JPH04342797A - Cleanser composition - Google Patents

Abstract

PURPOSE:To provide a cleanser composition excellent in cleansability, low foamability and rinsability and usable for wide fields such as clothes, tablewares and houses by compounding a specific alpha-sulfofatty acid alkyl ester or water-soluble salt thereof. CONSTITUTION:The objective composition comprising (A) an alpha-sulfofatty acid alkyl ester of the formula (R is C1-16C alkyl, alkenyl; R<1> is C3-6 alkyl; M is cation) or a water-soluble salt thereof and, if necessary, (B) a C14-18 alpha-sulfofatty acid methyl or ethyl ester (or its water-soluble salt) in a weight ratio of 95/5 to 20/80. The component (A) is produced by with mixing a C14-18 alpha-sulfofatty acid methyl or ethyl ester with a C3-6 middle chain alcohol in a molar ration of 1/0.9 to 1/20 and transesterifying the mixture at 80-160 deg.C.

Description

[Detailed description of the invention]

0001

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detergent composition that has excellent detergency, low foaming properties, and excellent rinsing properties, and can be used in a wide range of applications such as detergents for clothing, tableware, and household use.

0002

[Prior art and problems to be solved by the invention] Currently,
Consumers tend to prefer cleaning agents that are highly foaming when used, so various cleaning agents contain highly foaming surfactants such as sodium alkylbenzene sulfonate, sodium α-olefin sulfonate, and sodium higher alcohol ethoxy sulfate. General-purpose anionic activators are widely used.

[0003] On the other hand, in recent years, due to changes in lifestyle, Western-style rotating drum type clothes washing machines and water jet type fully automatic dishwashers are becoming popular in Japan as well. but,
If these devices are cleaned using the above-mentioned general-purpose anion activator-containing cleaning agents, the amount of foam generated will be too large, which will significantly reduce the cleaning effect, and the foam will overflow to the outside of the device, making it impractical for practical use. It is known to cause irresistible damage.

[0004] Therefore, in order to improve such problems,
Conventionally, it has been common practice to add antifoaming or antifoaming agents such as silicone oil and soap to detergent compositions (German Published Patent Application No. 2115082, Japanese Unexamined Patent Publication No. 48-4371).
(See Publication No. 0). However, although the addition of antifoaming or antifoaming agents is effective in suppressing the foaming properties of cleaning compositions, it has the disadvantage that it tends to reduce the cleaning effect and is also economically disadvantageous. Therefore, it has been desired to develop a detergent composition that has high detergency, low foaming properties, and good rinsing properties without adding antifoaming or foam suppressing agents.

[0005]

[Means and effects for solving the problem] In view of the above circumstances, the present inventors have made extensive studies and found that a long-chain fatty acid methyl or ethyl ester having 14 to 18 carbon atoms in a fatty acid residue can be obtained by sulfonating a long-chain fatty acid methyl or ethyl ester. α-sulfo fatty acid methyl or ethyl ester and a medium chain alcohol having 3 to 6 carbon atoms are mixed in a molar ratio of 1/0.9 to 1/20, and at a temperature range of 80 to 160°C. By incorporating as a surfactant α-sulfo fatty acid alkyl ester or its water-soluble salt represented by the following general formula (1), which can be industrially advantageously produced by transesterification, conventional general-purpose anions It has excellent cleaning power equivalent to that of an activator, and has low foaming properties even without the addition of anti-foaming or foam-inhibiting agents at normal usage concentrations, making it suitable for rotary drum-type clothes washing machines, fully automatic dishwashers, etc. It has been found that a detergent composition can be obtained that does not cause a decrease in the cleaning effect or cause foam failure even when applied, and has excellent foam removal properties during rinsing.

[0006]

embedded image (wherein R is an alkyl group or alkenyl group having 12 to 16 carbon atoms, R1 is an alkyl group having 3 to 6 carbon atoms,
M is a cation. )

Furthermore, together with the α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt, α-sulfo fatty acid methyl or ethyl ester having 14 to 18 carbon atoms of a fatty acid residue, which has poor rinsability when used alone, It was also discovered that when the water-soluble salt is blended in a weight ratio of 95/5 to 20/80, rinsability can be favorably improved while maintaining detergency at a high level, and this has led to the present invention. It is.

[0008] To explain the present invention in more detail below, the cleaning composition of the present invention contains an α-sulfo fatty acid alkyl ester represented by the following general formula (1) or a water-soluble salt thereof as a surfactant. .

