WO2004092314A1

WO2004092314A1 - Oligomeric surfactants and detergent compositions containing the same

Info

Publication number: WO2004092314A1
Application number: PCT/JP2003/004683
Authority: WO
Inventors: Shigeyoshi Uenoyama
Original assignee: Uenoyama Giken Co., Ltd; Meiwa Corporation
Priority date: 2003-04-14
Filing date: 2003-04-14
Publication date: 2004-10-28
Also published as: JPWO2004092314A1; AU2003236242A1; AU2003236242A8

Abstract

Oligomeric surfactants having a high safety, little irritating the skin, being free from unnecessary foaming and being excellent in emulsifying power and detergency; surfactant compositions containing the same; and detergent compositions containing these surfactant compositions. The oligomeric surfactants contain oligolactic acid fatty acid esters represented by the following general formula (1) or salts thereof and surfactants containing 30% by mass or more of the same are usable as detergents for foods, fibers, skin, hair, hard surfaces and so on. (1) wherein R1 represents C7-23 alkyl or alkenyl; M represents hydrogen or at least one member selected from among alkali metals, alkaline earth metals, alkanolamines, ammonia, basic amino acids and lower alkylamines; and n is from 2 to 15.

Description

TECHNICAL FIELD The present invention relates to an oligomer type surfactant and a detergent composition containing the same.

The present invention relates to an oligomer type surfactant used for a detergent and the like, a surfactant composition containing the same, and uses thereof.

Light

Background art

Generally, detergent compositions include anionic surfactants such as alkyl sulfates, polyoxyalkylene alkyl sulfates, monosulfo fatty acid ester salts, α-olefin sulfonic acid salts, and the like, and polyoxyethylene alkyl ethers. Nonionic surfactants such as polyalkyl darcoside and polyoxyethylene glycerin fatty acid ester are used. Since these surfactants have excellent detergency and emulsifying power, they are widely used in detergents, emulsifiers, cosmetics, and the like.

However, in recent years, surfactants with high safety as well as detergency and emulsifying power have been demanded in consideration of the effects on the environment and the human body. As highly safe cleaning agents, for example, sucrose fatty acid esters, glycerin mono fatty acid esters, and the like are known. In particular, surfactants that are highly safe, mild on the skin, and excellent in detergency, emulsifying power, etc. are required for washing foods that are taken orally and kitchen utensils that are frequently in contact with the human body. However, a surfactant that can achieve both of them has not been obtained.

By the way, conventionally, various compounds using lactic acid are known. For example, lactic acid has a bacteriostatic and fungicidal effect, which improves the shelf life of food It is used as a food preservative. Polylactic acid-based polymers are attracting attention as biodegradable polymers. It is known that fatty acid lactic acid ester salts are useful as anionic surfactants in applications such as buns, cosmetics, detergents, etc. (Japanese Patent Application Laid-Open Nos. Sho 62-62337, Hei 4_ Publication No. 230900).

Japanese Patent Application Laid-Open No. 9-208484 discloses an ester derivative of a fatty acid and a lactic acid or a salt thereof having a cis-l-octadecenoic acid content of 85% or more, with a content of 0.05 to 5%. A cosmetic containing 5% by weight is disclosed. Fatty acid chloride is obtained by reacting a fatty acid with a high content of cis-19-octadecenoic acid with phosphorus oxychloride, and then reacting the fatty acid chloride with lactic acid to synthesize lactic acid octadecane. This improves the moisturizing of the stratum corneum of the skin, keeps the skin young and healthy, and avoids the problem of irritation to the skin due to heavy use.

Japanese Patent Application Publication No. 2000-530093 discloses stearoyl lactinate as an OZW type emulsifier for the preparation of cosmetic and pharmaceutical preparations such as shampoos for hair, hair lotions and skin creams. It is disclosed that a fatty acid lactic acid ester such as sodium is used. It is described that this improves the emulsifying power and emulsion stability.

