JP2013237819A - Alkylene oxide adduct, method for producing the same, and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkylene oxide adduct excellent in detergency, low foaming properties, and defoaming properties; a method for producing the same; and use thereof.SOLUTION: In an alkylene oxide adduct represented by general formula (1): RO-[(PO)p/(EO)q]-(PO)r-H (1); parameters of a randomization index Eobtained by making substitutions of N, N, N, N, N, N, Nand Nrespectively defined based on the charts obtained by measuring aC-NMR spectrum and aH-NMR spectrum of the alkylene oxide adduct, a percentage Eof oxyethylene groups directly bonded to an R group, a percentage Eof oxyethylene groups directly bonded to a terminal hydroxy group, and a conversion percentage Eof the terminal hydroxy group to a secondary hydroxy group are respectively within specific numerical ranges and further satisfy E<100×q<(p+q).

Description

  The present invention relates to an alkylene oxide adduct, a method for producing the same, and use thereof.

Alkylene oxide adducts such as ethylene oxide / propylene oxide adducts of higher alcohols are excellent in fluidity and stability at low temperatures, so they are detergents, antifoaming agents, emulsifiers, dispersants, oil phase component modifiers, penetrants. It has been used in various industrial applications such as polymer raw materials. In these applications, it is desirable to have excellent handling performance such as low foaming property. However, when the low foaming property and antifoaming property are increased, there may be a demerit that the cleaning power, which is inherently important performance, is reduced.
Various structural designs have been studied to optimize the performance of alkylene oxide adducts. For example, Patent Document 1 discloses a random adduct of ethylene oxide and propylene oxide; Patent Document 2 discloses a block adduct obtained by adding ethylene oxide and then propylene oxide in this order to an alcohol; Patent Document 3 Is a block adduct obtained by adding propylene oxide and then ethylene oxide in this order to the alcohol; Patent Document 4 discloses the random addition of ethylene oxide and propylene oxide to the alcohol first, followed by A block adduct obtained by adding ethylene oxide to ethylene; Patent Document 5 discloses that random addition of ethylene oxide and propylene oxide is first performed on alcohol, followed by addition of ethylene oxide, and further propylene oxide. Block adduct obtained by adding an id; Patent Document 6 discloses a block adduct obtained by first adding ethylene oxide and then propylene oxide to an alcohol, and further adding ethylene oxide. Yes.

However, these alkylene oxide adducts do not sufficiently satisfy the required properties such as detergency, low foaming property and antifoaming property. In addition, the alkylene oxide adducts described in Patent Documents 5 and 6 have a problem in production such that the production process is complicated and multistage, and thus the production time is long.
As described above, the alkylene oxide adducts of Patent Documents 1 to 6 have problems, but the current situation is that the conventional alkylene oxide adducts must be used while having these problems.

JP-A-7-303825 Japanese Patent Publication No. 63-12192 JP-A-53-58508 Japanese Patent Laid-Open No. 10-461189 JP-A-10-130690 JP-A-10-195499

  An object of the present invention is to provide an alkylene oxide adduct excellent in detergency, low foamability and antifoaming property, a method for producing the same, and use thereof.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. 1) First, in the first step, when an alcohol, ethylene oxide and propylene oxide are subjected to an addition reaction, the weight ratio of ethylene oxide and propylene oxide. 2) Then, the knowledge that an alkylene oxide adduct that solves the above problems can be obtained by addition reaction of propylene oxide at a specific temperature or lower was obtained, and the present invention was completed. .

The alkylene oxide adduct of the present invention has the following general formula (1):
RO-[(PO) p / (EO) q]-(PO) r-H (1)
(However, 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. PO represents an oxypropylene group, and EO represents an oxyethylene group. P, q and r represent the average number of moles added, where p = 1 to 20, q = 1 to 30 and r = 1 to 10. [(PO) p / (EO) q] is p (This is a polyoxyalkylene group formed by randomly adding mol PO and q mol 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 The parameters of the secondaryization rate E _OH satisfy the following formulas (IA) to (IV-A), respectively, and the relationship between E _EO-R and the average added mole numbers p and q represents the following formula (VI). Further, the alkylene oxide adduct is more satisfactory.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 70 (II-A)
0 ≦ E _EO-OH ≦ 20 (III-A)
80 ≦ E _OH ≦ 100 (IV-A)
E _EO-R <100 × q / (p + q) (VI)