[0009]

embedded image (wherein R is an alkyl group or alkenyl group having 12 to 16 carbon atoms, R1 is an alkyl group having 3 to 6 carbon atoms,
M is a cation. )

Here, R in the above formula (1) has 12 carbon atoms.
-16, preferably 14-16 alkyl or alkenyl groups, and examples of the R-CH-COO group include myristyl, palmityl, and stearyl groups. Further, R1 is an alkyl group having 3 to 6 carbon atoms, preferably 4 to 5 carbon atoms, and if the number of carbon atoms is less than 3, the cleaning composition may have poor rinsing properties, and if the number of carbon atoms exceeds 6, the cleaning power may be poor. It may be inferior. This R1 may be linear or branched, such as n-propyl, i-propyl, n-butyl, i
-butyl, sec-butyl, i-amyl, n-hexyl and the like. Furthermore, M is a cation, such as sodium, potassium, monoethanolamine, diethanolamine, triethanolamine, and the like.

Specific examples of such α-sulfo fatty acid alkyl esters or water-soluble salts thereof include α-sulfomyristic acid n-propyl ester, α-sulfopalmitic acid i-propyl ester, α-sulfostearic acid s
Examples include ec-butyl ester, α-sulfomyristic acid i-amyl ester, α-sulfostearic acid i-propyl ester, or a water-soluble salt thereof.

The α-sulfo fatty acid alkyl ester or its water-soluble salt of formula (1) above is an α-sulfo fatty acid alkyl ester obtained by sulfonating a long-chain fatty acid methyl or ethyl ester.
Sulfo fatty acid methyl or ethyl ester and carbon number 3-6
It can be efficiently produced by carrying out a transesterification reaction with a medium-chain alcohol.

In this case, the long-chain fatty acid methyl or ethyl ester preferably has a fatty acid residue having 14 to 18 carbon atoms, particularly 16 to 18 carbon atoms, such as myristic acid,
Examples include methyl or ethyl esters of palmitic acid, stearic acid, and the like.

Furthermore, the sulfonation of the long-chain fatty acid methyl or ethyl ester is carried out by a conventional method, for example, by reacting the long-chain fatty acid methyl or ethyl ester with gaseous SO3 using a continuous thin-film sulfonation apparatus, followed by an aging reaction. Alternatively, long chain fatty acid methyl or ethyl esters are dissolved in an inert solvent such as carbon tetrachloride or 1,2-dichloroethane and gaseous SO3 is blown into the solution, or liquid SO3 is dissolved.
It can be carried out by adding dropwise and then carrying out a ripening reaction, and by this sulfonation, the number of carbon atoms in the fatty acid residue is 14 to 1.
The α-sulfo fatty acid methyl or ethyl ester of No. 8 can be obtained. Here, in the above sulfonation method, gaseous or liquid SO3 is added to the long chain fatty acid methyl or ethyl ester.
are mixed at a molar ratio of 1/1 to 1/1.5, and
Preferably, the reaction is carried out at a reaction temperature in the range of 70°C,
Further, it is preferable that the aging reaction is carried out at 60 to 100°C for 30 to 120 minutes.

[0015] Next, the obtained α-sulfo fatty acid methyl or ethyl ester is transesterified with a medium chain alcohol. In this case, the medium chain alcohol is one having 3 to 6 carbon atoms, such as propanol. , butanol, pentanol, hexanol, etc. are used,
These may be linear or branched.

Furthermore, in this transesterification reaction, it is preferable to use the above-mentioned medium chain alcohol in a molar ratio of 0.9 to 20 times, particularly 1 to 10 times, relative to the α-sulfo fatty acid methyl or ethyl ester. If the amount of medium-chain alcohol used is less than 0.9 times the mole, the transesterification rate may be too low, and even if it is more than 20 times the mole, the transesterification rate remains constant, which may be economically disadvantageous. In addition, the reaction can be carried out at 80 to 160°C, especially 90 to 140°C, usually for 1 to 5 hours, and the reaction temperature is 80°C.
If it is lower, the transesterification rate may be lower, and 16
Conversely, if the temperature is higher than 0°C, the transesterification rate may be partially cut off. Furthermore, although the reaction can be carried out either under normal pressure or reduced pressure, it is generally preferable to carry out the reaction under normal pressure. In this transesterification reaction, the above-mentioned medium-chain alcohol may be synthesized in advance by a normal method and once isolated, and then subjected to the transesterification reaction, but usually, the medium-chain alcohol is synthesized and then isolated. It is advantageous in terms of cost to use it in the transesterification reaction without separating it.

[0017] The compound represented by general formula (1) is
Of course, it may be produced by a known method such as direct sulfonation of the fatty acid medium chain ester or direct esterification of the α-sulfo fatty acid.

The blending amount of the α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt is 3 to 50% (weight %, the same applies hereinafter) of the entire detergent composition, particularly 10 to 40%.
% is preferable. If the amount is less than 3%, sufficient cleaning power and rinsing performance may not be obtained.
%, manufacturing may become difficult.