Japanese Patent Application Laid-Open No. 9-278686 has disclosed that in order to solve the problems of the conventional fatty acid lactate ester salts, fatty acid lactate ester salts having 14 to 22 carbon atoms and 14 to 22 carbon atoms were used. An emulsifier composition comprising a sucrose fatty acid ester of the formula (I), wherein the former has a molar fraction of 0.008 to 0.15. As a specific example, there is described an example in which soybean oil and liquid paraffin are emulsified using a mixture of potassium stearate lactate and sucrose fatty acid ester. As a result, an emulsifier with high versatility, high safety, gentle to the human body, excellent dispersibility, low foaming property, and excellent emulsion stability was obtained. Therefore, it can be used as an emulsifier for foods and cosmetics.

However, in the above-mentioned literature, an ester of a fatty acid such as palmitic acid / stearic acid and lactic acid is used in order to impart the stability of the emulsified caemulsion. Although excellent, there is a problem that the cleaning power is hardly exhibited.

The present invention has been made in view of the above-mentioned conventional problems, and provides an oligomeric surfactant having high safety, less skin irritation, no unnecessary foaming, and excellent emulsifying power and detergency. An object of the present invention is to provide a surfactant composition containing the same, and a detergent composition containing the surfactant composition. Disclosure of the invention

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that esters of oligolactic acid and fatty acids, which are dehydration-condensation polymers of lactic acid, have superior detergency compared to fatty acid lactic acid esters, and are of the oligomer type. Because of this, it has low critical micelle concentration (cmc) and exhibits surfactant properties even in a small amount, so it can be used in a smaller amount than conventional surfactants, and also has excellent surfactant properties such as good emulsifying power. And found that the present invention was completed.

That is, the present invention provides an oligomer type I surfactant comprising an oligolactic acid fatty acid ester represented by the following general formula (1) or a salt thereof.

R, C O (1)

(Wherein, is an alkyl or alkenyl group having 7 to 23 carbon atoms, M is at least one selected from a hydrogen atom or an alkali metal, an alkaline earth metal, an alkanolamine, an ammonia, a basic amino acid, and a lower alkylamine. , N is 2 to 15.

In the oligomer type surfactant according to the present invention, it is preferable that (e) is an alkyl or alkenyl group having 10 to 14 carbon atoms. Further, it is preferable that the average n is 3 to 5.

The oligomer type surfactant of the present invention can be obtained by an esterification reaction between a fatty acid having 8 to 24 carbon atoms and oligolactic acid.

Further, the present invention provides an oligomer type surfactant composition wherein the content of the oligolactic acid fatty acid ester represented by the above formula (1) or a salt thereof is 30% by mass or more, and the surfactant composition The present invention provides a detergent composition having a content of 0.1 to 60% by mass. Further, a detergent composition containing 0.1 to 60% by mass of the oligomer type surfactant composition, 0.1 to 30% by mass of an anionic surfactant and 0.1 to 30% by mass of a Z or nonionic surfactant. Is provided. The cleaning composition of the present invention is suitably used for cleaning foods, dishes, automatic dishwashers, or kitchen utensils. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the present invention will be described in detail. The oligomer type surfactant of the present invention contains an oligolactic acid fatty acid ester represented by the formula (1) or a salt thereof as an essential component. As the fatty acid constituting the oligolactic acid fatty acid ester or a salt thereof used in the present invention, a fatty acid having 8 to 24 carbon atoms, preferably 10 to 18 carbon atoms, more preferably 10 to 14 carbon atoms is used. When the fatty acid chain length is less than 8, the affinity of the hydrophobic portion with the oil is reduced, so that the detergency and the emulsion stability are deteriorated. If the fatty acid chain length exceeds 24, the hydrophobicity is strong. It becomes too soluble and insoluble in water, resulting in poor detergency and emulsion stability. If the fatty acid chain length is outside the above range, it becomes difficult to obtain raw materials. As long as the number of carbon atoms is within the above range, the fatty acid may be saturated or unsaturated, and may be linear or branched. In the case of a branched chain, the length of the longest chain is preferably 8 or more, more preferably 10 or more. Further, a hydroxyl carboxylic acid having a hydroxyl group may be used. Specific examples of these fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, araquinic acid, behenic acid, tetradecenoic acid, hexadecenoic acid, oleic acid, and elaidin. Acid, linoleic acid, linolenic acid, ricinoleic acid, eicosenoic acid, eicosatetraenoic acid (arachidonic acid), docosenoic acid (eric acid), isostearic acid, hexyldecanoic acid, 'hexyl decanoic acid, octyldecanoic acid, Examples include hydroxytetradecanoic acid, hydroxyhexadecanoic acid, hydroxyoctadecanoic acid, 12-hydroxystearic acid, 10-hydroxyoctadecanoic acid, and 2-hydroxydecanoic acid.

