JPS6339993A - Liquid detergent composition - Google Patents

Abstract

(57) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a liquid detergent composition that is low in odor and exhibits extremely little odor due to changes over time.

More specifically, improved aliphatic secondary compounds having 8 to 20 carbon atoms
An aliphatic 211 alcohol ethoxylate with a carbon number of 8 to 20 obtained by reacting an alcohol with ethylene oxide is added with a specific neutralizing agent, and then sulfated to obtain a stabilized carbon number with extremely little change over time. 8-20
The invention relates to the use of aliphatic secondary alcohol ethoxy sulfate as a base material for liquid cleaning compositions.

Aliphatic secondary alcohol ethoxy sulfates having 8 to 20 carbon atoms are used in a wide range of fields as the main cleaning active ingredient in liquid cleaning compositions. For example, dishwashing detergent,
Used in shampoos, wool washing detergents, heavy duty laundry detergents, other powder household detergents, household detergents, cleaning detergents, automobile detergents, etc.

Generally, a variety of fragrances are added to these liquid detergents depending on their use. However, if there is a problem with the odor of aliphatic secondary alcohol ethoxy sulfate having 8 to 20 carbon atoms, which is the main cleaning active ingredient, the fragrance may not be able to exhibit its original effects. The present invention uses secondary alcohol ethoxy sulfate containing lactic acid and/or lactate as a liquid detergent raw material to provide a high-quality liquid detergent that is low in odor and exhibits extremely little odor due to changes over time. It is.

(Prior art) As a raw material for liquid detergent, carbon number 8 is particularly important in terms of detergency, easy non-adhesive property, hard water resistance, compatibility, easy solubility, low temperature stability (cold resistance), foam removal, and rinsability. ~20 aliphatic secondary alcohol ethoxy sulfates have been used. In general, ethoxylated aliphatic secondary alcohols having 8 to 20 carbon atoms include alkali catalysts such as sodium hydroxide, potassium hydroxide, and sodium alkoxide, boron trifluoride, boron trifluoride-forms, antimony pentachloride, It is produced by adding ethylene oxide to a 211th alcohol or a second paper mole ethoxylate in the presence of an acidic catalyst such as tin tetrachloride.

The aliphatic secondary compound having 8 to 20 carbon atoms obtained by such a method
Alcohol ethoxylate has 8 to 20 unreacted carbon atoms.
In addition to containing aliphatic secondary alcohol, it also contains trace amounts of catalysts, aldehydes, free acids, esters, peroxides, and other impurities that may cause odor or coloration.

These impurities such as aldehydes, free acids, esters, and peroxides are removed by washing with an aqueous alkali solution, saponification, and distillation, and alkaline catalysts are usually removed by adding mineral acids such as sulfuric acid, phosphoric acid, or acetic acid. It is purified by neutralization. The secondary @alcohol ethoxy sulfate obtained by further sulfating the secondary alcohol ethoxylate obtained in this way contains impurities that cause bad odor and coloration, and the bad odor will change over time. There are problems that occur. In addition, when aliphatic secondary alcohol ethoxylate with a carbon number of 8 to 20 that has changed over time is sulfated with a sulfating agent such as sulfur dioxide or silyl sulfonic acid, the hue of the sulfate produced becomes significantly worse. There's a problem. As mentioned above, when aliphatic secondary alcohol ethoxy sulfate having 8 to 20 carbon atoms obtained by the conventional technology is used to make a liquid cleaning product, there are problems that cause quality deterioration such as the odor and color of the product. This is not desirable.

In particular, sodium hydroxide used when producing an aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms by reacting a low mole ethoxylate of an aliphatic secondary alcohol having 8 to 20 carbon atoms with ethylene oxide, Alkaline catalysts such as potassium hydroxide and sodium alkoxide are usually
It is purified by neutralization treatment by adding a neutralizing agent such as mineral acids such as sulfuric acid or phosphoric acid or acetic acid, but aliphatic secondary alcohols having 8 to 20 carbon atoms can be purified using these conventional neutralizing agents. When ethoxysulfate is used as a raw material for a liquid cleaning agent, it already has an odor at the time of formulation, and the odor is lost to the seller due to changes over time, which is a major problem in producing a liquid cleaning agent with little odor.