Furthermore, the α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt according to the present invention has excellent detergency and extremely low foaming properties, and therefore can be used in detergent compositions. It can be used alone as an anionic activator, but general high-foaming activators such as alkylbenzene sulfonates, α-olefin sulfonates, alcohol polyethoxy sulfates, and those other than those of formula (1) may also be used. It can also be used to improve the ability to remove foam during rinsing, which is a problem when these other active agents are used in combination with α-sulfofatty acid alkyl esters or water-soluble salts thereof. In particular, α- with fatty acid residues having 14 to 18 carbon atoms.
Although sulfo fatty acid methyl or ethyl esters or their water-soluble salts have extremely high detergency, they have poor foam removal properties during rinsing. By doing so, rinsing performance can be improved while maintaining the cleaning effect at a high level. In this case, α− of the above equation (1)
Sulfo fatty acid alkyl ester or water-soluble salt thereof (A)
and α-sulfo fatty acid methyl or ethyl ester or a water-soluble salt thereof (B) whose fatty acid residue has 14 to 18 carbon atoms
The weight ratio of (A)/(B) = 95/5 to 20/80,
In particular, it is preferable to combine them in a ratio of 80/20 to 50/50 in order to obtain good detergency and rinsability. If the ratio of (A)/(B) exceeds 95/5, the original (B)
) The high detergency of the components may not be exhibited, and if the ratio is less than 20/80, rinsing performance may be poor.

In addition to the above-mentioned active agents, other surfactants such as higher alcohol sulfates, alkylbenzene sulfonates, soaps, and alcohol polyethoxylates can also be added. Note that the amount of other activators added can be set to a normal amount within a range that does not impede the effects of the present invention.

[0021] The cleaning composition of the present invention can be made into various forms of cleaning agents by blending other optional components depending on its intended use. When the composition of the present invention is used as a granular detergent for clothing, optional ingredients such as zeolite, alkali builders such as sodium citrate, nitrilotriacetic acid, and sodium polyacrylate, bleaching agents such as sodium sulfate, fragrances, and dyes may be added. It can be prepared in a conventional manner by adding the required amount. In addition, when using liquid detergents such as food and dishwashing detergents and shampoos, for example, organic solvents such as ethanol and propylene glycol, hydrotropes such as paratoluenesulfonate and benzenesulfonate, colorants, static It can be prepared by a conventional method by appropriately blending fungicides, chelating agents, etc. In addition, since the α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt has good hydrolysis resistance, the composition of the present invention can be sufficiently prepared as a liquid detergent.

[0022]

[Effects of the Invention] The cleaning composition of the present invention has excellent cleaning power, low foaming properties, and good rinsing properties.
It can be suitably used in situations where a large amount of foam is disadvantageous when used, such as rotating drum type clothes washing machines, water jet type fully automatic dishwashers, and cleaning systems for the food industry, which have become popular in recent years. In addition, the foam removal during rinsing can be improved even under the conditions of use of current pulsator-type clothes washing machines, so water and energy resources can be saved, which is also useful.

[0023]

[Examples] The present invention will be specifically explained below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In addition, all % in each example is weight %. [Examples 1 to 21, Comparative Examples 1 to 8] Cleaning compositions having the following compositions containing various surfactants shown in Table 1 were prepared,
The cleaning power, foaming, and rinsability of these cleaning compositions were evaluated by the following methods. The results are also listed in Table 1.

Composition of cleaning composition:

[0025] Method for evaluating cleaning power: 5 pieces of soiled cloth (5 x 5 cm) in which the following composition of soil was applied to cotton cloth and a washed knitted cloth were used to adjust the bath ratio to 30 times, and the mixture was washed with a Targ Autometer [T].
erg-O-tometer (U.S.Testing
), 120 rpm] under the following conditions. This was rinsed and dried, and the brightness before and after washing was measured with a reflectance meter, and the cleaning rate was calculated according to the following formula. Soil Composition Organic Soil: Oleic acid (45%), cholesterol oleate (19.5%), triolein (25%), liquid paraffin (4%), squalene (4%), cholesterol (2.5%) ) Inorganic dirt: clay organic dirt/inorganic dirt/gelatin/carbon black = 6
2.7/29.8/7.0/0.5 (weight ratio) Cleaning conditions Cleaning agent concentration: Dissolve 0.75 g of the cleaning agent composition in 900 ml of cleaning water (Hardness: 3 degree hard water used) Cleaning temperature, Time: 25℃, 10 minutes

[0026]

[Math 1]

Method for evaluating foaming: 10 ml of a solution of the cleaning composition was placed in an Epton tube under the same cleaning conditions as in the evaluation of detergency, and after immersion 20 times, the amount of foam (ml) was measured 1 minute later.

