JP2002265989A - Nonionic surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a surface active agent which utilizes inexpensive 1-11C aliphatic alcohols having not utilized heretofore and can be used in the field of detergents and the like. SOLUTION: The nonionic surface active agent is represented by formula (1): RO-(AO<1> )m -(AO<2> )n -H [wherein R is a 1-11C aliphatic hydrocarbon group; AO<1> is an oxypropylene (PO) group and/or an oxybutylene (BO) group; (AO<2> )n is a polyoxyalkylene group obtained by the homopolymerization of ethylene oxide (EO) or the copolymerization of EO with a >=3C alkylene oxide; and m and n are each a number of 1 or more, provided that x representing the number of carbons in R, p representing the number of PO groups in (AO<1> )m , and b representing the number of BO groups in (AO<1> )m are numbers which meet formula (2): 8<=(x+0.4×p+0.8×b)<=13]. A detergent composition comprises this nonionic surface active agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a nonionic surfactant and a cleaning composition containing the same.

[0002]

2. Description of the Related Art In the field of detergents and the like, alkylene oxide adducts of alcohols having 12 to 18 carbon atoms or alkylphenols have been conventionally used as nonionic surfactants. In recent years, concerns have been raised about the so-called endocrine problem that nonylphenol may have a pseudohormonal effect on living organisms and disrupt the endocrine system. Alternatives to alkylene oxide adducts are being actively sought. For this reason,
The demand for aliphatic alcohols having 12 to 18 carbon atoms is tight,
It is expected to skyrocket, and the relatively cheap carbon number 1
There has been a demand for the development of nonionic surfactants using aliphatic alcohols as raw materials.

[0003] In the field of detergents and the like, conventionally, the number of carbon atoms is 1 to 4;
A low molar addition product of an aliphatic alcohol of ethylene oxide or propylene oxide is used as a solvent or the like, but an alkylene oxide addition product of an aliphatic alcohol having 1 to 11 carbon atoms has an interfacial tension lowering ability, permeability, emulsifying property, etc. Was not used as a nonionic surfactant because its performance as a surfactant was insufficient.

[0004]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide an inexpensive aliphatic alcohol having 1 to 11 carbon atoms which has been rarely used in the field of cleaning agents and the like. It is to provide a possible surfactant. Therefore, the present inventors have studied diligently, and have found that carbon atoms which have not been used as a raw material for nonionic surfactants so far.
Completed the present invention by finding that a compound obtained by polymerizing an oxypropylene group and / or an oxybutylene group, and further a group containing an oxyethylene group with a specific structure to an aliphatic alcohol having a specific structure shows high surface activity. did.

[0005]

That is, the present invention is a nonionic surfactant represented by the following general formula (1). RO- (AO ¹ ) _m- (AO ² ) _n -H (1) wherein R represents an aliphatic hydrocarbon group having 1 to 11 carbon atoms, and AO ¹ represents an oxypropylene group and / or an oxybutylene group Wherein (AO ² ) _n represents a polyoxyalkylene group formed by homopolymerization of ethylene oxide or copolymerization of ethylene oxide with an alkylene oxide having 3 or more carbon atoms, and m and n each represent a number of 1 or more. However, the number of carbon atoms of R x, (AO ¹⁾ a number of oxypropylene groups in the _m p, the number of oxybutylene groups in (AO ¹⁾ _m b
X, p and b are numbers that satisfy the following expression (2). 8 ≦ (x + 0.4 × p + 0.8b) ≦ 13 (2)｝ The present invention is a cleaning composition containing the nonionic surfactant represented by the general formula (1).

[0006]

DETAILED DESCRIPTION OF THE INVENTION The surfactant of the present invention has 1 carbon atom.
An oxypropylene group and / or an oxybutylene group are added to the aliphatic alcohols of the formulas (1) to (11) so as to satisfy the above-mentioned formula (2), and an oxyethylene group or an oxyalkylene group containing an oxyethylene group is further added thereto It is addition polymerized.

In the general formula (1), R represents 1 to 1 carbon atoms.
Represents one aliphatic hydrocarbon group. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and a cycloalkyl group. Examples of the alkyl group having 1 to 11 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, Hexyl, heptyl, secondary heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl,
Secondary decyl, undecyl, secondary undecyl and the like can be mentioned.

The alkenyl group having 2 to 11 carbon atoms includes, for example, vinyl, allyl, propenyl, isopropenyl,
Butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl,
Decenyl, undecenyl and the like.