In the synthesis of oligolactic acid fatty acid esters (salts), lower alkyl (1 to 3 carbon atoms) esters of these fatty acids can also be used. Specific examples of these fatty acid alkyl esters include methyl laurate, methyl myristate, and the like. In the transesterification at this time, it is desirable to add about 0.1% (mol) of sodium hydroxide or the like to the fatty acid alkyl ester.

Of these fatty acids, chloropric acid, lauric acid, myristic acid and the like are particularly preferred because of their excellent washing performance and easy availability. In the oligolactic acid fatty acid ester (salt), these fatty acids may be a mixture of two or more kinds in an arbitrary ratio, or coconut fatty acids. Oligolactic acid in oligolactic acid fatty acid ester (salt) is lactic acid An oligomer obtained by polymerizing is used, and its synthesis method does not matter. Lactic acid may be produced by either a fermentation method or a synthetic method,

D body L body does not matter. Examples of a method for synthesizing oligolactic acid include a method in which lactic acid is directly dehydrated in the presence of a catalyst and polycondensed. The degree of polymerization n of the oligolactic acid in the oligolactic acid fatty acid ester (salt) is in the range of 2 to 15. When the degree of polymerization n is less than 2, the cleaning power tends to decrease, and disadvantages such as precipitation of crystals at low temperatures occur. When the degree of polymerization exceeds 15, the detergency tends to decrease as in the case where the degree of polymerization is low. If the degree of polymerization is more than 15, the distribution of the degree of polymerization is broadened, so that the characteristics of a low polymer of a molecule having a smaller surfactant (such as a dimer) become remarkable. The degree of polymerization n in the oligolactic acid fatty acid ester (salt) is more preferably 2 to 10, and even more preferably 2 to 8. In particular, it is preferable that the average value n of the polymerization degree is in the range of 3 to 5. The oligolactic acid fatty acid ester or a salt thereof is usually obtained by reacting a fatty acid or a reactive derivative such as a fatty acid chloride, a fatty acid salt or a fatty acid ester with a lactic acid oligomer or a salt thereof. The reaction is usually carried out at a temperature of 80 to 250 and 2 to 10 hours, and can be performed in the presence or absence of a solvent. In particular, when fatty acid chloride is used in a basic solvent, 10 to 90,:! It can be done in ~ 3 hours. Generally, it is obtained by esterifying a lactic acid oligomer and a fatty acid (or an ester thereof). In this case, the reaction is performed in the presence of a catalyst (for example, an acid catalyst such as sulfuric acid) using a fatty acid in a ratio of 0.8 to 1.2 moles per mole of the lactic acid oligomer. Alternatively, oligomerization and esterification may be simultaneously performed while mixing 0.3 to 0.6 mol of a fatty acid with respect to 1 mol of lactic acid and dehydrating the mixture under reduced pressure. The reaction is usually carried out at a temperature of 80 to 150 ° C. for 2 to 10 hours. The reaction solution of oligolactic acid fatty acid ester or salt thereof produced by a known method contains, in addition to oligolactic acid fatty acid ester, unreacted fatty acid or salt thereof, lactic acid or salt thereof, fatty acid lactate ester or salt thereof, and solvent. If used, additional solvent is present. At this time, the content of the target oligolactic acid fatty acid ester or its salt in the reaction product excluding the solvent varies depending on the ratio of the fatty acid used for the reaction to the oligolactic acid, but the oligolactic acid fatty acid ester or its salt It is about 30 to 70 mol% based on the total amount of unreacted fatty acids or salts thereof, lactic acid or salts thereof, and fatty acid lactic acid esters or salts thereof. The oligolactic acid fatty acid ester or a salt thereof of the present invention can be obtained by purifying the esterification reaction product by a usual purification technique.