(Problems to be Solved by the Invention) The object of the present invention is to obtain a product obtained by reacting an aliphatic secondary alcohol having 8 to 20 carbon atoms or a secondary alcohol low mole ethoxylate with ethylene oxide and sulfating it. When aliphatic secondary alcohol ethoxy sulfate with a carbon number of 8 to 20 is used as a cleaning active ingredient in a liquid cleaning agent, there is little odor at the time of compounding the liquid cleaning agent, and it is also extremely resistant to odor over time. The purpose is to provide less liquid cleaning agents.

(Means for solving problem v!1) The present invention provides a liquid detergent composition containing an aliphatic secondary alcohol ethoxy sulfate having 8 to 20 carbon atoms as a detergent active ingredient. C8-20 aliphatic secondary alcohol ethoxy sulfate containing salt is obtained by reacting a C8-20 aliphatic secondary alcohol low mole ethoxylate with monoethylene oxide in the presence of an alkali catalyst. is obtained by adding lactic acid and/or lactate to an unneutralized aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms, followed by sulfation, or An unneutralized aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms obtained by reacting a secondary alcohol low mole ethoxylate with ethylene oxide in the presence of an alkali catalyst is in a neutralized state or A liquid detergent composition containing a secondary alcohol ethoxylate obtained by adding lactic acid and/or lactate to an aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms from which the catalyst has been removed by filtration, and then sulfating the mixture. It is about things.

The lactic acid used in the present invention may be produced by either the WavI method or the synthetic method.
l! ′ is not particularly suitable for cellulose, but it can be used for any of the commercially available industrial purposes, brewing purposes, and for adding to strained products.

The lactate salts used in the present invention include alkali gold R salts of lactic acid such as sodium lactate, potassium lactate, and potassium lactate, alkaline earth metal salts of lactic acid such as calcium lactate, magnesium lactate, and barium lactate, aluminum lactate, and lactic acid. zinc,
'Silver lactate, copper copper, milk! Examples include iron, manganese lactate, and ammonium lactate, with sodium lactate and potassium lactate being particularly preferred.

The addition l of lactic acid and/or lactate used in the present invention is 5 to 0°0011' per 100f4ffi parts of C8 to C20 abacus group "design grade" alcohol ethoxylate.
parts by weight, preferably 1 to 0.05 parts by weight. Addition-
However, the pH of the aqueous solution is preferably in the range of 4 to 9, preferably 5 to 7.

The method of adding lactic acid and/or lactate of the present invention is to add a low mole ethoxylate of an aliphatic secondary alcohol having 8 to 20 carbon atoms and ethylene oxide in the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, and sodium alkoxide. Unneutralized carbon number 8-20 obtained by reacting with
An aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms from which the catalyst has been removed by adding lactic acid to the aliphatic secondary alcohol ethoxylate, or by a known method such as neutralizing the catalyst or passing through the mouth. There is a method of adding lactic acid and/or lactate to.

To add lactic acid and/or lactate, add lactic acid and/or lactate as is or as a solution to aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms, stir for about 30 minutes, and dissolve completely. is preferred.

The second alcohol used in the present invention has 8 to 20 carbon atoms.
This is a random secondary alcohol obtained by liquid-phase oxidation of n-paraffin with molecular oxygen in the presence of a boron compound.

The secondary alcohol ethoxy sulfate used in the present invention is made by adding an acid catalyst to a random secondary alcohol obtained by liquid phase oxidation of n-paraffin having 8 to 20 carbon atoms with molecular oxygen in the presence of a boron compound. 0.1 to 6 mol of ethylene oxide on average, preferably 1 to 6 mol on average.
A low mole ethoxylate containing substantially no free alcohol by reacting 4 moles, neutralizing or removing the catalyst, and sufficiently removing unreacted free alcohol by distillation, extraction, or other methods, or the low mole ethoxylate containing substantially no free alcohol. To,
In the presence of an alkali catalyst such as sodium hydroxide, potassium hydroxide, and sodium alkoxide, ethylene oxide is added, although not particularly limited, usually in the range of 0.1 to 100 moles on average, particularly 1 to 50 moles. Various second methods obtained by the method □
alcohol ethoxylate.

