JPH01142000A - Production of high-density detergent from higher alcohol and detergent composition - Google Patents

Abstract

PURPOSE:To obtain at low cost a powdery detergent having a high solubility and a high bulk density, by neutralizing a sulfuric acid monoester of a particular higher alcohol (ethylene oxide adduct) with a mixture of an at least equimolar amt. of sodium carbonate and zeolite. CONSTITUTION:A sulfuric acid monoester of a higher alcohol of formula I (wherein R is an 8C or higher alkyl), a sulfuric acid monoester of a higher alcohol ethylene oxide adduct of formula II (wherein n is at least 2) or a mixture thereof in arbitrary proportions is neutralized with a mixture of an at least equimolar amt. of sodium carbonate and an arbitrary amt. of zeolite to form sodium bicarbonate without the generation of carbon dioxide. By the above procedure, a high-density powdery detergent derived from a higher alcohol is obtd. while maintaining the fluidity of powder and improving the solubility without the necessity of energy for drying.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is directed to the oxidation of higher alcohols and the oxidation of higher alcohols to produce higher alcohol-based powder detergents which have a higher bulk density than powder detergents produced by conventional spray drying methods. The present invention relates to a method for directly producing an ethylene adduct from a sulfuric acid monoester, and a cleaning composition obtained by the method.

[Conventional technology]

Conventional higher alcohol-based powder cleaning agents are produced by neutralizing sulfuric acid monoester obtained by sulfating higher alcohols and ethylene oxide adducts of higher alcohols with sulfuric anhydride or chlorsulfonic acid with an aqueous solution of caustic soda, and removing inorganic builders and recontamination. Manufactured by spray drying an aqueous slurry containing an inhibitor, etc., with a bulk specific gravity of 0.2-0.4.
It is commercialized as a powder.

Recently, powdered cleaning agents with high bulk density have been attracting attention for the purpose of saving energy, reducing packaging and transportation costs, and making it easier for consumers to use.

A known method is to pulverize a low bulk density detergent powder obtained by spray drying and then granulate it.

[Issues that the invention attempts to resolve]

The method of pulverizing and granulating a powdered detergent with a low bulk density obtained by a spray drying method deviates from the purpose of energy saving and inevitably increases costs.

The biggest drawback when producing higher alcohol-based powder detergents using the spray drying method is the pollution caused by the odor of the exhaust gas, and methods such as cooling and washing with water are being used.
At present, we have not yet achieved fully satisfactory results.

[Means for solving problems]

The present inventors have conducted extensive research to solve the problems of these known methods, and as a result, they can be carried out using a simple device that does not require energy for drying. We were able to establish a method for manufacturing a higher alcohol-based high bulk density powder detergent with excellent meltability.

The method of the present invention is based on the equimolar reaction of a higher alcohol sulfuric acid monoester, a sulfuric acid monoester of a higher alcohol ethyl oxide adduct, and sodium carbonate as shown by the following formula.

rlO503H+ Na, Co3→ll08O, Na
+ Na1lC03RO(CH,CI,0)ns03I
Place + NBJ, Q3 → RO (CIl ICI (20
) nsO, lNa + NaHCO3R represents an alkyl group having 8 or more carbon atoms, preferably an average carbon number of 12-13.

The higher alcohols used include natural higher alcohols such as coconut reduced alcohol, matcha vapor alcohol, and beef tallow reduced alcohol, as well as synthetic higher alcohols such as those obtained by the oxo method and Ziegler method, and ethylene oxide addition of these natural and synthetic higher alcohols. You can use things.

These alcohols can be sulfated with sulfuric anhydride or chlorsulfonic acid, and the resulting sulfuric acid monoester or ethoxysulfuric monoester can be neutralized with a mixture of equimolar or more of soda ash and any amount of zeolite.

The reaction heat generated by the neutralization reaction can be removed by passing cooling water through the jacket of the neutralization reactor or by introducing cold air into the reactor.

It is known that this anhydrous reaction is generally promoted and completed by adding a lower alcohol, but the present inventors added an appropriate amount of the sulfuric acid monoester of the higher alcohol and the higher alcohol ethylene oxide adduct to be used as raw materials. It has been found that the following great effects can be obtained by adding and mixing a higher alcohol ethylene oxide adduct with an added mole number of ethylene oxide of 5 or more.

(1) Accelerating the neutralization reaction rate in anhydrous conditions (2) Improving the stability of sulfuric acid monoester (suppressing changes in color tone over time) (3) Improving the detergency of the resulting powder base (4) Powder base Therefore, according to the method of the present invention, the neutralization reaction can be promoted and completed without using flammable lower alcohols, and the waiting time until the neutralization process of the sulfuric acid monoester produced in the sulfation equipment can be reduced. Suppression of color tone deterioration within time,
It can be expected that the detergency of the obtained powder base will be improved.

In addition, the granulation properties of the powder particles are better than in the case of alcohol sulfate alone, and the formation of fine particles that are easy to dust is suppressed.
Furthermore, it is possible to prevent detergent particles from floating to the water surface during use.