Purification methods include, for example, liquid-liquid extraction of the reaction mixture with an aqueous solvent and an organic solvent to generate an organic solvent phase rich in oligolactic acid fatty acid ester and an aqueous solvent phase rich in lactic acid, and the two phases are separated. Then, the oligolactic acid fatty acid ester in the organic solvent phase is separated from the coexisting fatty acid by crystallization, or an aqueous acid solution is added to the reaction mixture to precipitate an oligolactic acid fatty acid ester as an oil. Is obtained by dissolving the resultant in an organic solvent to obtain a solution, and crystallizing and obtaining an oligolactic acid fatty acid ester from the solution.

The molar ratio of the basic substance to the oligolactic acid fatty acid ester thus obtained in an aqueous solution or an alcoholic aqueous solution such as ethanol (oligolactic acid fatty acid ester basic substance) 1 / 0.8 to 1Z 1. By reacting in addition in step 2, an oligolactic acid fatty acid ester salt can be obtained. By maintaining the molar ratio between the oligolactic acid fatty acid ester and the basic substance in this range, the surface activity can be kept good. When the molar ratio of the basic substance is too large, hydrolysis of the oligolactic acid fatty acid ester is caused by an increase in the basic substance. Is promoted, the oligolactic acid fatty acid ester salt decreases, and the ratio of stone and oligolactic acid increases. Therefore, the stability of the oligolactic acid fatty acid ester salt with time in the presence of water is reduced, and the detergency and the emulsifying power are reduced. On the other hand, if the molar ratio of the basic substance is too small, the hydrolysis rate of the oligolactic acid fatty acid ester is low, but the performance as an ionic surfactant is reduced due to the small amount of basic ion, and the oligolactic acid fatty acid ester salt Surface activity is reduced. Bases that form salts with oligolactic acid fatty acid esters include alkali metals such as sodium and potassium, alkaline earth metals such as calcium and magnesium, alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine, ammonia, The surfactant composition of the present invention includes a basic amino acid such as arginine and a lower alkylamine such as triptylamine. The surfactant composition of the present invention mainly comprises oligolactic acid fatty acid ester (salt), a trace amount of fatty acid lactate ester, and unreacted fatty acid. , Lactic acid and the like, and the content of the oligolactic acid fatty acid ester (salt) in the surfactant composition is preferably 30% by mass or more. The content of the oligolactic acid fatty acid ester is preferably 30 to 70% by mass, more preferably 35 to 70% by mass, and particularly preferably 40 to 70% by mass. The content of the oligolactic acid fatty acid ester is defined as follows. When the content of the ester is less than 30% by mass, the lactic acid fatty acid ester having low surface activity due to equilibrium between the compositions, fatty acid, This is because the increase in lactic acid or the like causes the oligolactide fatty acid ester to exhibit insufficient surface activity, and the surfactant has a reduced detergency. On the other hand, if it exceeds 70% by mass, the cost of purification from the reaction solution increases, and the economic efficiency is poor. In the surfactant composition of the present invention, the total content of oligolactic acid fatty acid ester and fatty acid lactic acid ester is preferably 90% by mass or more. Said The total content is specified because if it is lower than 90% by mass, the unreacted fatty acids increase and the odor worsens. Further, the mass ratio between the oligolactic acid fatty acid ester and the fatty acid lactic acid ester is 50 to 99Z1 to 50, preferably 55 to 95Z5 to 45, more preferably 60 to 90Z10. It is appropriate to set to ~ 40. The reason for limiting the mixing ratio in this way is that if the mixing ratio is smaller than 50/50, the ratio of oligolactic acid fatty acid ester decreases, and the detergency decreases due to the increase in lactic acid fatty acid ester having low surface activity. When the ratio is larger than 99/1, the distribution of the degree of polymerization of lactic acid is broadened, so that the characteristics of the surfactant are apt to fluctuate. It is.

