JPH107620A - Production of nonionic surfactant and liquid detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyalkylene oxide addition type nonionic surfactant without causing turbidity in a solution even when mixed into a transparent liquid detergent and stored for a long time. SOLUTION: An alkylene oxide is added to a compound containing active hydrogen and/or a fatty acid alkyl ester in the presence of a nonlayered alkoxylization catalyst containing MgO as a main component and the resultant reaction crude product is brought into contact with activated clay and/or acidic clay and water and then treated.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a polyalkylene oxide-added nonionic surfactant, and an aqueous liquid detergent composition containing the nonionic surfactant.

2. Description of the Related Art Alkylene oxide adducts to higher alcohols and fatty acid alkyl esters are used as various nonionic surfactants incorporated in liquid detergents for clothing, shampoos, dishwashers, household detergents, and the like. It is useful as an intermediate for producing a corresponding anionic surfactant by performing sulfate esterification or carboxymethylation or an intermediate for other industrial products. In recent years, as an alkoxylation catalyst for obtaining a reactant having a narrow alkylene oxide addition molar distribution, for example, a metal ion-added magnesium oxide (Japanese Patent Publication No. 6-1)
No. 5038) and aluminum-magnesium hydroxide calcined products (Japanese Patent Application No. 7-94417).
Mg-based composite oxide catalysts or surface-modified catalysts thereof (Japanese Patent Application No. 6-334772) have been proposed.

However, the reaction crude product (alkylene oxide adduct) obtained by using these alkoxylation catalysts has a narrow addition molar distribution range, a lower pour point, excellent water solubility, and an active hydrogen Although it has excellent properties such as a low content of residual compounds and a low level of odor, when used for applications such as liquid detergents for clothing, hair detergents, dishwashers, and household detergents, There is a disadvantage that the detergent becomes cloudy immediately after blending various detergents or during long-term storage. Such turbidity that occurs immediately after the compounding of the liquid detergent can be prevented to some extent, for example, by increasing the amount of addition of lower alcohols such as ethanol or glycols, or by reducing the compounding amount of the surfactant.
Such a method is not effective in preventing turbidity occurring during long-term storage. On the other hand, Japanese Unexamined Patent Publication (Kokai) No. 6-5055986 discloses that a crude product of a polyalkylene oxide-added nonionic surfactant produced using a layered compound as an alkoxylation catalyst is mixed with water and a filter aid (diatomaceous earth, wood flour). , A substance selected from the group consisting of cellulose and cellulose acetate) to remove the catalyst and the generated polyglycol ethers, improve the filtration characteristics, and describe that the filtrate is transparent at both high and low temperatures. ing. However, when such a nonionic surfactant having improved filtration characteristics is blended with a transparent liquid detergent, the liquid may become cloudy due to long-term storage.

[0003]

DISCLOSURE OF THE INVENTION The present invention provides a method for producing a polyalkylene oxide-added nonionic surfactant which does not become turbid even when stored in a transparent liquid detergent and stored for a long time. The purpose is to do. Another object of the present invention is to provide an aqueous liquid detergent composition containing a polyalkylene oxide-added nonionic surfactant, which does not cause turbidity even when stored for a long period of time.

According to the present invention, a non-layered compound mainly composed of MgO is used as an alkoxylation catalyst, and the obtained reaction crude product is brought into contact with activated clay and / or acid clay and water. After the treatment, the obtained polyalkylene oxide-added nonionic surfactant is used as an aqueous liquid detergent composition, especially a foaming stabilizer as another surfactant component,
This is based on the finding that when blended in an aqueous liquid detergent composition containing a neutralizing agent, a detergency improving agent, and the like, turbidity does not occur even after long-term storage.

