KR102351930B1 - Method for producing fatty acid aklyl ester alkoxylate - Google Patents

Abstract

In the method for producing a fatty acid alkyl ester alkoxylate by adding an alkylene oxide to a fatty acid alkyl ester represented by the following general formula (I), selected from the group consisting of alkaline earth metal compound (B) and sulfuric acid, hydrochloric acid and phosphoric acid At least one selected from the group consisting of an alkoxylation catalyst formed by reacting at least one acid (C) in a liquid dispersion medium (A), and 0.05 to 0.20 moles of a monohydric alcohol and a dihydric alcohol based on 1 kg of the fatty acid alkylester a step of adding 5 to 25 moles of the alkylene oxide to 1 mole of the fatty acid alkylester in the presence of an alcohol of a species, wherein the molar ratio of the acid (C) to the alkaline earth metal compound (B) (C/B B) is 0.8 or more and less than 1. A method for producing a fatty acid alkyl ester alkoxylate.
R ¹¹ COOR ¹² ...(I)
[In formula (I), R ¹¹ is a hydrocarbon group having 7 to ^{17 carbon atoms, and R 12} is a straight chain alkyl group having 1 to 3 carbon atoms.]

Description

The manufacturing method of fatty acid alkylester alkoxylate {METHOD FOR PRODUCING FATTY ACID AKLYL ESTER ALKOXYLATE}

The present invention relates to a method for producing a fatty acid alkylester alkoxylate.

This application claims priority based on Japanese Patent Application No. 2014-090579 for which it applied to Japan on April 24, 2014, The content is used here.

Fatty acid alkyl ester alkoxylate in which alkylene oxide is added to fatty acid alkyl ester is widely used as a cleaning component in liquid detergents.

Fatty acid alkylester alkoxylates are used as nonionic surfactants in medical detergents and the like. Since the fatty acid alkylester alkoxylate has a small gelation area even when blended at a high concentration, it is utilized as a particularly suitable thing for a concentrated liquid detergent containing a surfactant in a high concentration (see Patent Document 1).

As a manufacturing method of this fatty acid alkylester alkoxylate, the method of adding an alkylene oxide to fatty acid alkylester in presence of an alkoxylation catalyst is mentioned.

In general, for alkoxylation reactions such as alcohols and amines having active hydrogens such as hydrogen in a hydroxyl group in a molecule, homogeneous catalysts such as acids or alkalis and/or heterogeneous catalysts such as composite metal oxides are used as alkoxylation catalysts. However, the addition reaction of an alkylene oxide to a fatty acid alkylester having no active hydrogen in the molecule (also referred to as an alkoxylation reaction) does not proceed with an acid catalyst, which is a homogeneous catalyst, or an alkali catalyst such as sodium hydroxide. For this reason, a composite metal oxide catalyst or the like is used in the alkoxylation reaction. Examples of the composite metal oxide catalyst include aluminum-magnesium composite metal oxides such as aluminum hydroxide/magnesium fired products (see Patent Document 2).

When the alkoxylation reaction of a fatty acid alkyl ester is performed using a composite metal oxide catalyst such as the aluminum-magnesium composite metal oxide, a process such as filtration is required to remove the catalyst after the reaction. In addition, when a composite metal oxide catalyst such as the aluminum-magnesium composite metal oxide is used, by-products such as polymers (molecules having a weight average molecular weight of 10000 or more measured by gel permeation chromatography method) polyalkylene glycol are generated during the reaction. , When a fatty acid alkylester alkoxylate containing such a by-product is used for a liquid detergent, there exists a problem that a liquid detergent becomes turbid easily. Accordingly, it is necessary to remove such by-products such as polyalkylene glycol having a high molecular weight together with the catalyst. However, this high molecular weight polyalkylene glycol or the like easily causes clogging of the filter cloth, and as a result, the filtration speed is slowed, so industrially, extensive filtration equipment is required, and there is a problem that the equipment burden on the operator is increased.

Therefore, in the alkoxylation reaction of fatty acid alkyl esters, as a catalyst for reducing the amount of these by-products, alkaline earth metal salts of carboxylic acids, alkaline earth metal salts of hydroxycarboxylic acids, alkaline earth metal oxides and alkaline earth metals An alkoxylation catalyst comprising at least one alkaline earth metal compound selected from the group consisting of hydroxides and sulfuric acid reacting in a liquid dispersion medium, wherein the molar ratio expressed by the acid/alkaline earth metal compound is 0.8 to 1 has been proposed. See Patent Document 3). Hereinafter, a catalyst formed by reacting such an alkaline earth metal compound with an acid in a liquid dispersion medium is referred to as an acid/alkaline earth metal compound catalyst.

International Publication No. 2011/007778 International Publication No. 2008/078768 International Publication No. 2013/154189 International Publication No. 2008/001797

However, as a result of investigation by the present inventors, when the fatty acid alkyl ester alkoxylate obtained using the acid/alkaline earth metal compound catalyst described in Patent Document 3 is used in a liquid detergent, the liquid detergent solidifies under low temperature conditions of less than 0 ° C. It was found that there is a problem that is easy to generate. Liquid detergents are required to maintain a liquid state without causing solidification or precipitation at low temperatures for use and storage in cold regions. Therefore, the compounding composition is comprised so that a liquid phase may be maintained in the storage test of -5 degreeC, 1 month, for example.

Here, it is known that the added mole number distribution of the ethylene oxide of the fatty acid alkylester alkoxylate used for a liquid detergent affects the viscosity of a liquid detergent (patent document 4).

On the other hand, according to the studies of the present inventors, the problem that liquid detergents are easy to cause solidification under low temperature conditions of less than 0 ° C. In the manufacture of liquid detergents, fatty acid alkyl ester alkoxylates prepared using the composite metal oxide catalyst are used. It does not occur when done (refer to the comparative example of this application). However, as described above, when a composite metal oxide catalyst is used, there is a problem that a burden is applied to the filtration of the catalyst and by-products.

The present invention is made in view of the above circumstances, and in the production of fatty acid alkyl ester alkoxylate, fatty acid alkyl ester alkoxylate is prepared by using the acid/alkaline earth metal compound catalyst in order to reduce the generation of the by-product Moreover, it makes it a subject to provide the manufacturing method of the fatty-acid alkylester alkoxylate useful as a washing|cleaning component of the liquid detergent which solidification does not easily generate|occur|produce under low-temperature conditions below 0 degreeC.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining, the present inventors provide the following means in order to solve the said subject.

That is, the method for producing a fatty acid alkyl ester alkoxylate of the present invention comprises an alkaline earth metal compound ( B) and an alkoxylation catalyst formed by reacting at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid in a liquid dispersion medium (A), and 0.05 to 0.20 moles of 1 with respect to 1 kg of the fatty acid alkylester 5 to 25 moles of the alkylene oxide are added to 1 mole of the fatty acid alkyl ester in the presence of at least one alcohol selected from the group consisting of a polyhydric alcohol and a dihydric alcohol (hereinafter, also referred to as a monohydric/bihydric alcohol). It is characterized in that the molar ratio (C/B ratio) of the acid (C) to the alkaline earth metal compound (B) is 0.8 or more and less than 1.

R ¹¹ COOR ¹² ...(I)

[In formula (I), R ¹¹ is a hydrocarbon group having 7 to ^{17 carbon atoms, and R 12} is a straight chain alkyl group having 1 to 3 carbon atoms.]