When the surfactant composition of the present invention is used as a detergent, it is usually appropriate to incorporate 0.1 to 60% by mass of an oligolactic acid fatty acid ester (salt) in the detergent composition. The amount is more preferably from 1 to 45% by mass, and even more preferably from 5 to 30% by mass. The reason for limiting the mixing ratio in this manner is that if the blending amount in the detergent composition is too small, the detergency decreases, and if it is too large, the handleability deteriorates, and in some cases, the detergency decreases and the surfactant In some cases.

To the cleaning composition of the present invention, any one of the commonly used additive components for detergents can be selected and added as long as the object of the present invention is not impaired. Examples of such additional components include surfactants such as anionic surfactants, nonionic surfactants, surfactants such as carboxybetaine-type, imidazolidinum-type or sulfobetaine-type amphoteric surfactants, carrageenan, Natural bean gum, guar gum, evening malin gum, gum arabic, xanthan gum, pectin, pullulan, casein, gelatin, albumin, casein, soy protein, dartene, etc. Natural viscosity stabilizers, methylcellulose, sodium caseinate, polyacrylic acid Which synthetic thickeners, chelating agents such as citric acid, builders such as inorganic salts, hydrotropes such as aromatic sulfonates, viscosity modifiers, fragrances, coloring agents, antioxidants, preservatives, and disinfectants , Anti-inflammatory agents, medicinal ingredients, enzymes and the like. The solvent of the detergent composition is usually water, but may further contain another liquid solvent such as a lower alcohol, glycol or the like.

Here, as the anionic surfactant, for example, one or more anionic functional groups selected from the group consisting of a carboxylic acid group, a sulfonic acid group, a sulfate group, and a phosphate group as a polar group Are particularly preferred. Specifically, fatty acid soaps, alkyl ether carboxylate, amino acid-based anionic surfactants represented by N-alkyliminodicarboxylic acid, N-alkyliminodicarboxylic acid, or salts thereof, 0.1% sulfo fatty acid salts, Alkylsulfonates, alkylsulfosuccinates, ο; —sulfuric acid sulfonates, alkyl sulfates, polyoxyethylene alkyl ether sulfates, alkyl phosphates, alkyl ether phosphates, alkyl phosphate esters, etc. No. Among them, polyoxyethylene alkyl ether sulfate, a-olefin sulfonic acid salt, alkyl ether carboxylate, fatty acid soap, acyl taurate, alkyl phosphate ester salt and the like are particularly preferable. These anionic surfactants can be used alone or in combination of two or more. When the anionic surfactant is blended, the amount is preferably in the range of 0.1 to 30% by mass, particularly preferably in the range of 1 to 15% by mass, in the detergent composition.

Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyglycerin fatty acid esters, glycerin monofatty acid esters, glycerin difatty acid esters, pull-mouth nicks, sorbitan fatty acid esters, and polyoxyethylene sorbitan. Evening fatty acid esthetic Sucrose fatty acid ester, polyoxyethylene acyl ester, alkyl polyglycoside, fatty acid methyl daricoside ester, alkylmethyl glucamide, fatty acid alkanolamide and the like. Among these, fatty acid esters of polyhydric alcohols such as polyglycerin fatty acid ester, glycerin mono, difatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester and sucrose fatty acid ester are safe. It is more preferred because it has high potency and is approved as a food additive. These nonionic surfactants can be used alone or in combination of two or more. When the nonionic surfactant is blended, the blending amount is preferably in the range of 0.1 to 30% by mass, particularly preferably in the range of 1 to 15% by mass in the detergent composition.

When the oligomer type surfactant composition of the present invention is used in combination with an anionic surfactant and another surfactant such as Z or nonionic surfactant, the compounding ratio (oligomer type surfactant composition / other surfactant) The amount of the agent is 10 to 99Z1 to 90, preferably 15 to 90710 to 85, and more preferably 20 to 80/20 to 80 by mass ratio. The reason for limiting the combination ratio in this manner is that if the ratio is less than 10 90, the detergency decreases, and if it is greater than 991, the solubility of the oligolactic acid fatty acid ester in water decreases. By using together the oligomer type surfactant composition and the anionic surfactant and the no or nonionic surfactant within the above range, the lipophilic oligolactic acid fatty acid ester is solubilized and the whole becomes an aqueous solution. The stability of the aqueous surfactant solution is also improved. In addition, because it contains an oligolactic acid fatty acid ester that has a high affinity for oil stains, the detergency against oil stains is significantly greater than when only other anionic surfactants and nonionic surfactants are used. improves.