That is, the present invention relates to a method for producing an active hydrogen-containing compound and / or a fatty acid alkyl ester to which an alkylene oxide is added in the presence of a non-layered alkoxylation catalyst containing MgO as a main component, to obtain an active crude product. Provided is a method for producing a nonionic surfactant, which comprises treating a clay and / or an acid clay with water after contacting the clay with the clay. The present invention also provides an aqueous liquid detergent composition containing the nonionic surfactant produced by the above method.

BEST MODE FOR CARRYING OUT THE INVENTION The non-layered alkoxylation catalyst containing MgO as a main component used in the present invention is preferably an MgO-based composite oxide, particularly preferably magnesium oxide added with metal ions, a calcined product of aluminum hydroxide / magnesium hydroxide and One or more non-layered compounds selected from those surface modified products. Here, as the metal ion-added magnesium oxide, JP-B-6-15038, JP-A-7-227540, and JP-A-6-19816
No. 9, No. 6-182206, No. 5-1706
No. 88, for example. The descriptions of magnesium oxide added with metal ions in these publications are included in the description of this specification.

[0005] Examples of calcined products of aluminum hydroxide and magnesium include those described in Japanese Patent Application No. 7-94417. Specifically, nMgO.Al ₂ O ₃
A co-precipitate of aluminum hydroxide and magnesium hydroxide represented by mH ₂ O (n: not particularly limited, but preferably about 2.5, m: not particularly limited); Things. The firing temperature is 40
0-950 ° C. is preferred, and more preferably 400-70 ° C.
0 ° C. Aluminum hydroxide in the above specification
The description of the magnesium baked product is included in the description of this specification. Further, examples of the surface-modified product of a metal ion-added magnesium oxide and a calcined product of aluminum / magnesium hydroxide include those described in Japanese Patent Application Nos. 6-33481 and 6-334772. Specifically, the calcined product of aluminum / magnesium hydroxide is surface-modified with a metal hydroxide or metal alkoxide to obtain a modified calcined alumina / magnesium hydroxide catalyst. The metal hydroxide is preferably an alkali metal or alkaline earth metal hydroxide, more preferably sodium hydroxide or potassium hydroxide. The metal alkoxide is preferably an alkali metal or alkaline earth metal alkoxide, more preferably a sodium alkoxide or a potassium alkoxide. The description of the surface modified product in the above specification shall be included in the description of this specification. Among the above various catalysts, the above-mentioned surface-modified products are particularly preferable.

The active hydrogen-containing compound used in the production of the alkylene oxide adduct of the present invention may be any compound as long as it is alkoxylated, and is not particularly limited, and includes alcohols, polyols, amines, and alkanols. Amides and the like;
More than one species can be used as a mixture. Among them, it is preferable to use a straight-chain or branched saturated or unsaturated alcohol having 8 to 22 carbon atoms. As alcohols, n-octanol, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol,
a higher aliphatic primary alcohol having a saturated or unsaturated straight-chain alkyl group having 8 to 22 carbon atoms, such as n-octadecanol, oleyl alcohol, eicosanol, behenol, nonanol, undecanol, tridecanol, or 2-ethyl; Examples include branched alkyl primary alcohols such as hexanol and Guerbet alcohols having 16 to 36 carbon atoms, secondary alcohols such as 2-octanol, 2-decanol and 2-dodecanol, and benzyl alcohol. Examples of the polyols include ethylene glycol, propylene glycol, diethylene glycol, glycerin, sorbitol, trimethylolpropane, and pentaerythritol. As amines, octylamine, dioctylamine, laurylamine, dilaurylamine, stearylamine, primary or secondary amine having a saturated or unsaturated alkyl group having 8 to 36 carbon atoms such as distearylamine, And polyamines such as ethylenediamine and diethylenetriamine. Examples of the alkanolamide include lauryl monoethanolamide and lauryl diethanolamide.