Commercially available secondary alcohol ethoxylates include Nippon Shokubai Kagaku Kogyo ■, trade name: Softanol, alcohol ethoxylate of secondary alcohols with 12 to 14 carbon atoms, and secondary alcohols with 10 to 12 carbon atoms. Alcohol ethoxylates and secondary alcohols with a carbon number of 11 to 15 of Tergitol, manufactured by Union Carbide Co., Ltd., trade name
alcohol ethoxylates. In all of these products, the free alcohol has been removed at the time of the 3-mole ethylene oxide adduct, and there is no substantial residue, and ethylene oxide is further added with a base catalyst as a raw material for the high-mole ethylene oxide adduct.

Specifically, the following secondary alcohol ethoxylates can be mentioned. Softanol・50 Adduct of secondary alcohol having 12 to 14 carbon atoms with an average of 5 moles of ethylene oxide Softanol・70 Adduct of secondary alcohol having 12 to 14 carbon atoms with an average of 7 moles of ethylene oxide Softanol・90 Carbon number 12 to Adduct of 14 secondary alcohols with an average of 9 moles of ethylene oxide Reaction temperature for low moles of secondary alcohols, ethoxylates obtained by reacting secondary alcohols with ethylene oxide in the presence of an acid catalyst The temperature range is preferably 150°C or lower, particularly 100°C or lower.

The reaction temperature for reacting secondary alcohol low mole ethoxylate with ethylene oxide in the presence of an alkali catalyst is:
A temperature range of 50-200°C, especially 120-180°C is preferred.

The reaction pressure is O~30K/aIG, especially 0.5~20K
A pressure range of y/dG is preferred.

The sulfation of the secondary alcohol ethoxylate of the present invention is
Sulfating agents such as sulfur trioxide, chlorosulfonic acid, sulfamic acid or fuming sulfuric acid can be used.

The sulfation of the secondary alcohol ethoxylate of the present invention is
The amount of the sulfating agent relative to the secondary alcohol ethoxylate is not particularly limited, but is in the range of 0.5 to 2 mol, preferably 0.8 to 1.5 mol.

The reaction temperature for sulfation of the secondary alcohol ethoxylate of the present invention is preferably in the temperature range of 40°C or lower, particularly 20°C or lower.

In the liquid detergent composition containing the C8-C20 aliphatic secondary alcohol ethoxy sulfate of the present invention as a cleaning and active ingredient, the C8-C20 aliphatic secondary alcohol ethoxysulfate containing lactic acid and/or lactate is In addition to secondary alcohol ethoxy sulfate, various additives are added depending on various uses, such as activators, hydrotropes, foaming agents, foam stabilizers, antifoaming agents, thickeners, low viscosity agents, and builders. A liquid cleaning composition having extremely good performance can be obtained by blending and combining anti-refouling agents, bleaching agents, fragrances, optical brighteners, fragrances, optical brighteners, dye brighteners, etc. The present invention has been completed.

In the liquid detergent composition containing the C8-C20 aliphatic secondary alcohol ethoxy sulfate of the present invention as a detersive active ingredient, the C8-C20 aliphatic secondary alcohol ethoxysulfate containing lactic acid and/or lactate is The content ratio of the liquid detergent composition of alcohol ethoxy sulfate is 1 to 90
Weight percent is preferred.

Characteristics of the liquid detergent composition of the present invention depending on its use, such as alkylbenzene sulfonates, alkyl ether carboxylates, and fatty acids as effective active agents for producing foaming, antifoaming, cleaning synergistic effects, finishing effects, and prevention of rough hands. Soaps, α-olefin sulfonates, higher alcohol sulfate ester salts, alkyl ether sulfates, fatty acid alkylolamide sulfate ester salts, alkyl ether phosphate ester salts, alkyl phosphate ester salts,
N-nialylmethyltaurine, N-acyl amino acid salts,
□Acylated peptides, alkylalkanolamides, aliphatic amines, salts, aliphatic quaternary ammonium salts, benzalkonium salts, imidazolinium salts, carboxybetaine types, amino carboxylates, imidazolinium betaines, It is preferable to add 0 to 30% by weight of one or a mixture of two or more of alkyl naminooxides, polyoxyethylene alkylamines, fatty acid alkanolamides, and the like.