The oligolactic acid fatty acid ester of the present invention is itself C〇D, BOD, It is a highly safe surfactant with low fish toxicity. Therefore, the cleaning composition of the present invention can be used for cleaning foods, fibers, skin, hair, hard surfaces, etc., but foods, dishes, kitchen utensils, kitchen utensils, and the like, in which safety is particularly required. Suitable for cleaning of types. In particular, it can be safely used as a detergent for removing contaminants, extra fat, protein, etc. from fruits, vegetables, meat, and fish. It can also be used as a rinse agent except for water spots on commercial dishes in the restaurant industry. Also, since it acts gently on the body, it can be used in household cleaners such as shampoos, body soaps, kitchen cleaners, and baby bottle cleaners. It can also be used to clean kitchen and kitchen utensils such as home and commercial refrigerators (inside and outside), microwave ovens (inside and outside), sinks, countertops, and cooking utensils. Furthermore, it can be used as a detergent for automatic dishwashers.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples. In the following examples, “% by mass” is abbreviated as “%” unless otherwise specified.

(Production Example 1)

Lactic acid (53 g, 0.5 mol) and toluene (80 ml) were placed in a reaction vessel, and allowed to react at 100 ° C. for 5 hours at 130 ° C. to synthesize oligolactic acid. To this, 50 g (0.25 mol) of lauric acid and 0.5 ml (0.01 mol) of sulfuric acid were added, and the mixture was reacted while being dehydrated at 100 ° (: up to 130 ° C for 3 hours). After the completion of the reaction, the reaction product was cooled to room temperature, and water was added to the obtained reaction product to add water 3 Om1. After transferring the components to the aqueous phase, the aqueous phase and the toluene phase were separated, and the remaining toluene phase was concentrated at a temperature of 125 ° C or lower to obtain 85.9 g of a reaction purified product. The yield was 99.88%.

The resulting reaction product is subjected to gel permeation chromatography (G (PC). The analysis results are shown in Table 1. As a result, a lauroyl oligolactic acid ester (LL-15) having a mass average molecular weight (Mw) of 509 and an average degree of polymerization of lactic acid of 4 was obtained. In addition, dimers, trimers, pentamers, and hexamers were present together with the tetramers. GPC analysis confirmed that the base peak (molecular ion peak) was a hexamer.

(Table_1) Oligolactic acid laurate composition *

*) Analysis was performed using a differential refractive index detector using Waters' GPC, and the solvent was used as the solvent.

(Stability of aqueous solution)

Lauroyl oligolactic acid ester (LL-5) was neutralized using an aqueous sodium hydroxide solution to prepare lauroyl oligolactic acid ester Na (LL-5-Na). The stability of the aqueous solution was evaluated by storing a 1% aqueous solution (pH 7.0) of L L-5-Na at room temperature for 52 days. As a result, the pattern of the GPC chromatogram immediately after the preparation of LL_5-Na and the pattern of the GPC chromatogram after 52 days had hardly changed, indicating that decomposition in an aqueous solution state did not occur. Was confirmed.

(Surface tension of surfactant, critical micelle concentration)

The surface tension and critical micelle concentration (cmc) of the LL_5-Na aqueous solution were measured by the ring method. The measurement temperature was 2 Ot :. As a result of measurement, LL— 5—N a Is, c mc = 0. 1 8% (3. 5 4 X 1 0 - 3 M), was r _cmc = 3 2. 0 mNZm. Further, LL- 5- N aZO. The in l MN a C l, cmc = 0. 0 6% (1. 1 8 X 1 0- 3 M), was _{r cmc = 3 0. 2 mN Zm} . As a comparative example, Measurements in the same way as for a representative Anion surfactants Lau Lil sulfate N a (SD S), cmc = 0. 2 2%, was r _cmc = 3 9. 8mNZm. From the above results, it was found that the oligolactic acid fatty acid ester had lower cmc and surface tension than SDS.