As the fatty acid alkyl ester, those represented by the general formula R ₁ COOR ₂ (where R ₁ is an alkyl group having 6 to 22 carbon atoms and R ₂ is an alkyl group having 1 to 30 carbon atoms) are preferable. . Here, the alkyl group is a concept including a so-called alkenyl group containing a double bond in a carbon chain. In addition, triglyceride, which is a fatty acid ester of glycerin, is also included in this. As the alkylene oxide used in the present invention, an alkylene oxide having 2 to 4 carbon atoms is preferable, and ethylene oxide, propylene oxide and a mixture thereof are particularly preferable. The alkylene oxide can be used in any amount with respect to the active hydrogen-containing compound and / or fatty acid alkyl ester, but it is preferably used in an amount of 1 to 50 mol per 1 mol of the active hydrogen-containing compound and the like, and is preferably used. 3 to 20 mol. The addition reaction of the alkylene oxide can be easily performed under well-known operating procedures and reaction conditions. Reaction temperature is 80 to 230
° C. Also, the reaction pressure depends on the reaction temperature, but is 0-2.
The pressure is 0 atm, preferably 2 to 8 atm, and the addition reaction of the alkylene oxide can be carried out under the condition of dilution with nitrogen, if necessary. The amount of the alkoxylation catalyst used is
The alkylene oxide and the active hydrogen-containing compound to be subjected to the reaction or the type of the hydrophobic raw material such as a fatty acid alkyl ester, etc.
It is preferably 3 to 5% by weight (hereinafter abbreviated as%).

The above reaction is preferably carried out by charging an active hydrogen-containing compound or a fatty acid alkyl ester and an alkoxylation catalyst in an autoclave and introducing an alkylene oxide under a predetermined temperature and pressure under a nitrogen atmosphere. . The reaction crude product thus produced is cooled, and activated clay and / or acid clay is used as an adsorbent and brought into contact with water (preferably after the activated clay and / or acid clay and water are added and mixed). , It is better to process. First, the amount of acid clay and / or activated clay added to the crude product as an adsorbent is preferably in the range of 0.01 to 3%, more preferably 0.02 to 2%, based on the crude product.
The amount of water to be added is preferably in the range of 3 to 30%, more preferably 5 to 20%, based on the crude product. The temperature when contacting (preferably adding / mixing) water with acidic clay and / or activated clay as an adsorbent for the crude product is not particularly limited, but is preferably 40 to 100 ° C. The mixing method is
The order of addition of acid clay and / or activated clay and water, such as simultaneous addition, divided addition, a method of adding acid clay and / or activated clay after adding water, or a reverse addition thereof, may be used. It is not limited. The mixing time is not particularly limited, but may be short as long as the processing effect is not impaired, and is usually preferably 5 to 90 minutes.

Further, the crude product is treated with acid clay and / or activated clay as an adsorbent and brought into contact with water, and then filtered to remove the alkoxylation catalyst and the activated clay and / or acid clay by filtration. If necessary, a filter aid may be added. As the filter aid, a known filter aid can be used. For example, the main component SiO
_As diatomaceous earth of amorphous silicic acid containing 80 to 95% of ₂ , for example, Radiolite # 100, Radiolite #
200, radio light # 500, radio light # 60
0, Radio Light # 900, Zem Light Super M,
Zemrite super 1, zemlite super 56, zemlite super 2, cellite 501, cellite 503,
Celite 535, Celite 545, Hyflo supercell, standard supercell, filter cell and the like. Examples of the aluminum silicate containing about 70% of SiO _{2 as} a main component include Topco # 31 and Topco # 34, and examples of the cellulose-based filter aid include:
KC Flock, SW40, BW20, BW40, BW1
00, BW200, BNB20 and the like.