Examples of the cycloalkyl group having 5 to 11 carbon atoms include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl and the like. Among these, an alkyl group having 4 to 11 carbon atoms or 6 to 11 carbon atoms
Is preferred, and an alkyl group having 8 to 11 carbon atoms is more preferred.

In the general formula (1), AO ¹ represents an oxypropylene group and / or an oxybutylene group. m represents a number of 1 or more, preferably 1 to 15, more preferably 1 to 12, and most preferably 1 to 6. Further, the number of carbon atoms of R is x, the number of oxypropylene groups in (AO ¹ ) _m is p,
(AO ¹ ) Assuming that the number of oxybutylene groups in _{m is} b,
x, p and b are numbers that satisfy the following equation (2). 8 ≦ (x + 0.4 × p + 0.8 × b) ≦ 13 (2) (where x represents a number of 1 to 11, p and b represent a number of 0 or more. However, the sum of p and b Is m in the general formula (1)
And the number is one or more. )

In the present invention, an oxypropylene group and / or an oxybutylene group is added to a hydrocarbon group having 1 to 11 carbon atoms so as to satisfy the condition of formula (2) to increase the hydrophobicity of the hydrocarbon group. However, a structure having a favorable balance between hydrophilicity and hydrophobicity was obtained by further adding a group containing an oxyethylene group as a hydrophilic portion to the structure, and as a result, it was possible to exhibit excellent surface activity. Things. Therefore, in the above equation (2), (x + 0.4 × p
When + 0.8 × b) is smaller than 8 or larger than 13, various properties when used as a surfactant for detergents, that is, sufficient permeability, emulsifying property, detergency, etc. are sufficient. Does not show good performance.

In the general formula (1), (AO ² ) _n is most preferably a homopolymer of ethylene oxide.
It may be a polyoxyalkylene group formed by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms. In this case, examples of the alkylene oxide having 3 or more carbon atoms include propylene oxide, butylene oxide, alpha-olefin oxide having about 5 to 18 carbon atoms, and styrene oxide. (AO
² ) When _n is a polyoxyalkylene group formed by copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, the form of copolymerization is not particularly limited, and block polymerization, random polymerization, or block polymerization may be used. And random polymerization may be used, but random polymerization is preferred when detergency is important, and block polymerization is preferred when low foaming is important. The ratio of oxyethylene groups in (AO ² ) _n is preferably at least 50 mol%, more preferably at least 70 mol%, and
Most preferably, it is at least mol%. n represents one or more numbers. n is preferably 1 to 25, more preferably 4 to 20, and most preferably 5 to 15.

The method for producing the nonionic surfactant of the present invention is not particularly limited. For example, starting from an aliphatic alcohol having 1 to 11 carbon atoms corresponding to R in the general formula (1) as a starting material, propylene oxide and / or butylene oxide are reacted in a molar amount, and then ethylene oxide or ethylene oxide and ethylene oxide having 3 or more carbon atoms. The nonionic surfactant of the present invention can be obtained by reacting n moles of the mixed alkylene oxide with the alkylene oxide. Also,
As a starting material, a compound in which propylene oxide is added to an aliphatic alcohol having 1 to 11 carbon atoms may be used. Examples of such a compound to which propylene oxide is added include, for example, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, and propylene glycol monotert-butyl ether. Propylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, and the like.

The surfactant represented by the general formula (1) is particularly useful as a detergent composition containing the surfactant as a cleaning active ingredient. Although the detergent composition of the present invention can contain the surfactant represented by the general formula (1) alone, it is constituted as a composition obtained by adding various additives to the detergent according to the purpose of the detergent. Is done. Examples of such additional components include nonionic surfactants such as alcohol ethoxylates, alkylphenol ethoxylates, alkylpolyglycosides, and alkanolamides; alkylbenzene sulfonates, alkyl sulfates,
Alkyl ether sulfate, α-olefin sulfonate, acylated isethionate, acylated amino acid,
Anionic surfactants such as acylated polypeptides, fatty acid soaps and alkyl ether carboxylates; Cationic surfactants such as stearyltrimethylammonium, cetyltrimethylammonium, polydimethyldiallylammonium; alkylcarbobetaines, amidopropylcarbobetaines, imidazo Amphoteric surfactants such as linium betaine; semipolar surfactants such as alkylamine oxide; ethylene glycol, propylene glycol,
Hydrotropes such as polyethylene glycol, polyalkylene glycol alkyl ether, ethanol, paratoluenesulfonic acid; ethylenediaminetetraacetate (EDTA), hydroxyethylethylenediaminetriacetic acid (HEDTA), nitrilotriacetic acid (NTA), diethylenetriaminepentaacetic acid (DTPA) Metal such as aminocarboxylic acids such as, aspartic acid-N, N-diacetic acid, N-hydroxyethyliminodiacetic acid or salts thereof, and oxycarboxylic acids such as citric acid, gluconic acid, glycolic acid, tartaric acid or salts thereof Ion sequestering agents; alkali builders such as magnesium sulfate, sodium sulfate (Glauber's salt), sodium carbonate, sodium bicarbonate, potassium carbonate, sodium silicate, potassium silicate; sodium hydroxide, potassium hydroxide, etc. Alkali; monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3- Alkanolamines such as propanediol and aminoethylethanolamine; dispersants such as sodium polyacrylate and sodium acrylate-olefin copolymer; preservatives, thickeners, enzymes, antibacterial agents, humectants,
Flavors, pigments and the like can be contained.