In addition, solubilizers (hydrotropes) that are considered essential for liquid detergents include lower alcohols, ethylene glycols, propylene glycols, glycerin,
One or a mixture of two or more selected from cellosolves, ethanolamines, toluene sulfonates, xylene sulfonates, and urea can be used in an amount of O to 10%.

As the viscosity modifier, inorganic salts such as sodium chloride, potassium chloride, magnesium chloride, sodium sulfate,
One or a mixture of two or more selected from sodium carbonate and potassium birophosphate can be used in an amount of 0 to 5% by weight.

The remainder is water, with deionized water or distilled water being particularly preferred.

Note that preservatives, bactericides, etc. may be added to prevent spoilage. Furthermore, additives such as builders, anti-restaining agents, bleaching agents, fluorescent agents, colorants, fragrances, and antioxidants can also be used.

(Function) A secondary alcohol ethoxylate obtained by reacting a secondary alcohol or a secondary alcohol low mole ethoxylate with ethylene oxide is made to contain lactic acid and/or a lactate, and then sulfated. When the secondary alcohol ethoxy sulfate was used as a cleaning agent, DHL
It was also found that the odor changes over time are extremely reduced.

(Example) Hereinafter, the implementation of the present invention will be specifically illustrated and explained by giving examples. The invention is not limited to the following embodiments.

The test methods used in the examples are as follows.

(1) Odorless distilled water 10 treated with activated carbon for odor samples o and Iat
Judgment was made by a paired comparison method with a standard product at a temperature of 50'G with addition of 0d. The odor was judged as follows.

5: Same as the standard product 4: Lighter than the standard product □ Crab odor 3: Slightly more odor than the standard product 2: Noticeably more odor than the standard product 1: Standard product with a much stronger odor than the standard product (A) Implementation For Examples 1 to 3 and Comparative Examples 1 to 3,
The cleaning agent of Example 1, which had not changed over time, was used as a standard product.

(B) For Examples 4 to 5 and Comparative Examples 4 to 5, the cleaning agents of Examples 4 to 5, which had not changed over time, were used as standard products.

■Cleaning power test (Method A) Add 10XI Q to liquid detergent aqueous solution 11 at specified concentration.
Put 3 pieces of Cm artificially contaminated cloth 65% polyester 35% cotton broadcloth into a turbotometer (rotation speed: 100rE).
llll).

(1) Cleaning conditions Cleaning agent '11! I: 0.067wt% Water used: Water flow Water temperature = 25℃ Washing time: 5 minutes Rinse: 5 minutes in tap water Soil composition of artificially contaminated cloth AI texture (wt%) Myristic acid 16.7 Oleic acid 16.7 tristearin 16.7 triolein
16.7 cholesterol
8.8 Cholesterol stearate
2.2 Paraffin wax (m, p, 50-52℃) 11
．． 1 Squalene 11.1B
Inorganic clay (Kanto loam passed through 250 mesh) C carbon carbon black (passed through 250 mesh) L quality 4
9.75% by weight, 49.75% by weight of free 81, and 0.5% of carbon were mixed to make dirt, and the reflectance was 45% ± 2.
The purified white cloth was contaminated to the extent of %.

■ Calculation of cleaning rate of artificially contaminated cloth Measure the reflectance at 530 mμ of the original cloth before cleaning and the artificially contaminated cloth before and after cleaning using a reflectance meter (Hiranuma Sangyo Model 15PR-3), and calculate the cleaning rate (%) using the following formula. was calculated.

Cleaning rate (%') -100X (Method B) Six model dirty glass pieces were washed using a Leanutt improved detergency tester in accordance with J Is-3370-4.9, and the detergency was measured.