Although a ribbon mixer, a Ledeige mixer (Matsusaka Trading Co., Ltd.), etc. can be used as an apparatus for the neutralization reaction, various powder mixing apparatuses can be used without being limited to a specific apparatus when carrying out the method of the present invention. It is possible to use

Higher alcohol sulfate (hereinafter abbreviated as AS) and higher alcohol ethoxy sulfate (hereinafter abbreviated as AS) produced by the neutralization reaction
(hereinafter abbreviated as AES), higher alcohol ethoxylate (hereinafter abbreviated as AE), soda ash, sodium bicarbonate, zeolite, and as a small amount of by-product, sodium sulfate,
A cleaning composition can be derived by using a mixture containing common salt, unreacted alcohol, and ethoxylate as a base and further adding various raw materials.

For example, alpha olefin sulfonates, alpha sulfo fatty acid salts, fatty acid soaps, higher fatty acid alkylolamides, inorganic builders such as sodium silicate, sodium metasilicate, sulfate, and sodium tripolyphosphate, and organic builders such as polyacrylates. , sodium citrate, sodium gluconate, etc. are used, and CMC is used as a recontamination prevention agent.
, polyethylene glycol, sodium percarbonate, sodium percarbonate, sodium chlorite, etc. as bleaching agents, fluorescent dyes, enzymes, fragrances, etc. can be arbitrarily blended and commercialized as a cleaning composition0. The present invention. When carrying out this method, unlike the conventional spray drying method, it does not require the thermal energy of personnel, but if the fluidity of the powder decreases due to moisture mixed in from the raw materials, it can be dried or dried with a small amount of heat. By standing and drying, the amount of attached moisture can be reduced and the fluidity of the powder can be improved.

Example 1゜Soda ash 0.75Kg (7.08mo/L/)
Zeolite 0.75Kg Palm reduced alcohol sulfuric acid monoester L, OKg (3.3 mol) Sulfuric ester L Soda ash Molar ratio = 1:2.1 Soda ash and zeolite were charged into a tabletop small ribbon mixer (ION) After uniformly mixing, sulfuric acid monoester of palm reduced alcohol produced by continuous method using anhydrous sulfuric acid method using a tubular reactor was gradually added, and cooling water was passed through the jacket of the mixer to bring the temperature of the reactant to 50°C. It was kept below.

The following raw materials were further added to the obtained powder base and mixed by stirring.

Soap dregs 0.1 Kg Sodium metasilicate 0.1 Kg 2.7 Kg of the obtained mixture was charged into a Henschel type small mixer, pulverized with high speed stirring for 10 seconds, and passed through a 12-mesh sieve to obtain 2.65 Kg of cleaning agent. A powder was obtained. The bulk density measurement result was 0.74.

In addition, 2% of the proteolytic enzyme Su'binase (Novo),
Tables 1 and 2 show the performance test results of the detergent compositions obtained by adding 0.2% fragrance.

Example 2 Soda ash 0.9 Kg (8.49 mol) Zeolite 0.9 to 1 g Palm reduced alcohol 11 [monoester 1.0 to 3.3 mol) Palm reduced alcohol ethylene oxide adduct ( 9 moles) 0.2 Kg (0,3
Mol) Sulfuric acid ester/soda ash molar ratio = 1:2.57 After charging and mixing soda ash and zeolite in a tabletop small ribbon mixer (IOL), palm reduced alcohol produced by anhydrous sulfuric acid method in a separate tank. The sulfuric acid monoester was mixed with a palm-reduced alcohol oxide ethylene adduct (n=9 mol) and gradually added to the mixture of soda ash and zeolite in a mixer while stirring.

Cooling water was passed through the jacket of the mixer to maintain the temperature of the reactants below 50°C.

The following raw materials were added to the obtained powder base and mixed by stirring.

Soap powder “ 0.12 Kg Sodium metasilicate 0.12 Kg Polyethylene glycol 0
．． 3.31 g of the 0.07 kg mixture was charged into a Henschel type small mixer, pulverized with high speed stirring for 10 seconds, and passed through a 12-mesh sieve to obtain 3.3 kg of detergent powder. The bulk density measurement result was 0.74.

Furthermore, 2% proteolytic enzyme savinase and 0°2 fragrance.
The performance test results of the cleaning composition obtained by mixing %
It is shown in Table and Table 2.

Example 3 Soda ash 0.9 Kg (8.4 G mol) Zeolite 0.9 & Coconut reduced alcohol oxide ethylene adduct (n=3) Sulfuric acid monoester 1.0 Kg (2.3 mol) Sulfuric ester l Soda ash molar ratio = 1:3.7 A palm-reduced alcohol oxide ethylene adduct produced by charging soda ash and zeolite into a small tabletop ribbon mixer (IOL) and mixing them uniformly, and then amizing the mixture with chlorsulfonic acid. of sulfuric acid monoester was gradually added with stirring. Cooling water was put into the jacket of the mixer to maintain the temperature of the reactant at 45'' C. The following raw materials were further added to the obtained powder base and mixed by stirring.