Further, activated carbon, synthetic zeolite, silica gel, activated alumina and the like can be mentioned.
It can be used as a mixture of more than one species. The use amount of the filter aid is preferably 0.05 to 5% based on the crude product. In the present invention, the thus obtained crude nonionic surfactant is contacted with water using activated clay and / or acidic clay as an adsorbent, and then filtered by a conventional method. For example, it is preferable to use a two-layer filter of cellulose and polyester as a filter paper, a metal mesh filter, or the like, and filter under reduced pressure or pressure at a temperature of 40 to 100 ° C. Furthermore, filtration using a centrifuge, for example, a decanter or a centrifugal clarifier, can be used. Thus, the nonionic surfactant can be obtained as an aqueous solution having a content of the nonionic surfactant of about 70 to 97%. In the present invention, in particular, using the above surface-modified alkoxylation catalyst, the reaction crude product obtained by adding an alkylene oxide to a fatty acid alkyl ester is contacted with activated clay and water, and then treated to obtain a non-ionic Preferably, a surfactant is obtained.

In the present invention, an aqueous liquid detergent composition can be prepared by blending the nonionic surfactant thus obtained together with other surfactant components. Other surfactant components include detergency improving agents such as anionic surfactants, amphoteric surfactants, and nonionic surfactants. Examples of the anionic surfactant include a polyoxyethylene sulfate, a saturated or unsaturated fatty acid salt (including a saturated or unsaturated fatty acid), an ether carboxylic acid or a salt thereof. Examples of the amphoteric surfactant include imidazoline, sulfobetaine, carboxybetaine and the like. Examples of the nonionic surfactant include those in which an alkylene oxide is added to an active hydrogen-containing compound in a block or random manner. Also, as a neutralizing agent or foam stabilizer
Examples thereof include diethanolamine, triethanolamine, and lauryldimethylamine oxide. Further, the aqueous liquid detergent composition of the present invention may contain an enzyme, a bleaching component, a bleaching activator, a softening agent, an inorganic salt, a viscosity modifier, a hydrotrobe agent, and a preservative as long as the purpose and effect are not impaired. , A bactericide, an antibacterial agent, an antioxidant, a humectant, an ultraviolet absorber, a pigment, a fragrance, and the like can be blended in any combination. Here, it is preferable that the amount of the nonionic surfactant in the aqueous liquid detergent composition is about 1 to 50%. Further, in the case where the aqueous liquid detergent composition contains the above-mentioned detergency enhancer, foaming stabilizer or neutralizer, coexistence with the nonionic surfactant causes turbidity. Therefore, in the present invention, an aqueous liquid cleaning agent containing 1 to 20% of a detergency enhancer, a foaming stabilizer or a neutralizing agent, and 5 to 40% of a nonionic surfactant as other surfactant components. In the case of an agent composition, it is particularly effective in preventing turbidity.

[0012]

The nonionic surfactant obtained by the method of the present invention does not cause turbidity when incorporated in a liquid detergent or the like, and is particularly useful for preparing a transparent liquid detergent composition. Such a transparent liquid detergent composition can be widely used as a liquid detergent for clothing, a shampoo, a dishwashing detergent, a household detergent, and the like. Next, the present invention will be described in detail with reference to examples, but the present invention is not limited thereto.

【Example】

Reference Example 1 (catalyst preparation example) Commercially available 2.5 MgOAl ₂ O ₃ .nH ₂ O [Kyowa Chemical Industry
Aluminum hydroxide / magnesium hydroxide having the chemical composition of Kyoward 300AS
Calcination at 750 ° C. for 2 hours gave a non-layered alkoxylation catalyst.