The detergent composition of the present invention containing the above-mentioned nonionic surfactant can be constituted by blending appropriate additives according to the object to be cleaned and the purpose of cleaning. Can be used for For example,
Cleaning agent for clothing for washing clothes, etc .; Cleaning agent for hair or body for washing hair, skin, nails, eyes, etc .;
Cleaning agent for kitchen to wash vegetables, etc .; Cleaning agent for house to wash walls, floors, tatami, furniture, ceilings, roofs, etc .; Washing toilets, bathtubs, bathrooms, ventilation fans, around microwave ovens, around sinks, around pipes, etc. Hard surface cleaners; automatic dishwasher cleaners; textile cleaners; and industrial cleaners for cleaning industrial products such as automobiles, aircraft, vehicles, and mechanical parts.

In this case, the amount of the nonionic surfactant used in the cleaning composition is not particularly limited, and varies depending on the cleaning application. It is about 20% by weight. In addition, the detergent composition of the present invention containing the nonionic surfactant is equivalent to or better than the conventional detergent containing an alkylene oxide adduct of an aliphatic alcohol having 12 to 18 carbon atoms. Show performance.

Further, the nonionic surfactant of the present invention can be used in all fields in which nonionic surfactants have been conventionally used. These areas include:
For example, humectants, emulsifiers, dispersants, solubilizers, humectants,
As a penetrant, spreading agent, foaming agent, antifoaming agent, leveling agent, rust inhibitor, antistatic agent, friction modifier, etc. Examples include synthetic resin additives and lubricating oil additives, and the nonionic surfactant of the present invention can be suitably used in these fields.

[0018]

EXAMPLES The present invention will be described more specifically with reference to the following examples. In the following examples, parts and percentages are by weight unless otherwise specified. EO is an oxyethylene group, PO
Represents an oxypropylene group, BO represents an oxybutylene group, and (EO) ₈ / (PO) ₂ represents ethylene oxide 8
And a polyoxyalkylene group obtained by random polymerization of 2 moles of propylene oxide.

The nonionic surfactants of the present invention 1 to 10 and comparative products 1 to 6 having the structures shown in Table 1 were synthesized by a conventional method. The surface tension of each 0.1% aqueous solution of each surfactant at 25 ° C. was measured by the Wilhelmy method. Table 1 shows the results.

[0020]

[Table 1]

These inventive products 1 to 10 and comparative products 1 to
Using the nonionic surfactant No. 6, various detergent compositions having the following formulations were prepared, and the following various detergency tests were performed to evaluate the detergency.

(I) Detergency test 1: Immersion test Alkaline detergent formulation: Surfactant of the present invention or comparative product 9% Trisodium citrate 3% Sodium hydroxide (40%) 4% Water Remainder The alkaline cleaning composition was tested by the following method. (1) About 1 g of the following artificial stain was uniformly applied to a 10 cm square glass plate and left for 24 hours. Artificial soil: a mixture of 50 parts of margarine / 52 parts of flour / 2 parts of oleic acid (2) A 0.2% aqueous solution of the above alkaline detergent composition is prepared, and the glass obtained in (1) to which the soil is attached is attached. The plate was immersed in this aqueous solution, and after 5 minutes, ultrasonic cleaning was performed for 30 seconds. (3) The glass plate was taken out, rinsed several times with accumulated water, drained, air-dried, and the surface condition was observed. These operations were performed on the alkaline detergent compositions using the nonionic surfactants of the present invention products 1 to 10 and comparative products 1 to 6, respectively.