In addition, the usage-amount of fatty acid alkylester, monohydric / bihydric alcohol, and alkylene oxide can be adjusted by manufacturing equipment etc., and if it is said ratio, it will not be limited.

Another aspect of the present invention is to prepare an alkoxylation catalyst by reacting an alkaline earth metal compound (B) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid in a liquid dispersion medium (A). a catalyst manufacturing process;

A catalyst dispersion step of mixing the catalyst and the fatty acid alkylester represented by the general formula (I);

An addition reaction step of further adding 5 to 25 moles of alkylene oxide to the reaction solution obtained in the catalyst dispersion step with respect to 1 mole of the fatty acid alkylester;

It is a method for producing a fatty acid alkyl ester alkoxylate comprising mixing 0.05 to 0.20 moles of a monohydric/bihydric alcohol with respect to 1 kg of a fatty acid alkyl ester to the reaction solution before adding the addition alkylene oxide.

(Effects of the Invention)

According to the method for producing a fatty acid alkyl ester alkoxylate of the present invention, by using a specific amount of a monohydric/bihydric alcohol in the reaction system, solidification under low-temperature conditions is suppressed and a fatty acid alkyl ester useful as a cleaning component of a liquid detergent with good fluidity. Alkoxylates can be prepared.

(Method for producing fatty acid alkyl ester alkoxylate)

The method for producing a fatty acid alkyl ester alkoxylate of the present invention is a specific amount of alkylene oxide in a fatty acid alkyl ester represented by the following general formula (I) in the presence of a specific alkoxylation catalyst and a specific amount of monohydric/bihydric alcohol has a process of adding

<Fatty Acid Alkyl Ester>

R ¹¹ COOR ¹² ...(I)

[In formula (I), R ¹¹ is a hydrocarbon group having 7 to ^{17 carbon atoms, and R 12} is a straight chain alkyl group having 1 to 3 carbon atoms.]

In the formula (I), the number of carbon atoms of R ¹¹ is a lower limit value is 7, and 9 are preferred, and 11 are more preferable, and the upper limit value is 17, 15 is preferred, more preferably 13. In said formula (I), 9-15 are preferable and, as for carbon number of ^{R<11>, 11-13 are more preferable.}

R ¹¹ may be linear or branched. R ¹¹ is preferably straight chain.

R ¹¹ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group. R ¹¹ is preferably a saturated hydrocarbon group.

In the formula (I), R ¹² is a linear alkyl group having 1 to 3 carbon atoms, preferably a methyl group having 1 carbon atom.

Specific examples of the fatty acid alkyl ester are fatty acid methyl esters or mixtures thereof, and more preferably methyl laurate, methyl myristate, or mixtures thereof.

Fatty acid alkylester may be used individually by 1 type, and may be used in combination of 2 or more type.

<Alkylene oxide>

The alkylene oxide is determined depending on the intended product. For example, in order to obtain a nonionic surfactant, ethylene oxide, propylene oxide, butylene oxide, etc. are preferable, and among these, ethylene oxide is more preferable.

An alkylene oxide may be used individually by 1 type, and 2 or more types may be combined and used for it.

<Specific amount of monohydric/bihydric alcohol>

At least one alcohol selected from the group consisting of monohydric alcohols and dihydric alcohols in specific amounts (also referred to as monohydric/bihydric alcohols) may be a saturated alcohol or an unsaturated alcohol.

Examples of the specific amount of monohydric/hydric alcohol include propanol such as methanol, ethanol and 2-propanol; octanol such as butanol, pentanol, hexanol, heptanol, n-octanol and 2-ethylhexanol; nonanol; monohydric alcohols such as decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, myristyl alcohol, pentadecyl alcohol, stearyl alcohol, isostearyl alcohol and oleyl alcohol; alkylene glycols such as ethylene glycol and propylene glycol; The alkoxyalkylene glycol etc. by which the single terminal was alkoxylated are mentioned.

Among these, as the monohydric/2hydric alcohol in a specific amount, monohydric alcohol is preferable, linear or branched monohydric alcohol having 1 to 18 carbon atoms is more preferable, and linear or branched alcohol having 1 to 8 carbon atoms is preferable. Monohydric alcohols are more preferred, and 2-propanol and 2-ethylhexanol are particularly preferred.

A specific amount of monohydric / bihydric alcohol may be used individually by 1 type, and 2 or more types may be used in combination.

<Alkoxylation catalyst>

The alkoxylation catalyst in the present invention is an alkaline earth metal compound (B) (hereinafter also referred to as “component (B)”) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid (hereinafter “component”). (C) Also referred to as "component") reacts in a liquid dispersion medium (A) (hereinafter also referred to as "(A) component") (hereinafter also referred to as "catalyst (α)"). That is, the catalyst (?) contains the reactant of the component (B) and the component (C) (salt of an alkaline earth metal which is the main catalytically active component).

An alkoxylation catalyst may be used individually by 1 type, and may be used in combination of 2 or more type.

The said catalyst ((alpha)) can be manufactured by mixing (B) component and (C)component in (A) component.

・(A) component: liquid dispersion medium

When component (A) produces catalyst (α), it does not gelatinize and can maintain the fluidity|liquidity of a reaction liquid, and in (A) component, especially if it can react (B) component and (C)component not limited

(A) The "liquid" in a component means that it is a liquid in the dispersion process and mixing process mentioned later.

As (A) component, it is preferable that it is a liquid at 30 degreeC from a viewpoint of improving the productivity in the manufacturing method of the catalyst (alpha) mentioned later.

(A) As a component, for example, the alcohol represented by the following general formula (1), the alkylene oxide adduct of the alcohol represented by the said formula (1), the fatty acid alkylester represented by the following general formula (2), the said formula At least selected from the group consisting of an alkylene oxide adduct of a fatty acid alkyl ester represented by (2), a fatty acid represented by the following general formula (3), and an alkylene oxide adduct of a fatty acid represented by the formula (3) One paper is preferred.

ROH...(1)

[In formula (1), R is a C3-C18 hydrocarbon group.]

R ¹ COOR ² ...(2)

[In formula (2), R ¹ is a hydrocarbon group ^{having 3 to 18 carbon atoms, and R 2} is a straight chain alkyl group having 1 to 3 carbon atoms.]

R ³ COOH ...(3)

[In formula (3), R ³ is a hydrocarbon group having 3 to 18 carbon atoms.]

In said formula (1), a lower limit is 3, and, as for carbon number of R, an upper limit is 18, 12 is preferable and 8 is more preferable. In said formula (1), 3 or more and 12 or less are preferable and, as for carbon number of R, 3 or more and 8 or less are more preferable. When carbon number of R is less than a lower limit, when manufacturing a catalyst (α), (A) component thickens in a gel form, loses fluidity|liquidity, and (B) component and (C)component hardly react. When the number of carbon atoms in R exceeds the upper limit, the melting point becomes high, and thus it is not suitable as a dispersion medium.

R may be linear or branched.

R may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.

The alcohol represented by the formula (1) is preferably a monohydric alcohol, more preferably a linear or branched monohydric alcohol having 1 to 18 carbon atoms, and a linear or branched monohydric alcohol having 1 to 8 carbon atoms. Alcohol is more preferred. As the alcohol represented by the formula (1), a specific amount of a monohydric/bihydric alcohol can be used.