The alkylene oxide adduct preferably satisfies at least one of the following 1) to 5).
1) The following mathematical formulas (II-B) to (IV-B) are further satisfied.
5 ≦ E _EO-R ≦ 50 (II-B)
0 ≦ E _EO-OH ≦ 10 (III-B)
90 ≦ E _OH ≦ 100 (IV-B)

2) The following mathematical formulas (III-C) and (IV-C) are further satisfied.
E _EO-OH = 0 (III-C)
E _OH = 100 (IV-C)
3) Carbon number of said R is 8-20.
4) The weight average molecular weight is 200 to 3000.
5) The cloud point measured by the butyl diglycol method (BDG method) is 20-95 degreeC.

Next, the production method of the alkylene oxide adduct of the present invention is represented by 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.)
Step 1 of simultaneously supplying ethylene oxide and propylene oxide to the alcohol represented by
After the completion of the step 1, a method for producing an alkylene oxide adduct, comprising the step 2 of supplying propylene oxide at 160 ° C. or less to cause an addition reaction,
In Step 1, the time when ethylene oxide and propylene oxide are started to be supplied is T0, and the time when ethylene oxide and propylene oxide are supplied is T100. 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] This is 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 <10 (D)

In this production method, it is preferable that at least one of the following (1) to (3) 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) In the said process 2, a propylene oxide is supplied at 100-150 degreeC, and is made to carry out an addition reaction.

The cleaning agent of the present invention is a cleaning agent containing the alkylene oxide adduct and / or the alkylene oxide adduct obtained by the production method as an essential component.
The antifoaming agent of the present invention is an antifoaming agent containing the alkylene oxide adduct and / or the alkylene oxide adduct obtained by the production method as an essential component.

The alkylene oxide adduct of the present invention is excellent in detergency, low foaming property and antifoaming property.
The method for producing an alkylene oxide adduct of the present invention can efficiently produce an alkylene oxide adduct having excellent detergency, low foamability and antifoaming property.
Since the cleaning agent of the present invention contains the alkylene oxide adduct of the present invention as an essential component, it has excellent cleaning properties.
Since the antifoaming agent of the present invention contains the alkylene oxide adduct of the present invention as an essential component, the antifoaming property is excellent.

2 is a chart showing the results of measuring the ¹³ C-NMR spectrum of the alkylene oxide adduct 1 obtained in Example 1. FIG. 2 is a chart showing the results of measuring the ¹ H-NMR spectrum of the alkylene oxide adduct 1 obtained in Example 1. FIG.

  Below, the manufacturing method of an alkylene oxide adduct is demonstrated first, Then, an alkylene oxide adduct and its use are demonstrated.

[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.)
The step of supplying ethylene oxide and propylene oxide simultaneously to the alcohol represented by the above formula (hereinafter, this step is sometimes referred to as “step 1”. For simplicity, “ethylene oxide and "Propylene oxide" is sometimes referred to as "alkylene oxide A"), and after Step 1, the step of supplying propylene oxide at 160 ° C or lower to cause an addition reaction (hereinafter, this step is referred to as "Step 2") Is a manufacturing method. Hereinafter, the adduct obtained in Step 1 may be referred to as an addition intermediate.

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.

The amount of the catalyst used is not particularly limited, but in Step 1, it is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 8 parts by weight, and still more preferably 0.001 parts by weight with respect to 100 parts by weight of the alcohol. 01 to 6 parts by weight, particularly preferably 0.05 to 5 parts by weight, and 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 step 1, it is preferable to supply while changing the weight ratio of ethylene oxide and propylene oxide to be supplied.

In 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 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 defoaming property of the resulting alkylene oxide adduct may be low. On the other hand, when [EO / PO] _T0 is 1 or more, the detergency of the resulting alkylene oxide adduct may be low.
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 poor detergency. 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 detergency of the resulting alkylene oxide adduct may be low. When [EO / PO] _T2 / [EO / PO] _T1 is 10 or more, the defoaming property 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 may be performed by an ordinary method. For example, when the catalyst is an alkaline catalyst, an acid such as hydrochloric acid, phosphoric acid, acetic acid, lactic acid, citric acid, succinic acid, acrylic acid, methacrylic acid, etc. may be used. It is preferable to perform the addition.