Reference Example 2 (Preparation of Crude Product 1) In a 4 liter autoclave, 97.7 g (0.52 mol) of lauryl alcohol and Diadol 13 (alcohol having 13 carbon atoms: manufactured by Mitsubishi Chemical Corporation) as an active hydrogen-containing compound.
293.1 g (1.45 mol) and 0.39 g of the catalyst of Reference Example 1
(0.1% / active hydrogen-containing compound)
The temperature was raised (160 ° C.) while stirring. Then, set the temperature to 1
While maintaining the pressure at 80 ° C. and the pressure at 3 atm, 608.9 g (7 mol) of ethylene oxide was introduced to carry out an addition reaction.
After aging for 0.5 hours at the same temperature, the mixture was cooled to 80 ° C and crude product 1
I got Reference Example 3 (Preparation of Crude Product 2) Crude product 2 was obtained by adding 6 mol of ethylene oxide to methyl laurate by the catalyst preparation method and the reaction method described in Example 1 of Japanese Patent Application No. 6-334772. . Specifically, it is obtained by calcining alumina / magnesium hydroxide having a chemical formula of 2.5MgO.Al ₂ O ₃ .nH ₂ O (Kyowad 300CY manufactured by Kyowa Chemical Industry Co., Ltd.) at 500 ° C. for 1 hour in a nitrogen stream. Fired alumina hydroxide / magnesium 1.
40 g of 0.15% potassium hydroxide methanol solution in 5 g
Was dried while spraying, and further dried at 100 ° C. for 10 hours to obtain a reforming catalyst. This reforming catalyst and 440 g of methyl laurate were charged into an autoclave,
Then, after the inside of the autoclave was replaced with nitrogen, 543 g of ethylene oxide was introduced while maintaining the temperature at 180 ° C. and the pressure at 3 atm, followed by stirring reaction to obtain a crude product 2.

Example 1 A crude product 1 was placed in a 1-liter four-necked flask equipped with a stirrer.
Was added and heated to 80 ° C. Next, 2.4 g of activated clay (first-class reagent) and 41 parts of ion-exchanged water
g, and the mixture was mixed for 1 hour. Then, the solid matter (alkoxylation catalyst, activated clay) was removed by filtration by a filtration operation to obtain a nonionic surfactant No. 1 (concentration: 83%). The filtration equipment used is a two-layer filter of cellulose and polyester,
The test was carried out at a temperature of 80 ° C. and a nitrogen pressure of 2 atm with a pressure filter having an inner diameter of 4 cm. Example 2 KC Floc W-50S as filtration aid before filtration operation
(Sanyo Kokusaku Pulp Co., Ltd.) A nonionic surfactant No. 2 (concentration of 83) was treated in the same manner as in Example 1 except that 1.2 g was added.
%).

Example 3 A nonionic surfactant No. 3 (concentration of 85) was treated in the same manner as in Example 2 except that 0.72 g of activated clay (first-class reagent) and 35.3 g of ion-exchanged water were added as adsorption treatment agents. %). Example 4 A non-ionic surfactant No. 4 was treated in the same manner as in Example 1 except that acidic clay (first-class reagent) was used instead of activated clay.
(Concentration 83%). Example 5 A nonionic surfactant No. 5 (concentration: 83%) was obtained in the same manner as in Example 2, except that the crude product 2 was used. Example 6 A non-ionic surfactant obtained in Examples 1 to 5 was blended in a predetermined amount to prepare a transparent liquid detergent, and the appearance was evaluated by the following method. Evaluation method After leaving the liquid detergent composition at -5 ° C or 50 ° C for 7 days,
The appearance was visually determined according to the following criteria. ：: transparency ×: cloudiness Table 1 shows the evaluation results.

[0016]

[Table 1] Table-1 Inventive product 1 2 3 4 5 Nonionic surfactant No1 No2 No3 No4 No5 (%) 25 29 27 18 23 C ₁₂ OH-15EO3PO (%) ¹⁾ 12 15 13 9 12 Unsaturated fatty acid (%) ²⁾ 2 2 2 1 2 Diethanolamine (%) 13 13 13 9 13 Trialkylene glycol butyl ether (%) 2 2 1 1 1 1 1 Ethanol (%) 5 5 5 4 5 Fragrance Small amount Small amount Small amount Small amount Small amount Small amount Small amount Small amount Small amount Small amount Small amount Water balance balance balance balance balance evaluation -5 ° C., after 7 days storage ○ ○ ○ ○ ○ results 50 ° C., 7 days after storage ○ ○ ○ ○ ○ 1) C 12 OH-15EO3PO is ethylene oxide dodecyl alcohol 15 moles and flop propylene It is a nonionic surfactant to which 3 moles of an oxide are added. 2) Unsaturated fatty acids having 18 to 22 carbon atoms