(a) Cleaning conditions Cleaning agent concentration 0.15% by weight Dirt m 0.163or/6 pieces Rust plate JIS R3703 No. 2 used water
3°OH water washing temperature 30°C Rotation speed 250rDm Washing time a 3 minutes rinsing time, 1 minute liquid Danger 700ml/pot (ro) Model stain creation Mixed oil of beef tallow and soybean oil (1:1) 20a, monoolefin 0 .25Q, oil red 0.1g chloroform 6
Prepare a sludge bath by dissolving it in 0ml.

Glass plates are immersed one by one in a contamination bath heated to 25±1°C for 1 to 2 seconds to a depth of about 55 mm to adhere dirt, and then taken out.

2 in a constant temperature and humidity chamber at a temperature of 25 ± 1°C and a humidity of 60 ± 5%.
It was air-dried for 4 hours, weighed, and immediately used for the detergency test.

(c) Calculation of cleaning power Measure the weight of 6 glass plates before and after contamination and after cleaning, air dry in a constant temperature and humidity tank for 6 hours, and calculate the cleaning rate (%) using the following formula. Calculated.

Cleaning rate (%) -100
An average of 3 mole ethoxylate of a secondary alcohol with an average molecular weight of 333 from 2 to 14 (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name: Softanol-30) 3939, 0.6 g of sodium hydroxide as a catalyst, and ethylene oxide 2079 were charged, and the temperature The reaction was carried out at 150° C. and a pressure of 6.0 Ky/dG. The ethylene oxide average of the obtained secondary alcohol was 7
Adding 2.8 g of a 50% by weight aqueous lactic acid solution to the molar adduct;
Stir well. 1 mol of the obtained secondary alcohol ethoxylate was placed in a stirring tank No. 11 and maintained at a temperature of 10 to 15°C. While vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by adding it to an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less. As a result, an aqueous solution of secondary alcohol ethoxysulfate was obtained. A liquid detergent composition shown in Table 1 was prepared using the obtained secondary alcohol ethylene oxide 7.0 mol average sulfate aqueous solution (sample-1) as the main detergent active ingredient,
Odor and cleaning power tests were conducted.

The results were as shown in Table 1.

Comparative example 1 Capacity ff11000m! 12 carbon atoms in stainless steel reactor
An average of 3 to 14 secondary alcohols with an average molecular weight of 333
Mol ethoxylate (manufactured by Nippon Shokubai Chemical Co., Ltd. Product name)
Softanol -30) 393q1 0.6Q of sodium hydroxide and 207Q of ethylene oxide were charged as catalysts, and the temperature was 150°C and the pressure was 6. OK! The reaction was carried out at g/dG. The ethylene oxide average of the obtained secondary alcohol was 7
Vinegar vi0.9a was added to the molar adduct and stirred well.

1 mol of the obtained secondary alcohol ethoxylate
The mixture was placed in a stirred tank, and the temperature was maintained at 10 to 15° C., and 1 mole of chlorosulfonic acid was dropped into the stirred tank over about 1 hour to cause a reaction while stirring vigorously. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, A secondary alcohol ethoxysulfate aqueous solution was obtained. The liquid detergent compositions shown in Table 2 were prepared using the obtained secondary alcohol ethylene oxide 7.0 mol sulfate aqueous solution (comparative test! 4-1) as the main detergent active ingredient, and were tested for odor 1 and detergency. I did it. The results were as shown in Table 2.

Example 2 A stainless steel reactor with a capacity of 10,100 O and a carbon number of 12 to 1
334.5 g of secondary alcohol with an average molecular weight of m333 (manufactured by Nippon Shokubai Kagaku Kogyo $I, trade name: Softanol -30), 334.5 g of sodium hydroxide, 0.6 a1 ethylene oxide, 265.50 g as a catalyst, The reaction was carried out at a temperature of 150° C. and a pressure of 6.0 m/aliG. 2.89% of a 50% by weight aqueous lactic acid solution was added to the obtained adduct of secondary alcohol with ethylene oxide on average of 9 moles, and the mixture was thoroughly stirred. 1 mole of the obtained secondary alcohol ethoxylate was placed in a stirring tank No. 11 at a temperature of 10 to 15°C.
While stirring vigorously, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, A secondary alcohol ethoxysulfate aqueous solution was obtained. Liquid detergent compositions shown in Table 1 were prepared using the obtained aqueous solution of secondary alcohol ethylene oxide with an average of 9.0 mol sulfate (Sample-2) as the main detergent active ingredient, and tests were conducted on odor and detergency. The results were as shown in Table 1.