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 Chemical Co., Ltd.); KC Flock (manufactured by Nippon Paper Industries), Fibracell ( 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 catalyst is not particularly limited, but for example, a method of solid-liquid separation after adsorbing the 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 catalyst.
The catalyst removal conditions 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 adsorbed by the above-mentioned solid-liquid separation method, or by preliminarily filling the column or the like with the adsorbent, allowing the catalyst to be adsorbed by passing the reaction mixture at a temperature of 20 ° C to 140 ° C, Examples include a method for removing the 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 remaining amount after removal of the 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.
Next, in step 2, after step 1, propylene oxide is supplied to cause addition reaction. In step 2, propylene oxide is added to the terminal hydroxyl group of the alkylene oxide adduct (addition intermediate) obtained in step 1. In Step 2, an addition reaction can be carried out in the same manner as in Step 1 except for the case specifically described below. For example, with respect to production type, reaction time, pressure in reaction vessel, use of inert solvent, use of catalyst, neutralization of catalyst, removal of catalyst, etc., except that propylene oxide is used in place of alkylene oxide A This is the same as the description of Step 1 above.

In step 2, 1) propylene oxide may be supplied to the reaction mixture obtained in step 1 as it is, and an addition reaction may be carried out, and 2) as described above for the reaction mixture obtained in step 1. Further, after the neutralization and / or removal of the catalyst or after the removal of the inert solvent, the addition treatment may be performed by supplying propylene oxide.
In step 2, a catalyst may be further added. The amount of the catalyst to be added is not particularly limited, but is preferably 0.001 to 10 parts by weight, more preferably 0.001 to 8 parts by weight, with respect to 100 parts by weight of the reaction mixture obtained in Step 1. More preferably, it is 0.01-6 weight part, Most preferably, it is 0.05-5 weight part, Most preferably, it is 0.05-3 weight part. 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 step 2, the reaction temperature of the propylene oxide addition reaction is 160 ° C or lower, preferably 70 to 160 ° C, more preferably 80 to 160 ° C, still more preferably 90 to 160 ° C, particularly preferably 100 to 150 ° C, Most preferably, it is 100-140 degreeC. If the reaction temperature is too low, the addition reaction may not proceed sufficiently. On the other hand, when the reaction temperature is higher than 160 ° C., the obtained alkylene oxide adduct may be colored or the decomposition of the polyoxyalkylene group in the obtained alkylene oxide adduct may be promoted.
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.

[Alkylene oxide adduct]
The alkylene oxide adduct of the present invention is represented by the following general formula (1).
The following general formula (1):
RO-[(PO) p / (EO) q]-(PO) r-H (1)
(However, 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. PO represents an oxypropylene group, and EO represents an oxyethylene group. P, q and r represent the average number of moles added, where p = 1 to 20, q = 1 to 30 and r = 1 to 10. [(PO) p / (EO) q] is p (This is a polyoxyalkylene group formed by randomly adding mol PO and q mol EO.)
It is the alkylene oxide adduct represented by these.
R in the general formula (1) is a group derived from the alcohol described in the above production method, and the description thereof is also as described above.

p represents the average number of moles added of the oxypropylene group in the polyoxyalkylene group ([(PO) p / (EO) q]), and r represents the polyoxypropylene group ((PO) r bonded to the polyoxyalkylene group. ) Represents the average number of moles of oxypropylene group added.
The average added mole number p of the oxypropylene group is not particularly limited, but is usually 1 to 20, preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, particularly preferably 2 to 8, Most preferably, it is 2-6. When the average added mole number p of the oxypropylene group is less than 1, the low foam property and the defoaming property may not be sufficient. On the other hand, when the average number of added moles of the oxypropylene group p is more than 20, the hydrophobicity becomes too strong and the detergency may be lowered.

The average added mole number r of the oxypropylene group is not particularly limited, but is usually 1 to 10, preferably 1 to 9, more preferably 1 to 8, still more preferably 2 to 8, particularly preferably 2 to 7, Most preferably, it is 2-6. If the average addition mole number r of the oxypropylene group is less than 1, the low-foaming property and the defoaming property may not be sufficient. On the other hand, when the average added mole number of the oxypropylene group r is more than 10, the hydrophobicity becomes too strong and the detergency may be lowered.
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 30, preferably 1 to 20, more preferably 1 to 18, still more preferably 2 to 16, particularly preferably 3 to 13, Most preferably, it is 4-10. If the average added mole number q of the oxyethylene group is less than 1, hydrophilicity and detergency may not be sufficient. On the other hand, when the average addition mole number q of the oxyethylene group is more than 30 mol, the hydrophilicity becomes too strong and the cleaning property may be lowered.