The evaluation of these detergency tests was carried out in five stages as follows. 5: Clean surface without residual dirt. 4: Almost no stain remains, but poor in rinsing properties. 3: Less than 5% of the total area remains. 2: Soil of 5 to 10% of the total area remains. 1: Almost no cleaning.

(Ii) Detergency test 2: Leanut test Kitchen detergent formulation: Surfactant of the present invention or comparative product 8% Palm oil alcohol EO 3 mol adduct sulfate ester Na salt 18% Polyoxypropylene chloride (25 ) Methyl 3% Diethylammonium Palm fatty acid diethanolamide 11% Palm alkyldimethylamine oxide 2% Others (Na-p-toluenesulfonate, sodium hydroxide, 17% ethanol, propylene glycol) Water balance

With respect to the kitchen cleaning composition of the above formula,
Detergency was evaluated in accordance with JIS K3370, a synthetic detergent test method for kitchens. That is, 10 g of tallow, 10 soybean oils
g, 60 mL of chloroform and 0.1 g of oil red, the slide glass was immersed in a mixed solution of 0.1 g of the slide glass. % Aqueous solution was used to perform cleaning with a Rinatsu detergency tester. The residual stain was extracted with 100 mL of chloroform from each set of washed slide glasses, the weight of the extracted components was measured, and the detergency was calculated by the following equation. Detergency ratio (%) = 100 × (E S -E W) / E S E S: prewashed chloroform extractables weight E _W: weight of the cleaning after chloroform extractables

(Iii) Detergency test 3: Cleaning brush test For the same kitchen detergent composition as in (ii) above, a mixture of 100 parts of margarine, 104 parts of flour and 4 parts of oleic acid was placed in a porcelain dish having a diameter of 21 cm. Was applied to the surface of the sample, and left overnight in a constant temperature bath at a temperature of 22 ° C. and a humidity of 50%, and a detergency test was performed in the following manner. The water used in the test was artificial hard water having a calcium concentration of 50 ppm.

That is, the kitchen cleaning composition was diluted at a ratio of 0.75 g to 1 liter of water at 25 ° C. to obtain a detergent liquid. 1 in a 30 cm diameter plastic wash tub
Liter of the above-mentioned detergent solution, and 500 mL from a height of 75 cm above the liquid level into a 500 mL separating funnel.
Was dropped into the center of a plastic tub to foam the detergent solution. In the foamed detergent solution, a diameter of 4.5 was obtained.
The contaminated dish was rubbed and washed 10 times with a 1 cm washing brush, rinsed with running water for 10 seconds, and dried. For the dried dishes, the residual oil was evaluated visually and by the tactile sensation of the fingers. These operations were performed according to the present invention products 1 to 10 and comparative product 1
This was carried out on kitchen detergent compositions using each of Nos. 6 to 6 nonionic surfactants. The test results were expressed as the number of dishes having no oil residue after drying.

(Iv) Detergency test 4: Metal cleaning test Detergent composition formulation: Surfactant of the present invention or comparative product 0.02% Sodium metasilicate 0.18% Water Remainder About the above detergent composition , Length 10cm, width 10c
A detergency test was carried out in the following manner using a test piece made of stainless steel having a thickness of 2 mm and a thickness of 2 mm to which about 100 mg of machine oil was adhered as a contamination test piece. That is, a contaminated test piece was added to the above cleaning composition at 25 ° C. for 3 hours.
And then dried at 105 ° C. for 2 hours.
The washing rate of the machine oil was calculated by the following formula by measuring the weight of the test piece before the machine oil was attached and the weight of the contaminated test piece to which the machine oil was attached before and after washing. Cleaning rate (%) = 100 × (M _S −M _W ) / (M _S −M _O ) M _O : Weight of test piece M _S : Weight before cleaning of contamination test piece M _W : After cleaning of contamination test piece Weight of

(V) Detergency test 5: Cotton cloth detergency test An artificial sebum stain (myristic acid 8.
4%, oleic acid 8.4%, tristearin 8.4%,
Triolein 8.4%, cholesterol 4.4%, cholesterol stearate 1.0%, paraffin 5.5
%, 5.5% squalene, 49.5% of cotton clay and 0.5% of carbon black) with a sponge to adjust the surface reflectance to 25 ± 2%. Was prepared.