Moreover, when the alcohol represented by said Formula (1) is used as (A) component, the alcohol derived from (A) component is contained in the monohydric / bihydric alcohol of the specific amount in manufacture of fatty acid alkylester alkoxylate. make it to be

Examples of the alcohol represented by the formula (1) include 1-hexanol, n-octanol, 2-ethylhexanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, and n- primary alcohols such as octadecanol, oleyl alcohol, nonanol, undecanol, and tridecanol; and secondary alcohols such as 2-propanol, 2-octanol, 2-decanol and 2-dodecanol. Among these, 2-propanol and 2-ethylhexanol are preferable from a viewpoint of further reducing the production amount of by-products, such as high molecular weight polyethyleneglycol.

In the alkylene oxide adduct of the alcohol represented by the formula (1), that is, an alcohol alkoxylate, examples of the alkylene oxide added to the alcohol include an alkylene oxide having 2 to 3 carbon atoms.

As for the average added mole number of the alkylene oxide of the alkylene oxide adduct of alcohol represented by said Formula (1), 1-7 are preferable, for example.

In said formula (2), ^{carbon number of R<1>} is 3-18, and temperature conditions at the time of manufacturing an alkoxylation catalyst WHEREIN: If fluidity|liquidity is good, it can select arbitrarily. In said formula (2) ^{, 7-17 are preferable, as for carbon number of R<1>} , 9-15 are more preferable, 11-13 are still more preferable.

R ¹ may be linear or branched. It is preferable that R<^{1> is linear.}

R ¹ may be a saturated hydrocarbon group, ie, an alkyl group, or an unsaturated hydrocarbon group such as an alkenyl group. R ¹ is preferably a saturated hydrocarbon group.

In said formula (2), R<^2> is a C1-C3 linear alkyl group, and a C1-C1 methyl group is preferable. When R<^2> is a C1-C3 linear alkyl group, melting|fusing point of (A) component is low, and fluidity|liquidity is good in the temperature conditions at the time of manufacture of an alkoxylation catalyst.

The fatty acid alkyl ester represented by the formula (2) is preferably a fatty acid methyl ester such as methyl decanoate, methyl laurate, methyl myristate, or methyl oleate, or a mixture thereof, and methyl laurate and myristine. Methyl acid, or a mixture thereof, is more preferred. As the fatty acid alkyl ester represented by the formula (2), it is preferable to use the same fatty acid alkyl ester represented by the general formula (I) because the content of components other than the target substance is smaller.

In the alkylene oxide adduct of the fatty acid alkylester represented by the said Formula (2), ie, fatty acid alkylester alkoxylate, a C2-C3 alkylene oxide is mentioned as an alkylene oxide to add.

As for the average added mole number of an alkylene oxide, 1-7 are preferable, for example.

In said formula (3), ^{carbon number of R<3>} is 3-18, Preferably it is 7-17, More preferably, it is 11-17. In said formula (3), ^{carbon number of R<3>} can be selected arbitrarily, if fluidity|liquidity is good in the temperature conditions at the time of manufacturing an alkoxylation catalyst.

R ³ may be linear or branched.

R ³ may be a saturated hydrocarbon group (alkyl group) or an unsaturated hydrocarbon group such as an alkenyl group.

Examples of the fatty acid represented by the formula (3) include octanoic acid, decanoic acid, lauric acid, palmitic acid, oleic acid, linoleic acid, and linolenic acid, and among these, oleic acid is preferable.

The alkylene oxide adduct of the fatty acid represented by said Formula (3) WHEREIN: A C2-C3 alkylene oxide is mentioned as an alkylene oxide to add.

As for the average added mole number of an alkylene oxide, 1-7 are preferable, for example.

(A) As a component, the alcohol represented by General formula (1) from a viewpoint of reducing the production amount of a by-product more, and fatty acid alkylester represented by General formula (2) are preferable.

(A) A component may be used individually by 1 type, and 2 or more types may be combined and used for it.

・(B) component: alkaline earth metal compound

(B) Component will not be specifically limited if it reacts with (C)component as a compound containing an alkaline-earth metal.

(B) "alkaline earth metal" in component shall contain magnesium and beryllium in addition to calcium, strontium, barium, and radium.

(B) As a component, for example, alkaline earth metal salt of carboxylic acid (it is also called "(b1) component" hereafter), alkaline earth metal salt of hydroxycarboxylic acid (it is also called "(b2) component" hereafter), alkaline earth As metal oxides (hereinafter also referred to as “(b3) component”), alkaline earth metal hydroxides (hereinafter also referred to as “(b4) component”) and carbonic acid alkaline earth metal salts (hereinafter also referred to as “(b5) component”)) At least one selected from the group consisting of is preferable.

(b1) As a component, Calcium salt of carboxylic acids, such as calcium acetate (calcium acetate anhydrate, calcium acetate monohydrate, etc.) and calcium formate; and barium salts of carboxylic acids such as barium acetate and barium formate. Among these, the calcium salt of a carboxylic acid is preferable from a viewpoint of improving catalytic activity, and calcium acetate is more preferable.

(b2) As a component, Calcium salt of hydroxycarboxylic acid, such as a calcium lactate, a calcium tartrate, a calcium citrate, and a calcium malate; and barium salts of hydroxycarboxylic acids such as barium lactate, barium stannate, barium citrate, and barium malate. Among these, the calcium salt of hydroxycarboxylic acid is preferable from a viewpoint of improving catalytic activity.

(b3) Calcium oxide, barium oxide, etc. are mentioned as a component, Especially, calcium oxide is preferable.

(b4) Calcium hydroxide, barium hydroxide, etc. are mentioned as a component, Especially, calcium hydroxide is preferable.

(b5) As a component, a calcium carbonate and barium carbonate are mentioned, for example, Among these, calcium carbonate is preferable.

(B) As component (B), from a viewpoint of improving catalytic activity and reducing the production amount of a by-product more, (b1) and (b3) component are preferable, and the calcium salt of carboxylic acid and calcium oxide are more preferable.

(B) A component may be used individually by 1 type, and 2 or more types may be combined and used for it.

・(C) Component: Acid

(C)component in this invention is an at least 1 sort(s) of acid chosen from the group which consists of sulfuric acid, hydrochloric acid, and phosphoric acid.

(C) From a viewpoint of stably expressing catalytic activity among a component, sulfuric acid is preferable. Concentrated sulfuric acid may be used for sulfuric acid, and diluted sulfuric acid may be used.

The catalyst (α) uses, for example, a fatty acid alkyl ester represented by the general formula (2) as the component (A), a calcium salt or calcium oxide of a carboxylic acid as the component (B), and sulfuric acid as the component (C). can

[Method for producing catalyst (α)]

As a manufacturing method of a catalyst ((alpha)), for example, the dispersion process which disperse|distributes (B) component in (A) component, and obtains a dispersion, and (C) component is added to the said dispersion, and (B) in (A) component ) The method of having a mixing process of mixing a component and (C)component is mentioned.

··Dispersion process

In a dispersion process, the reactor provided with the mixing tank provided with the jacket, and the stirring tank provided with the puddle stirring blades is used, for example. In a dispersion process, (A) component and (B) component are thrown in in a stirring tank, and these are stirred.

Although the temperature conditions in this process are not specifically limited, For example, it is set as normal temperature (5-35 degreeC). The temperature adjustment in the stirring tank is performed, for example, by passing a heating medium (eg, water) of an arbitrary temperature in the jacket.

The stirring time in this process is not specifically limited, It becomes time in which (B)component is disperse|distributed substantially uniformly in (A)component. The stirring time in this process is 10 to 60 minutes, for example. A substantially uniformity means the state which can judge that there is no lump of (B) component in the naked eye, and (B) component is disperse|distributing uniformly.