[(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.
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 a hydroxyl group: secondary hydroxyl group The sum of integral values of ^{1 H-NMR} spectrum attributed to protons bound methine group and each following equation and the resulting readings (I) ~ (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 The parameters of the secondaryization rate E _OH satisfy the following formulas (IA) to (IV-A), respectively, and the relationship between E _EO-R and the average added mole numbers p and q represents the following formula (VI). Furthermore, since it is satisfied, it is excellent in low-foam detergency and defoaming property.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 70 (II-A)
0 ≦ E _EO-OH ≦ 20 (III-A)
80 ≦ E _OH ≦ 100 (IV-A)
E _EO-R <100 × q / (p + q) (VI)

In general, when a polyalkylene oxide adduct is produced, when ordinary random addition is performed, the ratio of ethylene oxide and propylene oxide to be supplied is not changed as the addition reaction proceeds. Since a constant value is maintained, the R group side of the polyoxyalkylene group of the alkylene oxide adduct, the side opposite to the R group in the polyoxyalkylene group, the R group side of the polyoxyalkylene group, and the side opposite to the R group At any position of the polyoxyalkylene group such as an intermediate point, the molar ratio of the oxypropylene group and the oxyethylene group 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, in the alkylene oxide adduct of the present invention, the polyoxyalkylene group located closer to the R group and the position away from the R group can be obtained by changing the weight ratio of the supplied ethylene oxide and propylene oxide over time. The molar ratios of ethylene oxide and propylene oxide of the polyoxyalkylene group in are different values. 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 side opposite to the R group in the polyoxyalkylene group It becomes a structure.

The alkylene oxide adduct of the present invention has the randomization index E _r described above, the percentage of EO groups directly bonded to the R group, E _EO-R , the percentage of EO groups directly bonded to the terminal hydroxyl group, E _{EO -OH,} and ¹ H-NMR 2 quaternizing rate _{E OH} terminal hydroxyl groups which is calculated from the peak area of the spectrum, satisfy the equation (I-a) ~ a (IV-a), respectively, further _{E EO-R} And the added mole numbers p and q satisfy the above formula (VI).
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%, it may be difficult to obtain an alkylene oxide adduct by addition reaction. On the other hand, if _Er is more than 45%, the random addition rate cannot be said to be sufficient, and 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 is 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 ≦ 70, preferably 1 ≦ E _EO-R ≦ 60, more preferably 1 ≦ E _{EO -R≤50} , particularly preferably _5≤EEO- R≤50, most preferably _{5≤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 detergency 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 0 ≦ E _EO-OH ≦ 20, preferably 0 ≦ E _EO-OH ≦ 15, more preferably 0 ≦ E _EO-OH. ≦ 10, particularly preferably 0 ≦ E _EO—OH ≦ 5, most preferably E _EO—OH = 0. When _EO-OH is more than 20%, the low foaming property and antifoaming property may not be sufficient.

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 ratio E _OH (%) is usually 80 ≦ E _OH ≦ 100, preferably 85 ≦ E _OH ≦ 100, more preferably 90 ≦ E _OH ≦ 100, and particularly preferably 95 ≦ E _OH ≦ 100. Most preferably, E _OH = 100. If _EOH is less than 80%, the low foaming property and antifoaming property may not be sufficient. 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.
Formula (VI) showing the relationship between E _EO-R and the number of added moles p and q shows that the alkylene oxide adduct of the present invention has an oxypropylene group rather than a normal random addition on the R group side of the polyoxyalkylene group. This means that a large molar ratio of is added. Since the addition reaction efficiency of ethylene oxide and propylene oxide is generally higher in ethylene oxide, in the usual random addition reaction, the molar ratio of ethylene oxide and propylene oxide at the time of charging on the R group side of the polyoxyalkylene group There is a tendency that the molar ratio of the oxyethylene group is larger than that. In the present invention, the molar ratio of the oxypropylene group on the R group side of the polyoxyalkylene group can be increased by intentionally changing the weight ratio of the supplied ethylene oxide and propylene oxide.