(Penetration)

A 0.2 mm thick, 1 x 1 cm square cotton cloth (Daiwabo, canvas # 6) was used as a test piece. Place 20 cc of the sample aqueous solution in a 50 cc volume beaker, hold the test piece kept at 30 ± 1 C and 60% relative humidity at both ends of the tweezers, gently drop it on the liquid surface, and drop it on the sample solution surface. From the moment the cloth touched, the stopwatch was pressed and timed, and the number of seconds until the cloth completely separated from the liquid surface due to natural settling and settled was read. Incidentally, the sample, the sodium salt of oligo lactic acid fatty acid E ester (LL one 5) (- N a), Anmoniumu salt was used _{- - (Mg) (NH 4} ), arginine (_A rg), magnesium salt. Table 12 shows the measurement results.

(Table 1 2) Penetration

*) Ethanoloxide ラウ mol adduct of lauryl alcohol

Four (Lime soap dispersing power)

Into a 30 ml test tube, add 0.55% aqueous sodium oleate solution (5 tsp) and an arbitrary amount of the sample aqueous solution (starting with a small amount at first), and add 10 cc of model hard water to a total volume of 30 cc. did. The operation of stoppering, inverting, and shaking was repeated 20 times, and then allowed to stand for 30 seconds to observe whether or not the particles were uniformly dispersed. If it is dispersed, it will be uniformly cloudy. The amount of the sample aqueous solution at which a fine precipitate began to appear was determined. Table 13 shows the measurement results.

As a model hard _{water, C a C l 2 6 0} % and Mg C l ₂ and 40% mixed C a C_〇 ₃ hard water was adjusted to a total of 0.1% in terms of (C a C l ₂ - 2 H ₂ 0 8 8 2 1 g and Mg C 1 ₂ · 6 H ₂ 〇 0.81 32 g were added to make 100 cc). Precipitation occurred immediately when no sample was added or when soaps such as sodium laurate were added.

(Table 1 3) Lime soap dispersing power

(Detergency)

Lauroyl oligolactic acid ester Na (LL-5-Na) was diluted with ion-exchanged water to obtain aqueous solutions of 0.05 wt%, 0.1 wt% and 0.2 wt%, respectively, in terms of solid content. Prepared. As a comparative example, lauroyl lactate An aqueous solution of the same concentration was prepared using steal. The detergency of these aqueous solutions

Evaluation was made on the washing condition of the dish to which the salad oil was applied. Table 14 shows the results.

[Detergency Evaluation Method]; previously prepared that a salad oil Western dishes were coated with 0. 5 gZ2 0 cm ² of percentage, this sample solution (2 0 ° C)

Soaked for 15 minutes. Check the water repellency immediately after lifting the dish from the aqueous solution

It was judged with the naked eye.

Judgment criteria: 〇 ... Salad oil is completely dropped

△ ····· Slight salad oil remains

X · · · · Salad oil remains

(Table 1 4) Detergency

(B〇D, COD)

Using a 0.1% aqueous solution of L L—5—Na, BOD (measurement method: JISK 0102) and COD (measurement method: JISK0102) were measured. As a result, the COD was 110 mgZL and the BOD was 350 mgZL, indicating excellent biodegradability.

(Emulsifying power)

The emulsifying power of LL-5-Na to oily fragrance was evaluated. Table 15 shows the composition and evaluation results. As a result, oligo-lactic acid ester salt Had the same emulsifying power as nonionic surfactants <

(Table 1-5) Emulsifying power

*) C12-14 Secondary alcohol ethylene oxide 12 mol adduct

(Example 1)

Using the Na salt of lauroyl oligolactic acid ester (LL-5-Na) obtained in Production Example 1, the following dishwashing detergent for vegetables was prepared (pH 7.0). This composition showed good foaming, was excellent in detergency against oil stains, and was not irritating to hands.