Comparative example 2 12 carbon atoms in a stainless steel reactor with a capacity of 1000 mj
~． An average of 3 mole ethoxylate of secondary alcohol with an average molecular weight of 333 in 14 (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name: Softanol-30) 334°50, sodium hydroxide 0.6a as a catalyst, and ethylene oxide 265.5
0, temperature 150℃, pressure 6. OK! The reaction was carried out at l/mG. To the resulting secondary alcohol adduct with an average of 9 moles of ethylene oxide was added 0.0% of an 85% by weight aqueous phosphoric acid solution.
9Q was added and stirred well. 1 mol of the obtained secondary alcohol ethoxylate was placed in a stirring tank of 11 and the temperature was 10.
While maintaining the temperature at ~15°C and stirring vigorously, 1 mol of chlorsulfone M was dropped into the stirring tank over about 1 hour to cause a reaction.

After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove the by-product hydrogen chloride gas, and then the reaction solution was poured into an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, and the mixture was allowed to settle. , an aqueous solution of secondary alcohol ethoxysulfate was obtained. Liquid detergent compositions shown in Table 2 were prepared using the obtained secondary alcohol ethylene oxide aqueous sulfate solution (comparative sample-2) with an average of 9.0 mol as the main detergent active ingredient, and the odor and detergency tests were conducted. I did it.

The results were as shown in Table 2.

Example 3 Capacity ff11000mJ! 1 carbon in stainless steel reactor
2 to 14 average 3 mole ethoxylate of secondary alcohol with average molecule a333 (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name Softanol -30) 393q, potassium hydroxide 1.0G and ethylene oxide 207Q as catalysts were charged, and the temperature was 150. The reaction was carried out at a temperature of 6.0 kg/csfG. A 50% by weight aqueous lactic acid solution was added to the obtained secondary alcohol adduct with an average of 7 moles of ethylene oxide.3. Added IG and stirred well. 1 mol of the obtained 2nd alcohol ethoxylate was placed in a stirring tank 11, and the temperature was maintained at 10 to 15°C, and while stirring vigorously, 11 mol of alcohol ethoxylate was dropped into the stirring tank at about 1 hour to react. Ta. The supply of riOrusulfone has ended! Supply nitrogen gas into the itching tank,
By-product hydrogen chloride gas was removed, and then the reaction solution was neutralized in an aqueous sodium hydroxide solution while maintaining the temperature at 40° C. or less to obtain an aqueous solution of secondary alcohol ethoxysulfate. Liquid detergent compositions shown in Table 1 were prepared using the obtained secondary alcohol ethylene oxide 7.0 mol sulfate aqueous solution (Sample-3) as the main detergent active ingredient, and tests were conducted on odor and detergency. Ta.

The results were as shown in Table 1.

Comparative example' 3 Carbon number -1 in a stainless steel reactor with a capacity of 11,000 m1
Average 3 mole ethoxylate of secondary alcohol with average molecular weight t33s of 2 to 14 (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name Softanol-30) 393Q゛,゛Potassium hydroxide 1.00. Ethylene oxide 207 Q'
were charged and reacted at a temperature of 150° C. and a pressure of 6.0 kg/dG. To the obtained secondary alcohol adduct with ethylene oxide on average of 7 moles was added vinegar 1111. Added IG and stirred well. 1 mol of the obtained second alcohol ethoxylate was placed in a stirring tank 11 and the temperature was maintained at 10 to 15°C.
While vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of 0-ru sulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was placed in an aqueous sodium hydroxide solution for neutralization while maintaining the temperature at 40°C or less. , an aqueous solution of secondary alcohol ethoxysulfate was obtained. Liquid detergent compositions shown in Table 2 were prepared using the obtained secondary alcohol ethylene oxide 7.0 mol sulfate aqueous solution (comparative sample-3) as the main detergent active ingredient, and tests were conducted on odor and detergency. . The results were as shown in Table 2.