··Mixing process

In the mixing step, component (C) is added to the dispersion obtained in the dispersing step and mixed to form a reaction product of component (B) and component (C), that is, a salt of alkaline earth metal which is the main catalytically active component, (A) An alkoxylation catalyst in which the catalytically active component is dispersed in the component is obtained.

Although the mixing method in this process is not specifically limited, For example, the method of dripping (C)component in a dispersion, stirring the dispersion in a stirring tank is preferable.

10-60 degreeC is preferable and, as for the temperature condition in this process, ie, reaction temperature, 20-50 degreeC is more preferable. As a lower limit of the said reaction temperature, 10 degreeC is preferable, 20 degreeC is more preferable, as an upper limit, 60 degreeC is preferable and 50 degreeC is more preferable. If it is less than the said preferable lower limit, reaction of (B) component and (C)component may become slow too much, and there exists a possibility that the productive efficiency of catalyst (alpha) may become low. When the above-mentioned preferable upper limit is exceeded, there is a fear that the catalytic activity of the obtained catalyst (?) becomes low.

The reaction temperature is adjusted, for example, by passing a heating medium (for example, water) of an arbitrary temperature in the jacket.

The stirring time (i.e., reaction time) in this step is a time during which the (B) component and (C) component can sufficiently react, and is a time during which the heat generation due to the addition of the (C) component can be controlled. , for example, 1 to 2 hours. The stirring time in this process means time after adding (C)component completely.

0.8 or more and less than 1 are preferable and, as for the molar ratio (henceforth "C/B ratio") represented by (C)component/(B)component in the said mixing process, 0.9-0.98 are more preferable. As a lower limit, 0.8 is preferable as said C/B ratio, 0.9 is more preferable, as an upper limit, less than 1 is preferable, and 0.98 is more preferable.

When C/B ratio is more than the said preferable lower limit, the catalyst (alpha) obtained can reduce favorably the amount of by-products produced in the manufacturing process of a fatty-acid alkylester alkoxylate.

When C/B ratio is 0.9 or more, distribution of the added mole number of the alkylene oxide of the fatty-acid alkylester alkoxylate obtained in the manufacturing method of a fatty-acid alkylester alkoxylate will be easy to widen.

Distribution of the added mole number of the alkylene oxide of fatty-acid alkylester alkoxylate can be calculated|required by the gas chromatography method (it is also mentioned GC method). Distribution of the added mole number of alkylene oxide of fatty acid alkyl ester alkoxylate is derived from fatty acid alkyl ester alkoxylate obtained by, for example, measuring fatty acid alkyl ester alkoxylate by gas chromatography (also referred to as GC method). It is a value obtained by summing the area of the maximum peak of a peak and two peaks before and after it, and dividing by the total area of the peak. When a plurality of types of fatty acid alkyl ester alkoxylates are contained, for example, the maximum peak of the obtained fatty acid alkyl ester alkoxylate-derived peak and the total of the areas of two peaks before and after that are divided by the total peak area.

In order to widen the distribution of the added mole number of the alkylene oxide, it is more preferable that the C/B ratio be 0.93 or more.

When C/B ratio is below the said preferable upper limit, the catalytic activity of the catalyst (alpha) obtained becomes high, and fatty-acid alkylester alkoxylate can be manufactured efficiently. When the C/B ratio is less than 1, the catalytic activity of the resulting catalyst (?) can be remarkably improved.

Moreover, as for mass ratio (henceforth "(B+C)/A ratio") represented by [(B)component + (C)component]/(A)component in this process, 1/3-1 are preferable, , 1/2.5 to 1 or less are more preferable. As a lower limit of the said (B+C)/A ratio, 1/3 is preferable, 1/2.5 is more preferable, and 1 is preferable as an upper limit.

(B+C) If /A ratio is below the said preferable upper limit, it can stir easily and can mix (B)component and (C)component efficiently. If it is less than the said preferable lower limit, content of the catalyst active component in (A) component decreases, and when manufacturing a fatty acid alkylester alkoxylate, the addition amount of catalyst ((alpha)) increases too much, and it is inefficient.

··Other processes

After the mixing step, a catalyst aging step of stirring the catalyst (α) at an arbitrary temperature may be provided. 10-60 degreeC is preferable and, as for the temperature condition of a catalyst aging process, 20-50 degreeC is more preferable, for example. As a lower limit of the said temperature condition, 10 degreeC is preferable, 20 degreeC is more preferable, as an upper limit, 60 degreeC is preferable and 50 degreeC is more preferable. By providing this process, the quantity of unreacted (B)component can be reduced.

The stirring time in this step is, for example, 0.5 to 3 hours.

Further, the concentration of the catalytically active component in the catalyst (α) may be increased by filtering the catalyst (α) and performing static separation.

<Method for producing fatty acid alkyl ester alkoxylate>

Hereinafter, one Embodiment of the manufacturing method of the fatty acid alkylester alkoxylate of this invention is demonstrated.

1 mole of fatty acid alkylester represented by general formula (I) in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of monohydric/bihydric alcohol It is a method of adding 5-25 mol of alkylene oxide with respect to this, and the manufacturing method which has a catalyst dispersion process, an addition reaction process, and an aging process is mentioned.

≪Catalyst Dispersion Process≫

The catalyst dispersion step is a step of dispersing the catalyst (α) in a mixture of a fatty acid alkyl ester represented by the general formula (I) as a starting material and a specific amount of a monohydric/bihydric alcohol. In this step, a fatty acid alkyl ester, catalyst (α), and a specific amount of monohydric/bihydric alcohol are mixed.

In this process, for example, a stirred bath reactor is used.

The mixing ratio of the fatty acid alkyl ester and the monohydric/bihydric alcohol in the catalyst dispersion step is 0.05 to 0.20 moles, preferably 0.06 to 0.10 moles, per 1 kg of the fatty acid alkylester. The lower limit of the amount of the monohydric/bihydric alcohol is 0.05 mol, preferably 0.06 mol, and the upper limit is 0.20 mol, preferably 0.10 mol with respect to 1 kg of the fatty acid alkylester.

When the amount (mol) of the monohydric/bihydric alcohol with respect to 1 kg of the fatty acid alkyl ester is equal to or greater than the above lower limit, a fatty acid alkyl ester alkoxylate useful as a cleaning component of a liquid detergent having good fluidity under low-temperature conditions can be produced. This effect becomes a threshold when the upper limit is exceeded. If it is below the said upper limit, cost suppression will be attained. Moreover, when the said upper limit is exceeded, the addition mole number distribution of an alkylene oxide may become narrow too much.

Moreover, when a catalyst ((alpha)) is used, (A) component is carried in with a catalyst active component.

(A) When component contains the fatty acid alkylester of the said formula (I), the fatty acid alkylester corresponding to the said Formula (I) derived from (A) component in the amount of fatty acid alkylester of the starting material in this process is assumed to be included. That is, the amount of the fatty acid alkylester of the total amount of the fatty acid alkylester corresponding to the formula (I) derived from (A) component and the amount of the fatty acid alkylester corresponding to the formula (I) newly added in the catalyst dispersion step is the starting material. of fatty acid alkyl ester.

(A) When component contains monohydric/2hydric alcohol, it shall be assumed that the monohydric/2hydric alcohol derived from (A) component is contained in the quantity of monohydric/2hydric alcohol of a specific amount in this process. . That is, the amount of monohydric/2hydric alcohol of the sum of the monohydric/2hydric alcohol amount derived from (A) component and the monohydric/2hydric alcohol amount newly added in the catalyst dispersion process is 0.05-0.20 mol with respect to 1 kg of fatty acid alkylester do.