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. If the weight average molecular weight is less than 200, the detergency 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.
The cloud point of the alkylene oxide adduct is a value measured by the butyl diglycol method (BDG method) described in detail in the following examples. 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 detergency 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.

[Uses of alkylene oxide adducts]
Examples of the alkylene oxide adduct of the present invention and / or the alkylene oxide adduct obtained by the production method of the present invention include liquid detergents and powder detergents for clothing, household detergents, kitchen detergents, solid detergents, shampoos, Cleaning agents such as machine and metal detergents, antifoaming agents, antifoaming agents, lubricants, textile oil agents, paper chemicals, deresinating agents, deinking agents, degreasing agents, water reducing agents, flocculants, dispersing agents, emulsion polymerization In various uses such as an agent, 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 a cleaning agent and an antifoaming agent will be described in detail.

(Washing soap)
The cleaning agent of the present invention contains the alkylene oxide adduct and / or the alkylene oxide adduct obtained by the production method 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; builders such as carbonate, silicate, sulfate, zeolite, and tripolyphosphate; sodium hydroxide, Alkali compounds such as potassium hydroxide and ammonia; alkylamines such as ethylamine and butylamine; alkanolamines such as monoethanolamine and diethanolamine; hydrotropes such as ethanol and ethylene glycol; peroxides such as hydrogen peroxide; hydrofluoric acid and the like Other components such as acid, enzyme, fluorescent agent, dye, fragrance, disinfectant, antiseptic, moisturizer, thickener and the like may be further included.

The cleaning agent of the present invention can be used for cleaning various objects depending on purposes. The cleaning target of the cleaning agent of the present invention is not particularly limited. For example, precision processed parts such as liquid crystal panel plates, optical lenses, magnetic heads, printed wiring boards, semiconductors, step motors, bearings, screws, etc .; Wire drawing; Glass; Aluminum; Piping; Heat exchanger; Cotton, hemp, wool, rayon, acetate, cellulose fiber, polyester, polyamide fiber, acrylic, spandex, etc .; hair or body such as hair, skin, nails, eyes Food such as vegetables; tableware; walls, floors, tatami mats, furniture, ceilings, roofs, toilets, bathtubs, bathrooms, ventilation fans, houses around ranges, sinks, etc .; medical equipment; automotive parts.
The dirt targeted by the cleaning agent of the present invention is not particularly limited. For example, cutting oil, press oil, rolling oil, silicone, ester, grease, lubricating oil, mineral oil, rust preventive oil, and processing waste And inorganic powders such as abrasives, adhesives, waxes, rust, scales, fingerprints, release agents and the like.

The cleaning method using the cleaning agent of the present invention is not particularly limited. For example, immersion cleaning, ultrasonic cleaning, jet cleaning, rocking cleaning, bubbling cleaning, jet cleaning, spray cleaning, shower cleaning, steam cleaning, reduced pressure Examples include washing, vacuum washing, and hand washing.
The temperature (cleaning temperature) suitable for using the cleaning agent of the present invention is not particularly limited because it can be arbitrarily selected depending on the type of cleaning, but is usually 150 ° C. or less, preferably 5 to 140 ° C., more preferably It is 10-130 degreeC, More preferably, it is 15-120 degreeC, Especially preferably, it is 20-120 degreeC, Most preferably, it is 30-120 degreeC.
The method for drying the target after washing with the cleaning agent of the present invention is not particularly limited. For example, convection heating method, radiation heating method, induction heating method, steam heating method, displacement drying method, vacuum drying method The method etc. are mentioned.

(Defoamer)
The antifoaming agent of the present invention comprises the alkylene oxide adduct and / or the alkylene oxide adduct obtained by the production method as an essential component.
The antifoaming agent of the present invention may further contain water because of 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. When the mixing ratio of water is less than 1 part by weight, the cleaning power or defoaming power may be lowered. On the other hand, when the blending ratio of water is more than 10,000 parts by weight, handling properties may be inferior.