Example 4 A stainless steel reactor with a capacity of 10 to 1 carbon atoms
381 g of an average 3 mole ethoxylate of a secondary alcohol with an average molecule of m306 (manufactured by Nippon Shokubai Chemical Co., Ltd., trade name: Softanol L-30), thorium hydroxide 0-6Q, and ethylene oxide 2190 as catalysts, The reaction was carried out at a temperature of 150° C. and a pressure of 6.0 #/dG. 2.8 q of a 50% by weight aqueous lactic acid solution was added to the obtained secondary alcohol adduct with ethylene oxide on average of 7 moles, and the mixture was thoroughly stirred. Obtained secondary alcohol ethoxylate 1
Take the mole into a stirring tank of 11 and maintain the temperature at 10-15°C,
While vigorously stirring, 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove the nl raw hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less, A secondary alcohol ethoxysulfate aqueous solution was obtained. The ethylene oxide average of the obtained secondary alcohol was 7
．． Liquid detergent compositions shown in Table 1 were prepared using a 0 mol sulfate aqueous solution (Sample-4) as the main detergent active ingredient, and tested for odor and detergency.

The results were as shown in Table 1.

Comparative example 4 10 carbon atoms in a stainless steel reactor with a capacity of 1000 mJ
An average of 3 to 12 secondary alcohols with an average molecule of 1306
Mol ethoxylate (manufactured by Nippon Shokubai Chemical Co., Ltd. Product name)
Softanol L-30) 3810, sodium hydroxide 0.6Q and ethylene oxide 2199 as catalysts were charged, and the reaction was carried out at a temperature of 150° C. and a pressure of 6.0 at 9/1 siG. 0.9 g of acetic acid was added to the obtained secondary alcohol adduct with ethylene oxide on average of 7 moles, and the mixture was thoroughly stirred. 1 mol of the obtained secondary alcohol ethoxylate
The mixture was placed in a stirring tank of No. 1, maintained at 8° C. and 10 to 15° C., and 1 mole of chlorosulfonic acid was dropped into the stirring tank over about 1 hour while stirring vigorously to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then r! The reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at Aa, and the second
An aqueous solution of ti&alcohol ethoxysulfate was obtained.

The average ethylene oxide of the obtained secondary alcohol was 7.
Liquid detergent compositions shown in Table 2 were prepared using a 0 mol sulfate aqueous solution (Comparative Sample-4) as the main detergent active ingredient, and tested for odor and detergency. The results were as shown in Table 2.

Example 5 Capacity 100.0rrl stainless steel reactor with 12 carbon atoms
An average of 3 mole ethoxylate of a secondary alcohol with an average molecular weight of 11,333 (manufactured by Nippon Shokubai Chemical Industry ■) 393q, 0.6g of sodium hydroxide as a catalyst, and 207q of ethylene oxide were charged, and the temperature was 150°C. , the reaction was carried out at a pressure of 6.0 phantom/cjG. The ethylene oxide average of the obtained secondary alcohol was 7
Kyoward-600BuPS12Q was added to the molar adduct, treated at 80°C for 30 minutes, and then transferred to a mouth filter pre-coated with diatomaceous earth to adsorb the catalyst.
PS was removed. Next, 3.5% of a 50% by weight aqueous sodium lactate solution was added to the average 7 mol adduct of ethylene oxide.
9 was added and stirred well. 1 mole of the obtained secondary alcohol ethoxylate containing sodium lactate was added to 11
Add the sulfone to a stirring tank, maintain the temperature at 10-15℃, and stir vigorously. i! 21 mol of the solution was added dropwise into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then the reaction solution was neutralized by placing it in an aqueous sodium hydroxide solution while maintaining the temperature at 40°C or less. , an aqueous solution of secondary alcohol ethoxysulfate was obtained.The average ethylene oxide content of the obtained secondary alcohol was 7.0.
Liquid detergent compositions shown in Table 1 were prepared using an aqueous molsulfate solution (Sample-5) as the main detergent active ingredient, and tested for odor and detergency. The results were as shown in Table 1.