The amount of catalyst added to the raw material can be defined from the amount of metal in the catalyst (?), and the amount of the metal is preferably 0.01 to 0.25 mol, more preferably 0.02 to 0.10 mol, with respect to 1 kg of the fatty acid alkylester as the raw material.

≪Addition Reaction Process≫

In the addition reaction step, 5 to 25 moles of alkylene oxide are added to 1 mole of the fatty acid alkylester represented by the general formula (I) in the presence of a specific alkoxylation catalyst (catalyst (α)) and a specific amount of monohydric/bihydric alcohol. It is a process of obtaining a fatty acid alkylester alkoxylate by adding. This step is a step of performing an operation (condition setting operation) of setting arbitrary temperature and pressure conditions for the addition reaction, and then adding an alkyl It has a process of performing operation (AO contact operation) which makes ren oxide (it may call AO hereafter) contact.

The process of performing the condition setting operation:

In this process, suitable temperature and pressure conditions for the addition reaction are set. The temperature conditions for the addition reaction (addition reaction temperature) are, for example, preferably 150 to 180°C, more preferably 160 to 180°C.

The pressure conditions for the addition reaction are suitably determined in consideration of the addition reaction temperature, for example, 0.1 to 1 MPa is preferable, and 0.1 to 0.6 MPa or less is more preferable. As a lower limit of the said pressure condition, 0.1 is preferable, as an upper limit, 1 Mpa is preferable and 0.6 Mpa is more preferable.

The process of performing the AO contact operation:

In this step, the alkylene oxide is brought into contact with the mixture of the fatty acid alkyl ester obtained in the catalyst dispersion step, the catalyst (α), and a specific amount of a monohydric/bihydric alcohol. The introduction amount of AO with respect to 1 mol of fatty acid alkylester represented by general formula (I) in AO contact operation is 5-25 mol, and 10-20 mol is preferable. The lower limit of the introduction amount of AO is 5 mol, preferably 10 mol, and the upper limit is 25 mol, preferably 20 mol.

The greater the number of moles of AO added, that is, the greater the amount of AO introduced, the greater the amount of polymer polyethylene glycol produced.

≪Aging process≫

The aging step is a step in which the reaction product is stirred in a stirring tank after the addition reaction step, that is, the reactant at an arbitrary temperature. By providing this process, the quantity of unreacted fatty acid alkylester and the quantity of unreacted AO can be reduced. As for the temperature conditions of this process, 150-180 degreeC is preferable, for example, 160-180 degreeC is more preferable, and it is more preferable that it is the same as the addition reaction temperature. It is preferable that it is 10 to 20 minutes, and, as for the stirring time in an aging process, it is more preferable that it is 30 to 60 minutes.

In addition to the catalyst dispersion step, the addition reaction step, and the aging step, the production method of the present embodiment may include, if necessary, a purification step of removing the catalytically active component and the like remaining in the fatty acid alkylester alkoxylate. As a method of removing a catalytically active component etc., the method by water washing, centrifugation, filtration, etc. is mentioned, for example.

Especially, it is preferable to perform water washing and centrifugation.

In the purification step, for example, the reaction product obtained in the aging step is heated and dissolved at 70 to 120° C., 5 to 30 parts by mass of purified water is added with respect to 100 parts by mass of the reaction product, and the mixture is stirred for 30 to 120 minutes. Then, it cools to 50-70 degreeC, and stirs for 30-120 minutes again. Thereafter, the catalytically active component and the like are removed by centrifugation.

In the production method of the present embodiment described above, the entire amount of the monohydric/bihydric alcohol in a specific amount is blended in the catalyst dispersion step, but the present invention is not limited thereto, and the specific amount of monohydric alcohol is set by the condition setting operation in the addition reaction step. The whole amount of the /2-hydric alcohol may be blended; A part of the monohydric/bihydric alcohol in a specific amount may be blended in the catalyst dispersion step, and the remaining monohydric/bihydric alcohol may be blended in the condition setting operation in the addition reaction step.

In either case, before the AO contact operation, that is, at the time of adding the alkylene oxide to the fatty acid alkyl ester, the mixing ratio of the fatty acid alkyl ester and the monohydric/bihydric alcohol is 0.05 to 1 kg of the monohydric/bihydric alcohol with respect to 1 kg of the fatty acid alkyl ester. It becomes 0.20 mole.

In the method for producing a fatty acid alkyl ester alkoxylate of the present invention, in the presence of a specific alkoxylation catalyst and 0.05 to 0.20 moles of a monohydric/bihydric alcohol with respect to 1 kg of the fatty acid alkyl ester represented by the general formula (I), the general formula 5-25 mol of alkylene oxide is added with respect to 1 mol of fatty acid alkylester represented by (I). Thus, according to this production method, since the addition reaction step is carried out in the presence of a specific amount of monohydric/bihydric alcohol, fatty acid alkyl ester alkoxylate useful as a cleaning component of a liquid detergent having good fluidity under low-temperature conditions can be produced. .

(fatty acid alkyl ester alkoxylate)

According to the manufacturing method of this invention, the fatty-acid alkylester alkoxylate represented by the following general formula (II) is manufactured suitably.

R ¹¹ CO-(R ¹³ O) _m -R ¹² ...(II)

[In formula (II), R ¹¹ is a hydrocarbon group having 7 to 17 carbon atoms. R ¹² is a straight-chain alkyl group having 1 to 3 carbon atoms. R ¹³ O is an oxyalkylene group having 2 to 4 carbon atoms. m represents the average number of repetitions of R ¹³ O, and is a number of 5 to 25.

In the formula (II), R ¹¹ and R ¹² are the same as R ¹¹ and R ¹² in each of the formula (I).

R ¹³ O is an oxyethylene group, an oxypropylene group, or an oxybutylene group. (R ¹³ O) _m may be a mixture of two or more oxyalkylene groups among an oxyethylene group, an oxypropylene group, and an oxybutylene group. When two or more types of oxyalkylene groups are mixed, the oxyalkylene groups may be mixed in block shape, and may be mixed in random shape. As an oxyalkylene group, an oxyethylene group is especially preferable.

m is the number of 5-25, and the number of 9-20 is preferable. In addition, m has shown the "average" repetition number of an oxyalkylene group. That is, the compound represented by the general formula (II) is an aggregate of molecules having different repeating numbers of oxyalkylene groups. Further, the fatty acid alkyl ester alkoxylate produced by the method of the present invention may be an aggregate of other molecules of ^{R 11 . R 11} or R ¹² of each molecule of each molecule constituting the aggregate of molecules may be the same or different.

The fatty acid alkylester alkoxylate produced by the above production method is useful as a cleaning component of a liquid detergent, and the liquid detergent having this as a cleaning component has good fluidity under low-temperature conditions.

(liquid cleaner)

The fatty acid alkyl ester alkoxylate manufactured by the manufacturing method of this invention is used suitably for a liquid detergent. The liquid detergent containing the fatty acid alkylester alkoxylate produced by the production method of the present invention can be used for household and industrial use, is preferable as a medical liquid detergent, and is a concentrated type medical liquid detergent with a high surfactant concentration. It is particularly preferred.

In a liquid detergent, 10-50 mass % is preferable with respect to the gross mass of a liquid detergent, and, as for content of fatty-acid alkylester alkoxylate, 30-50 mass % is more preferable. As a lower limit, 10 mass % is preferable, 30 mass % is more preferable, and as an upper limit, 50 mass % is preferable.