The surfactants of the present invention and the comparative product were dissolved in tap water (hardness: 48 ppm in terms of calcium carbonate) to prepare 0.05% aqueous solutions, and respective aqueous detergent solutions were prepared. Using a Turgot meter, five cotton cloths contaminated with the artificial sebum dirt, each cut into 5 cm squares, were simultaneously washed with 800 mL of each of the above cleaning agent aqueous solutions.
The washing temperature was 25 ° C., the washing time was 10 minutes, and thereafter, rinsing with 800 mL of tap water for 3 minutes was repeated twice. Thereafter, the cleaning rate was calculated by the following equation. Detergency ratio (%) = 100 × (R W -R S) / (R O -R S) R O: reflectance of cotton fabric before pollution (%) R _S: reflectance before washing soiled cloth (% ) R _W: the reflectance (%) or more test after washing soiled cloth conducted four times with the same detergent solution, it was evaluated by the average value. These operations were performed on the detergent aqueous solution using each of the nonionic surfactants of the present invention products 1 to 10 and comparative products 1 to 6. Table 2 shows the evaluation results obtained from the above various detergency tests.

[0031]

[Table 2]

A detergent composition comprising an aliphatic alcohol having 11 or less carbon atoms as a starting material and a nonionic surfactant of the present invention within the range of the general formula (1) (Products 1 to 5 of the present invention)
10) In various detergency tests, Comparative Examples 1 to 4 containing a non-ionic surfactant (using an aliphatic alcohol having 12 carbon atoms) in which an aliphatic alcohol having 12 carbon atoms was used as a starting material were used. Detergency equivalent to or higher than that of the agent composition. On the other hand, the detergent compositions using aliphatic alcohols having 11 or less carbon atoms but containing comparative products 5 and 6 which are out of the range of the general formula (1) are better than the detergent compositions of the present invention. Detergency was poor.

[0033]

The effect of the present invention is to provide a nonionic surfactant which exhibits excellent detergency by using an aliphatic alcohol having 11 or less carbon atoms, which has not been used as a surfactant until now. It is in.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Kaoru Komiya 7-35 Higashiogu, Arakawa-ku, Tokyo Asahi Denka Kogyo Co., Ltd. F-term (reference) 4D077 AB10 AC05 BA02 BA03 BA15 DC19Z DD29Y DE02Y 4H003 AB31 AC08 AC13 AC15 AC23 AC24 DA01 DA02 DA05 DA11 DA14 DA17 DA19 EA21 EB04 EB08 EB19 EB22 ED02 FA21

Claims (4)

[Claims] 1. A nonionic surfactant represented by the following general formula (1). RO- (AO ¹ ) _m- (AO ² ) _n -H (1) wherein R represents an aliphatic hydrocarbon group having 1 to 11 carbon atoms, and AO ¹ represents an oxypropylene group and / or an oxybutylene group Wherein (AO ² ) _n represents a polyoxyalkylene group formed by homopolymerization of ethylene oxide or copolymerization of ethylene oxide with an alkylene oxide having 3 or more carbon atoms, and m and n each represent a number of 1 or more. However, the number of carbon atoms of R x, (AO ¹⁾ a number of oxypropylene groups in the _m p, the number of oxybutylene groups in (AO ¹⁾ _m b
Where x, p and b are numbers that satisfy the following equation (2). 8 ≦ (x + 0.4 × p + 0.8 × b) ≦ 13 (2)｝ 2. In the general formula (1), (AO ² ) _n
2. The nonionic surfactant according to claim 1, wherein the content of oxyethylene groups in the nonionic surfactant is at least 50 mol%. 3. The nonionic surfactant according to claim 1, wherein in the general formula (1), R is an aliphatic hydrocarbon group having 4 to 11 carbon atoms. 4. A cleaning composition containing a nonionic surfactant represented by the following general formula (1). RO- (AO ¹ ) _m- (AO ² ) _n -H (1) wherein R represents an aliphatic hydrocarbon group having 1 to 11 carbon atoms, and AO ¹ represents an oxypropylene group and / or an oxybutylene group Wherein (AO ² ) _n represents a polyoxyalkylene group formed by homopolymerization of ethylene oxide or copolymerization of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and m and n each represent a number of 1 or more. However, the number of carbon atoms of R x, (AO ¹⁾ a number of oxypropylene groups in the _m p, the number of oxybutylene groups in (AO ¹⁾ _m b
Where x, p and b are numbers that satisfy the following equation (2). 8 ≦ (x + 0.4 × p + 0.8 × b) ≦ 13 (2)｝