Comparative example 5 Capacity ff11000m! 12 carbon atoms in stainless steel reactor
An average of 3 to 14 secondary alcohols with an average molecular weight of 333
Mole ethoxylate (manufactured by Nippon Shokubai Kagaku Kogyo A, product name)
Softanol-30) 393Q1 0.6 g of sodium hydroxide and 207Q of ethylene oxide were charged as catalysts, and the reaction was carried out at a temperature of 150° C. and a pressure of 6.06/ajG.

Kyoward-600BLIPS12a was added to the resulting adduct of secondary alcohol with ethylene oxide on average of 7 mols, and the mixture was treated at 80°C for 30 minutes, then transferred to a filter made of diatomaceous earth and recorded, and Kyoward-600S adsorbed with the catalyst.
LIPS was removed. Next, 1 mole of the secondary alcohol ethoxylate obtained by mouth-filtering was placed in a stirring tank of 11, maintained at a temperature of 10 to 15°C, and stirred vigorously until 0 lsulfone was added. 11 mol of i was dropped into the stirring tank over about 1 hour to cause a reaction. After the supply of chlorosulfonic acid was completed, nitrogen gas was supplied into the stirring tank to remove by-product hydrogen chloride gas, and then
The reaction solution was neutralized in an aqueous sodium hydroxide solution while maintaining the temperature at 0° C. or lower to obtain an aqueous solution of secondary alcohol ethoxysulfate. Liquid detergent compositions shown in Table 2 were prepared using the obtained secondary alcohol ethylene oxide 7.0 mol sulfate aqueous solution (comparative sample-5) as the main detergent active ingredient, and tests were conducted on odor and detergency. . The results were as shown in Table 2.

(Effect of the invention) Alcohol ethoxysulfate obtained by reacting alcohol and ethylene oxide with lactic acid and/or lactate and then sulfating the alcohol ethoxysulfate has a change in odor over time. It was found that the effect of reducing the amount of Furthermore, the obtained alcohol ethoxysulfate has the effect of being usable in a wide range of fields as a surfactant.

Claims (7)

[Claims] (1) In a liquid detergent composition containing an aliphatic secondary alcohol ethoxy sulfate having 8 to 20 carbon atoms as a cleaning active ingredient, the cleaning active ingredient has 8 to 20 carbon atoms and contains lactic acid and/or lactate. A liquid cleaning composition characterized in that it is an aliphatic secondary alcohol ethoxy sulfate. (2) Containing lactic acid and/or lactate with 8 or more carbon atoms
20 aliphatic secondary alcohol ethoxy sulfate is an unneutralized 8-carbon aliphatic secondary alcohol ethoxy sulfate obtained by reacting a C8-20 aliphatic secondary alcohol low mole ethoxylate with ethylene oxide in the presence of an alkali catalyst. 2. The liquid detergent composition according to claim 1, which is obtained by adding lactic acid as a neutralizing agent to the aliphatic secondary alcohol ethoxylate of 1 to 20 and further sulfating it. (3) Contains lactic acid and/or lactate and has 8 or more carbon atoms
20 aliphatic secondary alcohol ethoxy sulfate is an unneutralized 8-carbon aliphatic secondary alcohol ethoxy sulfate obtained by reacting a C8-20 aliphatic secondary alcohol low mole ethoxylate with ethylene oxide in the presence of an alkali catalyst. Adding lactic acid and/or lactate to an aliphatic secondary alcohol ethoxylate having 8 to 20 carbon atoms from which the catalyst has been neutralized or from which the catalyst has been removed by filtration. The liquid cleaning composition according to claim 1, which is obtained by further sulfating the composition. (4) Secondary alcohol ethoxy sulfate is added by adding ethylene oxide to a random secondary alcohol obtained by liquid phase oxidation of n-paraffin having 8 to 20 carbon atoms with molecular oxygen in the presence of a boron compound. The liquid cleaning composition according to claim 1, which is obtained by further sulfating the composition. (5) The liquid cleaning composition according to claim 1, wherein the lactate is an alkali metal salt of lactic acid. (6) The liquid cleaning composition according to claim 1, wherein the lactate is sodium lactate. (7) Claim 1 in which the lactate is potassium lactate
The liquid cleaning composition described in Section 1.