The antifoaming agent of the present invention may further contain other components such as other known antifoaming agents such as organic solvents, mineral oil, silicone, animal and vegetable oils.
The use of the antifoaming agent of the present invention is not particularly limited, but for example, fermentation industry uses such as amino acid fermentation, carboxylic acid fermentation, enzyme fermentation, antibiotic fermentation; paper pulp manufacturing industry; construction industry; dye industry; It can be used in the dyeing industry; rubber industry; synthetic resin industry; ink industry; paint industry;
When using the antifoaming agent of the present invention, the blending ratio with respect to the aqueous medium that needs to be defoamed is not particularly limited. For example, it is usually 0.0001 to 10 parts by weight with respect to 100 parts by weight of the aqueous medium, Preferably it is 0.001-10 weight part, More preferably, it is 0.001-5 weight part, More preferably, it is 0.001-1 weight part, Especially preferably, it is 0.01-1 weight part, Most preferably, 0.01- 0.1 parts by weight.

  Examples of the present invention will be specifically described below together with comparative examples. 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 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.

[Example 1]
(Process 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.
Next, after the temperature was raised to 130 ° C., ethylene oxide and propylene oxide were simultaneously fed while maintaining a reaction temperature of 145 ± 5 ° C. and a 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, the supply amount was gradually increased, and the supply was completed at a final supply rate of 70 g / h, and a total amount of 95 g was supplied in about 100 minutes. In addition, for propylene oxide, the supply was started at a supply rate of 50 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 62 g was supplied in about 100 minutes.

The weight ratio [EO / PO] _T0 of ethylene oxide and propylene oxide supplied at the start of supply was 0.2. The weight ratio [EO / PO] _T100 of ethylene oxide and propylene oxide supplied at the end of the supply was 7.0. Here, the time (minutes) from the start of supply to the end of supply is taken on the x-axis, and the weight ratio [EO / PO] of ethylene oxide to propylene oxide is taken on the y-axis, and ethylene oxide and propylene change over time. When the weight ratio [EO / PO] to oxide is plotted on the xy plane, it becomes a monotonically increasing straight line connecting (0, 0.2) and (100, 7.0), and has a linear function relationship. . The supply of ethylene oxide and propylene oxide satisfied the condition of 0.8 <[EO / PO] _T2 / [EO / PO] _T1 <10.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant.

(Process 2)
Subsequently, after raising the temperature to 130 ° C., 94 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 the supply of 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, 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 2, a propylene oxide addition mole number (q) of 4, and an ethylene oxide addition mole number (r) of 3.

The integrated values of ¹³ C-NMR spectrum (FIG. 1) and ¹ H-NMR spectrum (FIG. 2) of the obtained alkylene oxide adduct were read, and N _PO-PO , N _PO2 , N _EO-R , N _R , N _{EO-OH, N PO-OH} , N 1OH, N 2OH was respectively 5.5,21.3,1.4,2.9,0,3.0,0,1.0. E _r , E _EO-R , E _EO-OH , and E _OH calculated from these integral values were 20.5, 48.3, 0, and 100, respectively. Moreover, the conditions of _EEO-R <100 * q / (p + q) were satisfy | filled. The resulting alkylene oxide adduct had a weight average molecular weight of 652. The cloud point was 43.9 ° C.

[Examples 2-3]
In Examples 2 to 3, 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.

[Comparative Example 1]
(Process 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.
Next, after the temperature was raised to 130 ° C., ethylene oxide and propylene oxide were simultaneously fed while maintaining a reaction temperature of 145 ± 5 ° C. and a reaction pressure of 3.5 ± 0.5 kg / cm ² . Ethylene oxide was fed at a feed rate of 57 g / h, and a total amount of 95 g was fed in about 100 minutes. In addition, propylene oxide was supplied at a supply rate of 37 g / h, and a total amount of 62 g was supplied in about 100 minutes.

The weight ratio [EO / PO] _T0 of ethylene oxide and propylene oxide supplied at the start of supply was 1.54. The weight ratio [EO / PO] _T100 of ethylene oxide and propylene oxide supplied at the end of the supply was 1.54. That is, from the start of supply to the end of supply, the weight ratio [EO / PO] of ethylene oxide to propylene oxide was a constant value of 1.54. The supply of ethylene oxide and propylene oxide did not satisfy the condition of 0.8 <[EO / PO] _T2 / [EO / PO] _T1 <10.
After the supply of ethylene oxide and propylene oxide was completed, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant.