When content of fatty-acid alkylester alkoxylate is more than the said preferable lower limit, the fluidity|liquidity under low-temperature conditions will become high. In addition, the cleaning power against contamination is increased. On the other hand, if it is below the said preferable upper limit, the viscosity increase of the liquid detergent under low-temperature conditions is suppressed more.

Other ingredients included in the liquid detergent include, for example, surfactants, chelating agents, alkali agents, antioxidants, enzymes, enzyme stabilizers, thickeners or solubilizers, preservatives, metal oxides or metal salts, feel improvers, optical brighteners, ash An antifouling agent, a soil release agent, a pearl agent, a bleaching agent, a flavoring agent, a coloring agent, an emulsifier, extracts such as natural products, a pH adjuster, and the like can be used.

The liquid detergent containing the fatty acid alkylester alkoxylate manufactured by the manufacturing method of this invention is hard to produce solidification under low-temperature conditions, and fluidity|liquidity is favorable. For this reason, such a liquid detergent can be sold and used in a wide area as a commercially available product in the market.

Example

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, in this Example, "%" represents "mass %" unless otherwise stated.

The raw materials used in this example are as follows.

· Fatty acid alkyl ester

Methyl laurate: Trade name "Pastel M12", manufactured by Lion Chemicals Co., Ltd.

Methyl myristate: Trade name "Pastel M14", Lion Chemicals Co., Ltd. product.

· Alkylene oxide

Ethylene oxide: Air Water Co., Ltd. product.

· Alkoxylation catalyst

A catalyst (α-1) (α-2) (α-3) (α-4) (β) synthesized by a production method described below.

・Monohydric/Bihydric Alcohol

2-EH:2-ethylhexanol, reagent, Junsei Chemical Co., Ltd. product.

2-PrOH:2-propanol, first-class reagent, manufactured by Kanto Chemical Co., Ltd.

・Components of liquid detergent

a-1-1 to a-1-12: Fatty acid alkyl ester alkoxylate (fatty acid methyl ester ethoxylate (MEE), EO average addition prepared by the production methods of Examples 1 to 7 and Comparative Examples 1 to 5) confiscation 15). ^{A mixture of one in which R 11} in the general formula (II) is an alkyl group having 11 carbon atoms and an alkyl group having 13 carbon atoms. In formula (II), R ¹² is a methyl group, R ¹³ O is an oxyethylene group, and m is 15;

a-2: What added ethylene oxide equivalent to an average of 15 mol with respect to P&G company natural alcohol CO-1217 (brand name).

[Synthesis of a-2]

In a pressure-resistant reaction vessel, 224.4 g of natural alcohol CO-1270 manufactured by P&G Corporation and 2.0 g of a 30 mass % NaOH aqueous solution were collected, and the inside of the reaction vessel was replaced with nitrogen. Next, after dehydration at a temperature of 100°C and a pressure of 2.0 kPa or less for 30 minutes, the temperature was raised to 160°C. Then, while stirring, 760.4 g of ethylene oxide (gas phase) was gradually added into the alcoholic liquid using a blowing tube while adjusting the addition rate so that the reaction temperature did not exceed 180°C. After completion of the addition of ethylene oxide, the mixture was aged at a temperature of 180°C and a pressure of 0.3 MPa or less for 30 minutes. Thereafter, unreacted ethylene oxide was distilled off at a temperature of 180°C and a pressure of 6.0 kPa or less for 10 minutes. Next, after cooling to a temperature of 100° C. or less, 70 mass % p-toluenesulfonic acid was added and neutralized so that the pH of a 1 mass % aqueous solution of the reactant was about 7, and a-2 was obtained.

b-1: Coconut fatty acid, manufactured by Nichiyu Corporation.

e-1: methylglycine diacetate trisodium (MGDA), trade name "Trilon M", manufactured by BASF.

Protease: Trade name "Corona agent 48L", manufactured by Novozymes.

Product made in SR: Soil release agent, brand name "TexCare SRN-170C", made by Clariant Japan.

LAS-H: Straight-chain alkylbenzenesulfonic acid, trade name "Lifon LH-200", manufactured by Lion Corporation.

MEA: Monoethanolamine, manufactured by Nippon Shokubai.

BHT: Dibutylhydroxytoluene, trade name "SUMILZER BHT-R", manufactured by Sumitomo Chemical.

Citric acid: trade name "citric acid", manufactured by Kanto Chemical Co., Ltd.

Ethanol: Brand name "Synthesis of 95 specific alcohols", manufactured by Nippon Alcohol Hanbai Co., Ltd.

Sodium lactate: Trade name "sodium lactate", manufactured by Kanto Chemical Co., Ltd.

Perfume: Perfume composition A described in Tables 11 to 18 of Japanese Patent Application Laid-Open No. 2002-146399.

Color: Green No. 3, trade name “Green No. 3”, manufactured by Mizunotomi Kasei Co., Ltd.

pH adjusters: sulfuric acid, sodium hydroxide, potassium hydroxide, monoethanolamine.

<Preparation of alkoxylation catalyst>

The following raw materials (liquid dispersion medium, alkaline earth metal compound, sulfuric acid) were used.

Liquid dispersion medium: A mixture of fatty acid methyl esters of methyl laurate and methyl myristic acid, trade name Pastel M124, manufactured by Lion Chemicals Corporation.

Alkaline earth metal compound: Calcium acetate monohydrate, special grade reagent, manufactured by Kanto Chemical Co., Ltd.

Calcium oxide, special grade reagent, Wako Pure Chemical Industries, Ltd.

Barium oxide, special grade reagent, Wako Pure Chemical Industries, Ltd.

Sulfuric acid: Special grade reagent, concentration 96% by mass, Kanto Chemical Co., Ltd. product.

By mixing the alkaline earth metal compound and sulfuric acid in a liquid dispersion medium, the catalyst (α-1), the catalyst (α-2), the catalyst (α-3), the catalyst (α-4), and the catalyst (β) are alkoxylation catalysts. was manufactured C/B ratios of catalyst (α-1), catalyst (α-2), catalyst (α-3), catalyst (α-4), and catalyst (β) are 0.90, 0.96, 0.90, 0.90, and 0.67, respectively, (B+C)/A ratio is 0.46, 0.47, 0.41, 0.40, 0.42. In addition, the compounding quantity of each following component is a pure part conversion value.

Method for preparing catalyst (α-1), (α-2), (β)

Specifically, the fatty acid methyl ester mixture and calcium acetate monohydrate were put into a 500 mL beaker, and the mixture was mixed at room temperature (25° C.) with a puddle stirring blade to obtain a dispersion (dispersion step).

While stirring this dispersion, 96 mass % of sulfuric acid was added over 10 minutes by a dropping funnel, and it mixed (mixing process). In the mixing step, since the addition of sulfuric acid generates heat, the beaker was cooled in a water bath and stirred for 1 hour while controlling the reaction temperature to 20 to 50°C.

After adding sulfuric acid, the alkoxylation catalyst (catalyst (α-1), catalyst (α-2), and catalyst (β)) was obtained by stirring again for 2 hours while maintaining at 20 to 50°C (catalyst aging step).

Method for preparing catalyst (α-3)

Specifically, the fatty acid methyl ester liquid mixture and calcium oxide were put into a 500 mL beaker, and the mixture was mixed at room temperature (25° C.) with a puddle stirring blade to obtain a dispersion (dispersion step).