Soap powder 0.12 Kg Sodium metasilicate 0.12 K [NSA (Sanyo Chemical, higher alcohol-based nonionic powder) 0.21 Kg 3.25 Kg of the obtained mixture was charged into a Henschel type small mixer at high speed for 5 seconds. After stirring, it was sieved through a J2 mesh to obtain 3.2 Kg of detergent powder. The bulk density measurement result was 0.80.

Furthermore, 2% proteolytic enzyme Savinase (Novo).

The performance test results of the detergent composition obtained by blending 0.2% fragrance are shown in Tables 1 and 2.

Comparative example Soda ash 0.2 g (1.9 mol) Zeolite 0.5 Kg Coconut reduced alcohol sulfate monoester 1.0 Kg (3.3 mol) Sulfuric ester/soda ash molar ratio = 1:0.58 - After charging soda ash and zeolite into a tabletop ribbon mixer (IOL) and mixing them uniformly, palm reduced alcohol sulfuric acid Kaminooh stellate produced by anhydrous sulfuric acid method was gradually added while stirring and mixing. The temperature of the reactants was kept below 45°C by passing cooling water.

The reactants generated carbon dioxide gas, and the resulting paste was lump-like and difficult to powder.

〔effect〕

According to the present invention, a high bulk density higher alcohol powder detergent can be obtained without requiring drying energy, and the solubility problem that was a concern has also been solved. The production cost is lower than that of conventional powder detergent products, and it can be carried out as a pollution-free process without worrying about exhaust gas pollution.It also reduces product transportation and storage costs, and has the purpose of energy conservation. can be achieved.

Table - Implementation number/Composition component 1 2 3 Comparative side AS
38.0 31.0 - 32.5AH5,9
6,34,0 AE5 79.5 - Soap
3.6 3.5 3.6 3.6 Zeola, (To) 24.5 23.9 24.3 24.0 Soda ash 13.7 15.6 14.8 10.0
Sodium bicarbonate 10.6 8.7 L7 - Sodium silicate 1.0 0.9 0.9 9.0 Sodium silicate 3.6 3.5 3.6 7. ! IJ salt
2.4-PEG#6000
- 2.0- 2.0 Moisture 2.
8 2.8 2.7 4.8 Enzyme 2.0
2.0 2.0 2.0 Fragrance 0.2 0
．． 2 0.2 0.2 Comparison Product of crushed and granulated spray-dried powder detergent No. 2 - Table 2 Performance test results Implementation number Test item 1 2 3 Comparison - 1 Electron specific gravity 0.74 0.74- 0.80 0 .70
Solubility -20000 Detergent Umbrella 3 72.3 77.0 79,3 7
6.1 Floatability (sec) 8 2 (Compared to 1184) A product obtained by crushing and granulating spray-dried powder detergent particles.

Add 1.7 g of detergent while stirring at a constant speed to 2000 ml of cold water with solubility 811C, and after 10 minutes, stop stirring and let it stand, and the presence of insoluble detergent is not detected. Pass O
It was marked as a mark.

13. Detergency: Artificially Contaminated Cloth A cotton cloth (desized) was mixed with 10,100 O of milk and 6 ml of black ink, and then soaked in an ultrasonic bath and dried naturally.

Testing machine Turbotometer water used Yao city tap water temperature 30”C Washing conditions Pre-soaking 20 minutes washing 10 minutes washing 5 minutes Usage concentration 0.85g/4 floatability in 1000+ol Tap water (188C) in a two-tank electric washing machine 25 grams of powdered detergent is poured into the container, and the stirring is stopped.The time (seconds) it takes for the detergent particles to settle is measured.

Showa [; March 3, 211

Claims (3)

[Claims] (1) For a sulfuric acid monoester of a higher alcohol represented by the following general formula and a sulfuric acid monoester of an ethylene oxide adduct of a higher alcohol, alone or in a mixture in any ratio, at least an equimolar amount of soda carbonate and an arbitrary amount of zeolite are added. A method for producing a higher alcohol-based high-density powder cleaning agent, which is characterized by neutralizing with a mixture to generate sodium hydrogen carbonate without generating carbon dioxide gas, thereby maintaining powder fluidity and improving solubility. ROSO_3H RO(CH_2CH_2O)_nSO_3HR represents an alkyl group having 8 or more carbon atoms, and n represents the number of moles of 2 or more ethylene oxide added. (2) A mixture of a sulfuric acid monoester of a higher alcohol and an ethylene oxide adduct of a higher alcohol represented by the following formula is neutralized with a mixture of at least an equimolar amount of soda carbonate and an arbitrary amount of zeolite to the sulfuric monoester, and carbon dioxide gas is generated. 1. A method for producing a higher alcohol-based high bulk density powder cleaning agent, which is characterized by generating sodium hydrogen carbonate without generating , thereby maintaining powder fluidity and improving solubility. RO(CH_2CH_2O)_nH R is an alkyl group having 8 or more carbon atoms, and n is the number of moles of added ethylene oxide of 5 or more. (3) In addition to the powder detergent base produced in the first and second claims, anionic and nonionic activators, inorganic builders, organic builders, anti-recontamination agents, and bleaching agents are added. A higher alcohol-based high bulk density powder detergent composition obtained by blending , fluorescent dyes, enzymes, fragrances, etc.