Rinseability evaluation method: surfactant concentration is 1
The amount of foam remaining on the liquid surface was measured after stirring for 5 minutes using a washing machine (manufactured by Hitachi, Ltd.) under the same washing conditions as for the detergency evaluation, except that the detergent composition was dissolved so that the cleaning composition was dissolved in ppm. Visual evaluation was performed using the following four-level criteria. Evaluation criteria for rinsing performance: Very good, very poor, and extremely poor.

[0029]

[Table 1]

From the results in Table 1, it can be seen that the number of carbon atoms in the fatty acid residue is 1.
The detergent compositions (Examples 1 to 21) containing sodium salts of alkyl esters having 3 to 6 carbon atoms of 4 to 18 α-sulfo fatty acids as surfactants have sufficient detergency, and It was confirmed that foaming during use was low and rinsability was good. On the other hand, a sodium salt of an alkyl ester having 1 or 2 carbon atoms of α-sulfo fatty acid whose fatty acid residue has 14 to 18 carbon atoms, and a fatty acid residue whose carbon number is 14
The cleaning compositions (Comparative Examples 1 to 8) containing α-olefin sulfonic acid sodium salt having 18 carbon atoms and alcohol ethoxysulfate sodium salt having 13 carbon atoms (average number of moles of added ethoxy group 3) as surfactants were Although it had high strength, it produced a lot of foam during use and had poor rinsing properties.

[Examples 22 to 26] α-Sulfo fatty acid methyl ester sodium salt having 18 carbon atoms of fatty acid residue (
A mixture of α-sulfofatty acid sec-butyl ester sodium salt (abbreviated as C18-SFsecBu) having 18 carbon atoms in the fatty acid residue (abbreviated as C18-SFMe) in the ratio shown in Table 2 was used as a surfactant. The cleaning power and rinsing properties of the same cleaning composition as in the above Example except for the following were evaluated by the above method. The results are also listed in Table 2.

[0032]

[Table 2]

According to the results in Table 2, C18- has poor rinsing properties.
The weight ratio of C18-SFsecBu to SFMe is 3
It has been found that by mixing at a ratio of 10% or more and 80% or less, rinsing performance can be improved while maintaining a high level of detergency.

[Reference Example] Using a continuous thin film type sulfonation apparatus, methyl palmitate was sulfonated at a reaction temperature of 60°C by mixing SO3/methyl palmitate at a molar ratio of 1.2, and then heated to 80°C. The mixture was aged for 1 hour to obtain methyl α-sulfopalmitate. Next, this methyl α-sulfopalmitate is mixed with various alcohols at a specific ratio [alcohol/α-methyl sulfopalmitate (molar ratio)] as shown in Table 3, and transesterified at the temperature shown in Table 3. After carrying out the reaction for 3 hours, it was neutralized with an aqueous NaOH solution and HP
The transesterification rate was determined by LC method (high performance liquid chromatography method). The results are also listed in Table 3.

[0035]

[Table 3]

From the results in Table 3, by reacting an alcohol having 3 to 6 carbon atoms with α-sulfofatty acid methyl ester at a molar ratio of 0.9 to 20 at a temperature in the range of 80 to 160°C, It was found that the method exhibited an excellent transesterification rate, and that the α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt could be efficiently produced.

Claims (3)

[Claims] 1. A cleaning composition comprising an α-sulfo fatty acid alkyl ester represented by the following general formula (1) or a water-soluble salt thereof. embedded image (wherein R is an alkyl group or alkenyl group having 12 to 16 carbon atoms, R1 is an alkyl group having 3 to 6 carbon atoms,
M is a cation. ) [Claim 2] The α-sulfo fatty acid methyl or ethyl ester having 14 to 18 carbon atoms in the fatty acid residue or the water-soluble salt thereof is added by weight to the α-sulfo fatty acid alkyl ester or water-soluble salt thereof of the formula (1). Ratio: 95/5 to 20/8
The cleaning composition according to claim 1, wherein the cleaning composition is blended in a proportion of 0. 3. The α-sulfo fatty acid alkyl ester of formula (1) or its water-soluble salt has a fatty acid residue having 14 carbon atoms.
The molar ratio of α-sulfo fatty acid methyl or ethyl ester obtained by sulfonating ~18 long chain fatty acid methyl or ethyl ester and a medium chain alcohol having 3 to 6 carbon atoms is 1/0.9 to 1. 3. The cleaning composition according to claim 1, wherein the cleaning composition is mixed at a ratio of 1/20 and is produced by transesterification at a temperature of 80 to 160C.