Example 7 A crude product obtained by adding 7 mol of ethylene oxide to lauryl alcohol by the catalyst preparation method and the reaction method described in Example 1 of JP-B-6-15038 (provided that
The reaction was carried out at a temperature of 180 ° C.) in the same manner as the nonionic surfactant No. 1 in the inventive product 1 of Example 6, and the transparent liquid detergent used in place of the surfactant No. 1 was − Neither storage at 5 ° C. for 7 days nor storage at 50 ° C. for 7 days resulted in no cloudiness. Comparative Example 1 Crude product example 1 in a 1-liter four-necked flask equipped with a stirrer
200 g of the alkylene oxide adduct obtained in the above was heated to 80 ° C. Subsequently, 41 g of ion-exchanged water was added and mixed for 1 hour. The mixture was charged into a pressure filter having an inner diameter of 4 cm equipped with a two-layer filter of cellulose and polyester, and filtered at a temperature of 80 ° C. and a nitrogen pressure of 2 atm. The obtained surfactant A was blended in a transparent liquid detergent, and the appearance was evaluated. Comparative Example 2 KC Floc W-50S as a filter aid before the filtration operation
Surfactant B was obtained in the same manner as in Comparative Example 1 except that 1.2 g (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was added, and this was mixed with a transparent liquid detergent, and the appearance was evaluated. After preparing a liquid detergent by mixing a predetermined amount of the surfactant treated in the comparative example, the appearance was evaluated in the same manner as in the example. Table 2 shows the evaluation results.

[0018]

[Table 2] Table-2 Comparative Example 1 2 Nonionic surfactant AB (%) 25 29 C ₁₂ OH-15EO3PO (%) ¹⁾ 12 15 Unsaturated fatty acid (%) ²⁾ 22 Diethanolamine (%) 13 13 Trialkylene glycol butyl ether (% ) 22 Ethanol (%) 55 5 Fragrance Small amount Small amount Colorant Small amount Small amount Water Balance Balance evaluation -5 ℃, 7 days storage × × Results 50 ℃, 7 days storage × ×

Reference Example 4 (Preparation of Crude Product 3) Crude product 3 obtained by adding 8 mol of ethylene oxide to methyl laurate by the catalyst preparation method and the reaction method described in Example 1 of Japanese Patent Application No. 6-334772. I got Specifically, it is obtained by calcining alumina / magnesium hydroxide having a chemical formula of 2.5MgO.Al ₂ O ₃ .nH ₂ O (Kyowad 300CY manufactured by Kyowa Chemical Industry Co., Ltd.) at 500 ° C. for 1 hour in a nitrogen stream. Fired alumina hydroxide / magnesium 1.
40 g of 0.15% potassium hydroxide methanol solution in 5 g
Was dried while spraying, and further dried at 100 ° C. for 10 hours to obtain a reforming catalyst. This reforming catalyst and 440 g of methyl laurate were charged into an autoclave,
Then, after the inside of the autoclave was replaced with nitrogen, 724 g of ethylene oxide was introduced while the temperature was raised and the temperature was maintained at 180 ° C. and the pressure at 3 atm, and an aging reaction was performed until the pressure did not decrease. Thus, a crude product 3 was obtained.

Reference Example 5 (Preparation of Crude Product 4) Crude product 4 was obtained by adding 8 mol of ethylene oxide to methyl laurate by the catalyst preparation method described in Example 3 of Japanese Patent Application No. 6-334772. . Specifically, 2.5M
Alumina / magnesium hydroxide having the chemical formula of gO.Al ₂ O ₃ .nH ₂ O (Kyowa Chemical Industry Kyoward 3)
00CY) in a nitrogen stream at a temperature of 600 ° C. for 1 hour to obtain 0.5 g of calcined alumina / magnesium hydroxide.
Add 2 ml of the specified potassium hydroxide ethanol solution,
Modification of calcined alumina / magnesium hydroxide was performed in an autoclave. Next, a crude product 4 was obtained in the same manner as in Reference Example 4.