(Process 2)
Subsequently, after raising the temperature to 130 ° C., 94 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 the supply of 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, 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 2, a propylene oxide addition mole number (q) of 4, and an ethylene oxide addition mole number (r) of 3.

The integrated values of ¹³ C-NMR spectrum and ¹ H-NMR spectrum of the obtained alkylene oxide adduct are read, and E _r , E _EO-R , E _EO-OH , E _OH calculated from these integrated values are They were 20.8, 81.5, 0, and 100, respectively. The condition of E _EO-R <100 × q / (p + q) was not satisfied. The resulting alkylene oxide adduct had a weight average molecular weight of 652. The cloud point was 43.4 ° C.

[Comparative Examples 2-3]
In Comparative Examples 2 to 3, an alkylene oxide adduct was obtained in the same manner as in Comparative Example 1 except that the raw materials were changed as shown in Table 1 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 1.

[Comparative Example 4]
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., 95 g of ethylene oxide was supplied in about 110 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, 156 g of propylene oxide was supplied in about 230 minutes.

After the supply of 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.
As shown in Table 2, the obtained alkylene oxide adduct is a block adduct obtained by adding ethylene oxide and then propylene oxide in this order, and the number of moles of ethylene oxide addition is 4. The number of moles of propylene oxide added was 5.
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 50.3, 100, 0 and 100. The resulting alkylene oxide adduct had a weight average molecular weight of 652 and a cloud point of 43.4 ° C.

[Comparative Example 5]
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., 156 g of propylene oxide was supplied in about 230 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, 95 g of ethylene oxide was supplied in about 110 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.

As shown in Table 2, the obtained alkylene oxide adduct is a block adduct obtained by adding propylene oxide in the order of ethylene oxide and then ethylene oxide, and the number of moles of propylene oxide addition is 5. The number of moles of ethylene oxide added was 4.
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 are 50.5, 0, 100, 0. The resulting alkylene oxide adduct had a weight average molecular weight of 652 and a cloud point of 45.2 ° C.

[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., 62 g of propylene oxide was supplied in about 120 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, 95 g of ethylene oxide was supplied in about 110 minutes. Furthermore, after aging until the internal pressure decreased and became constant, 94 g of propylene oxide was supplied in about 160 minutes.

After the supply of 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.
As shown in Table 2, the resulting alkylene oxide adduct was a block adduct obtained by adding propylene oxide first, then ethylene oxide, and finally propylene oxide. The number of moles of addition of the resulting alkylene oxide adduct was 2, propylene oxide addition moles, ethylene oxide addition moles 4, and propylene oxide addition moles 3 in the order of addition.

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 are 48.9, 0, 0, 0. The resulting alkylene oxide adduct had a weight average molecular weight of 652 and a cloud point of 45.5 ° C.
Using each of the alkylene oxide adducts obtained in Examples 1 to 3 and Comparative Examples 1 to 6, the detergency, low-foaming property and antifoaming property were evaluated by the following methods, and the results are shown in Table 2. .

[Evaluation of detergency (detergency)]
A cleaning agent was prepared by mixing 0.03 g of an alkylene oxide adduct, 0.6 g of sodium metasilicate, and 299.37 of 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: The detergency is 70% or more, and the detergency is excellent.
A: Detergency is 60% or more and less than 70%, and is excellent in detergency.
(Triangle | delta): Detergency is inferior to 50% or more and less than 60%, and is inferior.
X: Detergency is less than 50% and is inferior in detergency.

[Evaluation of low foamability (foaming power)]
A test liquid was prepared by mixing 0.1 g of an alkylene oxide adduct and 99.9 g of water. The test solution was allowed to flow down at 25 ° C. according to the Ross Miles method, and the height of the foam immediately after the flow down was measured.
(Double-circle): Foaming power is less than 25 mm, and is excellent in low foaming property.
A: The foaming power is 25 mm or more and less than 50 mm, and is excellent in low foaming property.
(Triangle | delta): Foaming power is 50 mm or more and less than 100 mm, and is inferior to low foaming property.
X: Foaming power is 100 mm or more and is inferior in low foaming property.