(Examples of tableware and vegetable detergent formulation)

Polyoxetylene lauryl sulfate Na (average number of moles added) 3 20% LL-5-Na 5% Polyoxyethylene lauryl ether (average number of moles added 5) 5% Coconut fatty acid diethanolamide 3% lauryl dimethyl Aminoxide 3% paratoluenesulfonic acid Na 2% Benzoic acid Na

PH adjuster

water (Example 2)

Using the triethanolamine salt of lauroyl oligolactic ester (LL-15-TEA) obtained in Production Example 1, the following shampoo composition was prepared (PH 6.0). This composition showed creamy foam, no squeaky feeling of the hair after washing, and no irritation to the skin.

(Example of shampoo formulation)

Polyoxyethylene lauryl sulfate Na (average number of moles added 3) 15% LL-5-TEA 5%

N-lauroyl-jQ-alanine Na salt 1% Coconut fatty acid diethanolamide 3% Cationized cellulose 1% Propylene dalicol 5% PH regulator

water

(Example 3)

Using the potassium salt of lauroyl oligolactic acid ester (LL-5-K) obtained in Production Example 1, the following body soap composition was prepared (pH 7.0). The composition exhibited creamy lather, fast rinsing, good refreshing feeling after rinsing, and no irritation to the skin.

(Example of body soap formulation)

Coconut fatty acid potassium 10% LL-5-K 5% Coconut fatty acid genoleamide 5% Propylene glycol 5% Hydroxypropyl methylcellulose 1% Spice

pH adjuster

Water Industrial potential

As described above, according to the present invention, oligomer type surfactant having high safety, low skin irritation, excellent performance as a surfactant, particularly excellent in detergency and emulsifying power, and having low foaming property Agent can be provided. Since this surfactant has high safety and excellent detergency, it can be used as various cleaning agents for foods, fibers, skin, hair, hard surfaces, etc., as well as for electronic parts, metals, It can be widely used as industrial detergents such as ceramics. It can also be used as an emulsifier, dispersant, antistatic agent, fiber treatment agent, and the like.

Claims

The scope of the claims

1. An oligomer type surfactant comprising an oligolactic acid fatty acid ester represented by the following general formula (1) or a salt thereof.

(In the formula, R is an alkyl or alkenyl group having 7 to 23 carbon atoms, Μ is selected from a hydrogen atom or an alkali metal, an alkaline earth metal, an alkanolamine, an ammonia, a basic amino acid, and a lower alkylamine. At least one kind, η is 2 to 15.)

2. The oligomer type surfactant according to claim 1, wherein is an alkyl or alkenyl group having 10 to 14 carbon atoms.

3. The oligomer type surfactant according to claim 1, wherein the average n is 3 to 5.

4. The oligomer type I surfactant according to any one of claims 1 to 3, which is obtained by an esterification reaction between a fatty acid having 8 to 24 carbon atoms and an oligolactic acid.

5. An oligomer type surfactant composition, wherein the content of the oligolactic acid fatty acid ester represented by the formula (1) or a salt thereof according to any one of claims 1 to 4 is 30% by mass or more.

6. A detergent composition wherein the content of the oligomer type surfactant composition according to claim 5 is 0.1 to 60% by mass.

7. The oligomer type surfactant composition according to claim 5, 0.1 to 60% by mass, an anionic surfactant and a Z or nonionic surfactant 0.1 to 0.1% A cleaning composition containing 30% by mass.

8. The cleaning composition according to claim 6 or 7, which is used for cleaning foods, dishes, kitchen utensils, or kitchen utensils.

Summary Oligomeric surfactant having high safety, less skin irritation, no unnecessary foaming, and excellent emulsifying power and washing power, a surfactant composition containing the same, and the surfactant It is a cleaning composition containing a cleaning composition. The oligomer type surfactant contains an oligolactic acid fatty acid ester represented by the formula (1) or a salt thereof, and a surfactant composition containing 30% by mass or more of the ester is used for food, fiber, skin, Used as a cleaning agent for hair and hard surfaces.

R, CO (1)

(Wherein, R is an alkyl or alkenyl group having 7 to 23 carbon atoms, M is a hydrogen atom or at least one selected from alkali metals, alkaline earth metals, alkanolamines, ammonia, basic amino acids, and lower alkylamines. And n is 2 to 15.