Example 8 Crude product 3 was placed in a 1-liter four-necked flask equipped with a stirrer.
Was added and heated to 80 ° C. Next, 2.4 g of activated clay (first-class reagent) and 41 parts of ion-exchanged water
g, and the mixture was mixed for 1 hour. Then, the solid matter (alkoxylation catalyst, activated clay) was removed by filtration by a filtration operation to obtain a nonionic surfactant No. 6 (concentration: 83%). The filtration equipment used is a two-layer filter of cellulose and polyester,
The test was carried out at a temperature of 80 ° C. and a nitrogen pressure of 2 atm with a pressure filter having an inner diameter of 4 cm.

Example 9 Before filtration, KC Floc W-50S was used as a filter aid.
(Sanyo Kokusaku Pulp Co., Ltd.) A nonionic surfactant No. 7 (concentration of 83) was treated in the same manner as in Example 8 except that 1.2 g was added.
%). Example 10 A nonionic surfactant No. 8 (concentration: 90%) was treated in the same manner as in Example 9 except that 0.72 g of activated clay (reagent first grade) and 22.3 g of ion-exchanged water were added as adsorption treatment agents. Obtained.

Example 11 A nonionic surfactant No. 9 was prepared in the same manner as in Example 8 except that acid clay (first-class reagent) was used instead of activated clay.
(Concentration 83%). Example 12 The procedure of Example 9 was repeated, except that the crude product 4 was used, to obtain a nonionic surfactant No10 (concentration: 83%). Example 8
After preparing a transparent liquid detergent by mixing a predetermined amount of the nonionic surfactant obtained in Nos. To 12, the appearance was evaluated by the following method.

Evaluation Method After leaving the liquid detergent composition at -5 ° C. or 50 ° C. for 7 days,
The appearance was visually determined according to the following criteria. ：: transparency ×: cloudiness The evaluation results are shown in Tables 3 and 4.

[0025]

[Table 3] Table 3 ─────────────────────────────────── Product of the present invention 8 9 10 11 12 Nonionic surfactant No8 No9 No10 No11 No12 (%) 22 26 18 15 20 C ₁₂ OH-15EO3PO (%) ¹⁾ 12 15 13 9 12 Unsaturated fatty acid (%) ²⁾ 2 2 1 2 2 Diethanolamine (%) 13 13 13 9 13 Trialkylene glycol butyl ether (%) 2 2 11 1 Ethanol (%) 5 5 5 4 5 Flavor Small amount Small amount Small amount Small amount Small amount Color element Small amount Small amount Small amount Small amount Small amount Water Balance Balance Balance evaluation -5 ° C ○○ ○ ○ ○ Results after storage at 50 ℃ for 7 days ○ ○ ○ ○ ○ 1) C ₁₂ OH-15EO3PO is non-ion in which 15 mol of ethylene oxide and 3 mol of propylene oxide are added to dodecyl alcohol. It is a surfactant. 2) Unsaturated fatty acids having 18 to 22 carbon atoms

[0026]

[Table 4] Table 4 ─────────────────────────────────── The present invention 8 9 10 11 12 Nonionic surfactant No8 No9 No10 No11 No12 (%) 10 8 6 10 12 Alkylamine oxide 2.5 2.5 2.5 2.5 2.5 2.5 Side (%) ³⁾ AES-Na (%) ⁴⁾ 5 5 5 5 5 CDE (%) ⁵⁾ 5 5 5 5 5 PEG # 1000 (%) 2 2 11 1 Ethanol (%) 3.5 3.5 3.5 3.5 3.5 3.5 Fragrance Small amount Small amount Small amount Small amount Small amount Colorant Small amount Small amount Small amount Small amount Small amount Water Balance Balance Balance Balance Balance evaluation After storage at -5 ℃ for 7 days ○ ○ ○ ○ ○ Result After storage at 50 ℃ for 7 days ○ ○ ○ ○ ○ 3) Alkyl of alkylamine oxide The group is lauryl 4) AES-Na is EO3 mole adduct 5) CDE is fatty acid diethanolamine C12

