene oxide adduct of Claim 1 or 2 which further satisfies the following numerical formula (D-1).
0.9 <[EO / PO] _T2 / [EO / PO] _T1 <1.2 (D-1) The method for producing an alkylene oxide adduct according to any one of claims 1 to 3, further comprising a step of adding one of alkylene oxides selected from ethylene oxide and propylene oxide to cause an addition reaction after the step.   The method for producing an alkylene oxide adduct according to claim 4, wherein the alkylene oxide is ethylene oxide. The following general formula (1):
RO-[(PO) p / (EO) q] -H (1)
(However, R represents an alkyl group or alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO represents an oxypropylene group, and EO represents an oxyethylene group. P and q denote the average number of moles added, respectively, where p = 1 to 20 and q = 1 to 50. [(PO) p / (EO) q] is p moles of PO and q moles. This is a polyoxyalkylene group formed by random addition of EO.)
An alkylene oxide adduct represented by the formula:
Based on the charts obtained by measuring the ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the alkylene oxide adduct, N _PO-PO , N _PO2 , N _EO-R , N _R , N _EO- defined below respectively. reading _{OH, N PO-OH,} the _{N 1OH} and _{N 2OH,}
N _PO-PO : Sum of integral values of ¹³ C-NMR spectrum attributed to primary carbon of PO-PO bonded PO N _PO2 : Integrated value of ¹³ C-NMR spectrum attributed to secondary carbon of PO Sum N _EO-R : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly ether-bonded to R group N _R : Integral of ¹³ C-NMR spectrum attributed to α-position carbon of R group Sum of values N _EO-OH : Sum of integral values of ¹³ C-NMR spectrum attributed to carbon of EO directly bonded to terminal hydroxyl group N _PO-OH : To carbon of PO directly bonded to terminal hydroxyl group sum _{N 1 OH} of the integrated value of the ¹³ C-NMR spectrum attributed: primary sum _{N 2OH} of ¹ H-NMR integral value of the spectrum attributable to protons bound methylene group of the hydroxyl group: coupling a secondary hydroxyl group The sum of the integral values of the ¹ H-NMR spectrum assigned to the proton of the methine group and the obtained reading values were calculated by the following formulas (I) to (IV):
_Er (%) = 100 * _NPO-PO / ( _NPO-PO + _NPO2 ) (I)
E _EO-R (%) = 100 × N _EO-R / N _R (II)
E _EO-OH (%) = 100 × N _EO-OH / (N _EO-OH + N _PO—OH ) (III)
_{E OH (%) = 100 ×} N 2OH / (N 1OH + N 2OH) (IV)
Randomized exponent E _r obtained by _{substituting,} the percentage E _EO-R oxyethylene groups connected directly to the R _group, oxyethylene group terminal hydroxyl groups are directly connected percent E _EO-OH, and the terminal hydroxyl group An alkylene oxide adduct in which the parameters of the secondaryization rate E _OH satisfy the following formulas (IA) to (IV-A), respectively.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 49 (II-A)
51 ≦ E _EO-OH ≦ 99 (III-A)
1 ≦ E _OH ≦ 49 (IV-A)   The alkylene oxide adduct according to claim 6, wherein p = 1 to 10 and q = 1 to 30.   The alkylene oxide adduct according to claim 6 or 7, wherein R has 8 to 20 carbon atoms.   The alkylene oxide adduct according to any one of claims 6 to 8, having a weight average molecular weight of 200 to 5,000.   The alkylene oxide adduct according to any one of claims 6 to 9, wherein a cloud point measured by a butyl diglycol method (BDG method) is 0 to 95 ° C. The alkylene oxide adduct according to any one of claims 6 to 10, further satisfying the following formulas (IB) to (IV-B):
10 ≦ E _r ≦ 35 (IB)
10 ≦ E _EO-R ≦ 40 (II-B)
65 ≦ E _EO-OH ≦ 95 (III-B)
10 ≦ E _OH ≦ 40 (IV-B) It is an alkylene oxide adduct obtained by supplying one kind of alkylene oxide selected from ethylene oxide and propylene oxide to the alkylene oxide adduct according to any one of claims 6 to 11,
The following general formula (2):
RO-[(PO) p / (EO) q]-(AO) r-H (2)
(However, R represents an alkyl group or an alkenyl group having 1 to 30 carbon atoms, and may be composed of a linear or branched structure. PO is an oxypropylene group, EO is an oxyethylene group, AO Represents one kind of oxyalkylene group selected from an oxyethylene group and an oxypropylene group, p, q and r represent the average number of moles added, p = 1 to 20 , q = 1 to 50 and r = 1 to 50. [(PO) p / (EO) q] is a polyoxyalkylene group formed by random addition of p mol of PO and q mol of EO.)
The alkylene oxide adduct represented by these.   The alkylene oxide adduct according to claim 12, wherein the AO is an oxyethylene group.   The alkylene oxide adduct obtained by the manufacturing method in any one of Claims 1-5 and / or the alkylene oxide adduct in any one of Claims 6-13 is an emulsifier which uses as an essential component.   The dispersing agent which uses the alkylene oxide adduct obtained by the manufacturing method in any one of Claims 1-5 and / or the alkylene oxide adduct in any one of Claims 6-13 as an essential component.   The cleaning agent which uses the alkylene oxide adduct obtained by the manufacturing method in any one of Claims 1-5 and / or the alkylene oxide adduct in any one of Claims 6-13 as an essential component.

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