[Evaluation of antifoaming properties (defoaming power)]
An aqueous solution obtained by mixing 0.05 g of an alkylene oxide adduct, 3 g of polyvinyl alcohol, and 97 g of water was subjected to air bubbling for 10 minutes while being kept at 50 ° C. The defoaming power was evaluated by calculating the volume increase rate of the aqueous solution after air bubbling. The defoaming force is calculated by the following formula, and the smaller the defoaming force value, the better the defoaming property.
Defoaming power (%) = (volume of aqueous solution after air bubbling−volume of aqueous solution before air bubbling) (ml) / volume of aqueous solution before air bubbling (ml) × 100
A: The defoaming power is less than 100% and the defoaming property is excellent.
A: The defoaming power is 100% or more and less than 200%, and the defoaming property is excellent.
Δ: The defoaming power is 200% or more and less than 300%, and the defoaming property is inferior.
X: Defoaming power is 300% or more, and the defoaming property is inferior.

From Table 2, when Examples 1 to 3 and Comparative Examples 1 to 3 corresponding to the numbers are compared, even if no structural difference can be found when the alkylene oxide adduct is expressed by a chemical formula, Example 1 In ~ 3, it turns out that it is excellent in detergency, low-foaming property, and defoaming property.
Further, the alkylene oxide adducts of Example 1 and Comparative Examples 4 to 6 are not different in that they were obtained by adding 4 mol of ethylene oxide and 5 mol of propylene oxide to 1 mol of lauryl alcohol. However, the special alkylene oxide adduct (Example 1) of the present invention is remarkably superior in terms of detergency, low-foaming properties and antifoaming properties over simple block adducts (Comparative Examples 4 to 6). I understand.

Claims (12)

The following general formula (1):
RO-[(PO) p / (EO) q]-(PO) r-H (1)
(However, 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. PO represents an oxypropylene group, and EO represents an oxyethylene group. P, q and r represent the average number of moles added, where p = 1 to 20, q = 1 to 30 and r = 1 to 10. [(PO) p / (EO) q] is p (This is a polyoxyalkylene group formed by randomly adding mol PO and q mol 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 The parameters of the secondaryization rate E _OH satisfy the following formulas (IA) to (IV-A), respectively, and the relationship between E _EO-R and the average added mole numbers p and q represents the following formula (VI). Further satisfying alkylene oxide adducts.
1 ≦ E _r ≦ 45 (IA)
1 ≦ E _EO-R ≦ 70 (II-A)
0 ≦ E _EO-OH ≦ 20 (III-A)
80 ≦ E _OH ≦ 100 (IV-A)
E _EO-R <100 × q / (p + q) (VI) The alkylene oxide adduct according to claim 1, further satisfying the following formulas (II-B) to (IV-B):
5 ≦ E _EO-R ≦ 50 (II-B)
0 ≦ E _EO-OH ≦ 10 (III-B)
90 ≦ E _OH ≦ 100 (IV-B) The alkylene oxide adduct according to claim 1 or 2, further satisfying the following formulas (III-C) and (IV-C):
E _EO-OH = 0 (III-C)
E _OH = 100 (IV-C)   The alkylene oxide adduct according to any one of claims 1 to 3, wherein R has 8 to 20 carbon atoms.   The alkylene oxide adduct according to any one of claims 1 to 4, having a weight average molecular weight of 200 to 3,000.   The alkylene oxide adduct according to any one of claims 1 to 5, wherein the cloud point measured by a butyl diglycol method (BDG method) is 20 to 95 ° C. 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.)
Step 1 of simultaneously supplying ethylene oxide and propylene oxide to the alcohol represented by
After the completion of the step 1, a method for producing an alkylene oxide adduct, comprising the step 2 of supplying propylene oxide at 160 ° C. or less to cause an addition reaction,
In Step 1, the time when ethylene oxide and propylene oxide are started to be supplied is T0, and the time when ethylene oxide and propylene oxide are supplied is T100. 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 <10 (D) The manufacturing method of the alkylene oxide adduct of Claim 7 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 7 or 8 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 7 to 9, wherein in the step 2, propylene oxide is supplied at 100 to 150 ° C to cause addition reaction.   The cleaning agent which uses the alkylene oxide adduct in any one of Claims 1-6 and / or the alkylene oxide adduct obtained by the manufacturing method in any one of Claims 7-10 as an essential component.   The defoamer which uses the alkylene oxide adduct in any one of Claims 1-6 and / or the alkylene oxide adduct obtained by the manufacturing method in any one of Claims 7-10 as an essential component.

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