Comparative Example 3 Crude product Example 3 was placed in a 1-liter four-necked flask equipped with a stirrer.
200 g of the alkylene oxide adduct obtained in the above was heated to 80 ° C. Subsequently, 41 g of ion-exchanged water was added and mixed for 1 hour. The mixture was charged into a pressure filter having an inner diameter of 4 cm equipped with a two-layer filter of cellulose and polyester, and filtered at a temperature of 80 ° C. and a nitrogen pressure of 2 atm. The obtained surfactant C was mixed with a transparent liquid detergent, and the appearance was evaluated. Comparative Example 4 Surfactant D was obtained in the same manner as in Comparative Example 3, except that 1.2 g of KC Floc W-50S (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) was added as a cellulosic filter aid before the filtration operation. It was blended into a liquid detergent and its appearance was evaluated.

Comparative Example 5 Surfactant E was obtained in the same manner as in Comparative Example 3 except that 1.2 g of reagent Celite 545 was added as diatomaceous earth as a filter aid before the filtration operation, and this was washed with a transparent liquid. And the appearance was evaluated. Comparative Example 6 Cellulose acetate as a filter aid was added as a filter aid before the filtration operation.
Surfactant F was obtained in the same manner as in Comparative Example 3 except that 4 g was added, and this was mixed with a transparent liquid detergent, and the appearance was evaluated. After preparing a liquid detergent by mixing a predetermined amount of the surfactant treated in the comparative example, the appearance was evaluated in the same manner as in the example. Table 5 shows the evaluation results.

[0029]

[Table 5] Comparative Example 3 4 5 6 Non-ion Surfactant CDEF (%) 22 26 22 22 C ₁₂ OH-15EO3PO (%) ¹⁾ 12 15 12 12 Unsaturated fatty acid (%) ²⁾ 2 22 2 Diethanolamine (%) 13 13 13 13 Trialkylene glycol 2 2 2 2 butyl ether (%) ethanol (%) 5 5 5 5 perfume small amount small amount small amount small amount color containing a small amount small amount small amount small amount of water balance balance balance balance evaluation -5 ° C., after 7 days storage × × × × results 50 ° C. , After 7 days storage × × × ×

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[Procedure amendment]

[Submission date] March 4, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

[0025]

[Table 3] ₁₎ C 12 OH-15EO3PO is a nonionic surfactant of ethylene oxide 15 mol of Russia propylene oxide was 3 moles added in dodecyl alcohol. 2) Unsaturated fatty acids having 18 to 22 carbon atoms

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0026

[Correction method] Change

[Correction contents]

[0026]

[Table 4] 3) The alkyl group of the alkylamine oxide is lauryl 4) AES-Na is an adduct of 3 moles of EO 5) CDE is a fatty acid diethanolamine having 12 carbon atoms

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical indication location C11D 1/68 C11D 1/68 1/74 1/74 (72) Inventor Itsuo Hama Sumida-ku, Tokyo 1-7-3 Honjo Lyon Co., Ltd.

Claims (2)

[Claims] An active clay and / or a reaction crude obtained by adding an alkylene oxide to an active hydrogen-containing compound and / or a fatty acid alkyl ester in the presence of a non-layered alkoxylation catalyst containing MgO as a main component. A method for producing a nonionic surfactant, comprising treating an acid clay with water after contacting the same with water. 2. An aqueous liquid detergent composition containing a nonionic surfactant produced by the method according to claim 1.