Sulfuric acid diluted to 76% by a dropping funnel was added over 10 minutes while stirring this dispersion and mixed (mixing step). In the mixing step, since the addition of sulfuric acid generates heat, the beaker was cooled in a water bath and stirred for 1 hour while controlling the reaction temperature to 20 to 50°C.

After adding sulfuric acid, the alkoxylation catalyst (catalyst (α-3)) was obtained by stirring again for 2 hours while maintaining the temperature at 20 to 50°C (catalyst aging step).

Method for preparing catalyst (α-4)

Catalyst (α-4) was obtained in the same manner as for catalyst (α-3) except that barium oxide was used instead of calcium oxide.

In addition, the quantity of the compound used is as having described in Table 1.

<Production of fatty acid alkyl ester alkoxylate>

(Examples 1-7, Comparative Examples 3-5)

12.5 g of the above-obtained alkoxylation catalyst (catalyst (α-1), catalyst (α-2), catalyst (α-3), catalyst (α-4), or catalyst (β)) obtained above in an autoclave; After putting 462 g of methyl urate and 166 g of the said methyl myristate, the monohydric/bihydric alcohol of predetermined amounts shown in Table 1 was added, and it stirred at room temperature (20 degreeC) (catalyst dispersion process).

Nitrogen substitution was performed in the autoclave while stirring. Then, it heated up to the ethylene oxide (EO) addition reaction temperature (160 degreeC), and adjusted the pressure to 0.1-0.5 MPa (condition setting operation). Then, under these temperature and pressure conditions, 1876 g of ethylene oxide (EO) (15 times mole of the total of methyl laurate and methyl myristate) was introduced, and the reaction proceeded while stirring (EO contact operation) (above, addition reaction process).

Then, it stirred at the said EO addition reaction temperature for 0.5 hour (aging process). Then, it cooled to 80 degreeC and 2516g of reaction products were obtained.

Then, 29.3 g of purified water was added to 250 g of the reaction product dissolved by heating to 80°C, and the mixture was stirred for 30 minutes while maintaining 80°C. Then, it cooled to 50 degreeC, and continued stirring for another 30 minutes. After that, the catalyst and the aggregate were removed by centrifugation, and purification was performed (purification step).

According to the above production method, a-1-1 to a-1-7 and a-1-10 to a-1-12 of the target fatty acid methyl ester ethoxylate (MEE) were obtained, respectively.

(Comparative Example 1)

A-1-8 of the target fatty acid alkylester alkoxylate was obtained in the same manner as in Example 1 except that the monohydric/2hydric alcohol was not added.

(Comparative Example 2)

What added ethylene oxide equivalent to an average of 15 mol with respect to 2-ethylhexanol (15EO adduct of 2-EH) was synthesize|combined.

The alkoxylation catalyst (?-1) obtained above was filtered, washed thoroughly with acetone, and the solid content was dried at 50°C. After putting 2.0 g of solid content of the alkoxylation catalyst obtained above and 285 g of 2-ethylhexanol in an autoclave, it stirred at room temperature (20 degreeC).

Nitrogen substitution was performed in the autoclave while stirring. Then, it heated up to the ethylene oxide (EO) addition reaction temperature (160 degreeC), and adjusted the pressure to 0.1-0.5 MPa (condition setting operation). Then, under these temperature and pressure conditions, 1447 g (15 times mole of 2-ethylhexanol) of ethylene oxide (EO) was introduced, and the reaction was allowed to proceed while stirring.

Then, it stirred at the said EO addition reaction temperature for 0.5 hour. Then, it cooled to 80 degreeC, and 1734 g of reaction products were obtained.

Subsequently, 250 g of the reaction product dissolved by heating to 50°C was filtered, the catalyst was removed, and purification was performed to obtain a 15EO adduct of 2-EH.

Then, the fatty acid alkyl ester alkoxylate prepared by the production method of Comparative Example 1 and 0.06 mol of the 15EO adduct of 2-EH with respect to 1 kg of this fatty acid alkyl ester alkoxylate are mixed (the 15EO adduct of 2-EH) was added), and a-1-9 was obtained.

<Production of liquid detergent>

(Test Example 1)

According to the compounding composition shown in Table 2, 1000 g of liquid detergents were manufactured by the conventional method (When there is an unmixed component, the component is not mix|blended.).

(Test Examples 2 to 12)

Except having changed fatty acid methyl ester ethoxylate (MEE) into a-1-2 to a-1-12 from a-1-1, respectively, it carried out similarly to Experiment 1, and produced 1000 g of liquid detergents.

The unit of the compounding quantity in Table 2 is mass %, and any component shows a net-part conversion amount. Moreover, the liquid detergent of each example was balanced and prepared with the remainder of water so that the sum total of each component described in a table|surface might be set to 100 mass %.

In the liquid detergent of each example, pH in 25 degreeC was adjusted to 7.0 by adding an appropriate amount of a pH adjuster, respectively. The pH of the liquid detergent is controlled by temperature of the liquid detergent at 25 ° C., using a glass electrode type pH meter (manufactured by Toa DK Co., Ltd., product name HM-30G), and the glass electrode is directly immersed in the liquid detergent, The value shown after 1 minute elapsed was measured.

<Evaluation>

The fluidity|liquidity of the liquid detergent was evaluated by the evaluation method shown below about the liquid detergent of each example. The results are shown in Table 2.

[Evaluation of fluidity of liquid detergent]

100 mL of the liquid detergent of each case was respectively taken in a transparent glass bottle (a wide-mouth standard bottle PS-NO.11), and the lid was closed and sealed. In this state, the sealed glass bottle was left still in a thermostat at -5°C and stored for 1 month.

After such storage, the glass bottle is taken out from the thermostat at -5°C, the glass bottle stored at -5°C is horizontally knocked down, the change in the liquid surface is visually observed, and the liquid is based on the following evaluation criteria. The fluidity|liquidity of a detergent was evaluated.

Evaluation standard

A: The liquid level became level within 10 seconds after the glass bottle was leveled down.

B: It took more than 10 seconds for the liquid level to level after dropping the glass bottle horizontally.

C: Since it was solidified, fluidity|liquidity was not confirmed at all.

From the results shown in Table 2, it was confirmed that the liquid detergents of Test Examples 1 to 7 containing fatty acid alkyl ester alkoxylate prepared by the production methods of Examples 1 to 7 to which the present invention was applied had good fluidity under low-temperature conditions. .

Moreover, it was also confirmed that the fatty acid alkylester alkoxylates manufactured by the manufacturing methods of Examples 1-7 to which this invention was applied are useful as a washing|cleaning component of a liquid detergent.

Hereinafter, solidification at low temperature of a liquid detergent using a fatty acid alkyl ester alkoxylate prepared by a sulfuric acid/alkaline earth metal catalyst and a liquid detergent using a fatty acid alkyl ester alkoxylate prepared by the composite metal oxide catalyst It demonstrates using an Example and a comparative example.

(Example 3, Test Example 3)

For comparison, Example 3 in which a fatty acid alkyl ester alkoxylate was prepared with a sulfuric acid/alkaline earth metal catalyst, and Test Example 3 prepared using the fatty acid alkyl ester alkoxylate a-1-3 obtained in Example 3 It described in Table 3 and Table 4 about the liquid detergent. The added mole number distribution of ethylene oxide measured by the following GC method of fatty-acid alkylester alkoxylate a-1-3 was 54 %.

(Comparative Example 6, Test Example 13) Liquid detergent using a fatty acid alkyl ester alkoxylate prepared by a composite metal oxide catalyst

(Comparative Example 6) A fatty acid alkyl ester alkoxylate was prepared using a composite metal oxide catalyst.

Aluminum/magnesium hydroxide (manufactured by Kyowa Kagaku Kogyo Co., Ltd., Kyowado _{300) having a chemical composition of 2.5MgO·Al 2} O ₃ ·mH ₂ O was calcined at 900° C. for 3 hours to obtain magnesium/aluminum composite metal oxide catalyst powder ( catalyst γ) was obtained.

Methyl laurate (Lion Chemical Co., Ltd., Pastel M12) 184.1 kg (859 mol), methyl myristate (Lion Chemical Co., Ltd., Pastel M14) 66.0 kg (272 mol), the above complex in a 2000 kL stirring reaction tank After adding 1.00 kg of a metal catalyst and 1.25 kg of glycerin as a polyhydric alcohol, 0.05 kg of potassium hydroxide was added thereto, followed by stirring for 10 minutes to perform alkali modification of the catalyst. Thereafter, while stirring and mixing, the inside of the reaction tank was replaced with nitrogen, heated to 100°C, and dehydrated for 30 minutes under reduced pressure of 1.3 kPa or less. Then, it heated to 180 degreeC, and introduce|transduced 747.6 kg (16972 mol, 15 times mol of fatty acid methyl ester) of ethylene oxide under the conditions whose upper pressure limit is 0.49 MPa. Furthermore, after performing the aging reaction for 0.5 hour, it cooled to 80 degreeC and extracted, 999 kg was obtained as a reaction crude product containing an alkylene oxide adduct, ie, fatty acid alkylester alkoxylate a-1-13. Fatty acid alkylester alkoxylate a-1-13 had an ethylene oxide average added mole number of 15, and the added mole number distribution of ethylene oxide measured by the following GC method was 54 %. In addition, the fatty acid alkylester alkoxylate a-1-13 contained 0.9% by weight of polyethylene glycol as a by-product.

(Test example 13) Except having changed fatty acid methyl ester ethoxylate (MEE) into a-1-13 from a-1-1, it carried out similarly to Example 1, and produced 1000 g of liquid detergents.

(Comparative Example 7, Test Example 14) Liquid detergent using a fatty acid alkyl ester alkoxylate prepared by a sulfuric acid/alkaline earth metal catalyst without adding a specific amount of monohydric/bihydric alcohol

(Comparative Example 7) Fatty acid alkyl except that 0.06 mol of glycerin was added with respect to 1 kg of fatty acid alkyl ester without adding isopropanol used as a monohydric/bihydric alcohol in a specific amount in the production of fatty acid alkyl ester alkoxylate In the same manner as in Example 3 of the present application in which ester alkoxylate a-1-3 was prepared, fatty acid alkyl ester alkoxylate a-1-14 was prepared. Fatty acid alkylester alkoxylate a-1-14 had an ethylene oxide average added mole number of 15, and the added mole number distribution of ethylene oxide measured by the following GC method was 54 %.

(Test example 14) Except having changed fatty acid methyl ester ethoxylate (MEE) into a-1-14 from a-1-1, it carried out similarly to Example 1, and produced 1000 g of liquid detergents.

[Measurement and calculation of distribution of added moles of alkylene oxide by gas chromatography method]

Distribution of the number of added moles of ethylene oxide in the reaction mixture (also referred to as EO added mole distribution) was determined by gas chromatography (also referred to as GC method).

The reaction sample was diluted and prepared with acetone so that the density|concentration of fatty-acid alkylester alkoxylate might become a 1% solution, and it was set as the analysis sample.

The conditions of the GC method are the following measurement conditions, and EO added mole number distribution (it is also mentioned GC area %) is computed by the following calculation method. The distribution of the number of added moles of EO becomes wide, so that the value of EO added mole number distribution is small.

(Measurement conditions for GC method)

・Gas chromatography: GC-2025 manufactured by Shimadzu Corporation

·Column: DB-1 HT manufactured by Agilent, 30 m in length, 0.25 mm in inner diameter, 0.1 μm in thickness

· Mobile phase: Helium

・Detector: Hydrogen salt ion detector (FID), 380℃

·Inlet: Split, 380℃

・Temperature: 100℃→380℃

(calculation method)

EO addition mole distribution was computed from the following formula from the peak area of the peak obtained by measuring the sample by GC method.

{(Area of the maximum peak (P1) derived from methyl laurate alkoxylate) + (the total area of two peaks before and after the maximum peak (P1)) + (maximum derived from methyl myristate ester alkoxylate) Area of peak P2) + (total area of two peaks before and after maximum peak P2)} ÷ total peak area

<Evaluation>

About the liquid detergent of each reference example, the fluidity|liquidity of the liquid detergent was evaluated by the same evaluation method as an Example. The results are shown in Table 4.

From the results shown in Tables 3 and 4, the problem that the liquid detergent easily causes solidification under low temperature conditions of less than 0 ° C. is a unique problem that occurs when a liquid detergent is manufactured using a sulfuric acid/alkaline earth metal catalyst. It became clear that this problem was solved by the present invention in which an amount of monohydric/2hydric alcohol was added.

In addition, even when a specific amount of monohydric/2hydric alcohol was not added, the distribution of the number of moles added to alkylene oxide did not significantly change from that when a specific amount of monohydric/2hydric alcohol was added. Therefore, it became clear that the liquid detergent using the fatty-acid alkylester alkoxylate manufactured by adding a specific amount of monohydric / bihydric alcohol became difficult to solidify not by the change of alkylene oxide added mole number distribution.

(Industrial Applicability)

According to the present invention, by using an acid/alkaline earth metal compound catalyst and producing a fatty acid alkyl ester alkoxylate in a reaction system containing a specific amount of monohydric/bihydric alcohol, cleaning of a liquid detergent that is difficult to solidify under low-temperature conditions Fatty acid alkylester alkoxylates useful as components can be prepared.

Claims (3)

In the method for producing a fatty acid alkyl ester alkoxylate in which an alkylene oxide is added to a fatty acid alkyl ester represented by the following general formula (I),
An alkoxylation catalyst formed by reacting an alkaline earth metal compound (B) and at least one acid (C) selected from the group consisting of sulfuric acid, hydrochloric acid and phosphoric acid in a liquid dispersion medium (A), and 0.05 for 1 kg of the fatty acid alkyl ester a step of adding 5 to 25 moles of the alkylene oxide to 1 mole of the fatty acid alkyl ester in the presence of 0.20 moles of at least one alcohol selected from the group consisting of monohydric alcohols and dihydric alcohols;
A method for producing a fatty acid alkyl ester alkoxylate wherein the molar ratio (C/B ratio) of the acid (C) to the alkaline earth metal compound (B) is 0.8 or more and less than 1.
R ¹¹ COOR ¹² ...(I)
[In formula (I), R ¹¹ is a hydrocarbon group having 7 to ^{17 carbon atoms, and R 12} is a straight chain alkyl group having 1 to 3 carbon atoms.] The method of claim 1,
A method for producing a fatty acid alkyl ester alkoxylate wherein the molar ratio (C/B ratio) of the acid (C) to the alkaline earth metal compound (B) is 0.9 to 0.98. The method of claim 1,
A method for producing a fatty acid alkyl ester alkoxylate, wherein the alcohol is a linear or branched monohydric alcohol having 1 to 18 carbon atoms.