JPH11349987A - Nonionic surfactant and detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject nonionic surfactant that exhibits excellent detergency, reduced skin irritation, lowered smell, good handleability, foam-breaking properties and solubility in water and is useful as a detergent by specifying the composition ratio of alcohol alkoxylates based on their substituents. SOLUTION: This nonionic surfactant comprises a compound (A) represented by the formula (R<1> and R<2> are each an alkyl where the total carbon number is 7-29 and R<1> <=R<2> ; M is a 2-6C alkylene; N is a 2-4C alkylene; m is 1-3; n is the average addition molar number of the alkylene oxide, namely 1-20) and the content of the compound bearing methyl as R<1> is 30-90 mol.% and that of the compound bearing alkyl of 2 or more carbon atoms as R<1> is 70-10 mol.%, and further, satisfies the relation represented by formula II [(m+n)max is the addition molar number of the alkylene oxide of the largest percent by weight; Yi is the proportion in % by weight, when the addition molar number of (m+n) is I].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel nonionic surfactant and a detergent composition containing the nonionic surfactant as a cleaning active ingredient.

[0002]

2. Description of the Related Art The present inventors have developed a novel substance in which a higher secondary alcohol alkoxylate obtained by an addition reaction of an olefin having 8 to 30 carbon atoms with a (poly) alkylene glycol is further reacted with an alkylene oxide. A higher secondary alcohol alkoxylate adduct obtained was obtained, and it was further discovered that this higher secondary alcohol alkoxylate adduct had excellent performance as a cleaning agent, and a patent application was filed earlier (Japanese Patent Application No. Hei 8 (1994)). -327365 and Japanese Patent Application No. 8-327366).

[0003]

SUMMARY OF THE INVENTION The present invention provides a novel nonionic surfactant having a narrow distribution of alkoxylation among the above-mentioned higher secondary alcohol alkoxylate adducts, and a novel nonionic surfactant containing this nonionic surfactant. It is an object of the present invention to provide a cleaning composition that is

[0004]

That is, the present invention provides a compound represented by the following general formula (1):

[0005]

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Wherein R ¹ and R ² are alkyl groups, the total number of carbon atoms of which is 7 to 29, and R ¹ ≦ R ² , and M is an alkylene group having 2 to 6 carbon atoms. , M is 1
N is an alkyl group having 2 to 4 carbon atoms, n indicates the number of moles of alkylene oxide added,
20) is a nonionic surfactant,
(1) Component (A) in which R ¹ is a methyl group 30 to 90 mol% and component (B) in which R ¹ is an alkyl group having 2 or more carbon atoms
(2) The alcohol in which m and n are 0 is 2% by weight or less, and (3) When the added mole number with the largest weight% is (m + n) max, The formula:

[0007]

(Equation 2)

(Wherein, Yi is a proportion (% by weight) of i moles of (m + n) added moles) is a nonionic surfactant.

[0009] The present invention is also a detergent composition containing the above-mentioned nonionic surfactant.

Hereinafter, the numerical value represented by the above equation is referred to as a "narrow value". This narrow value is the same as that described in, for example, JP-A-3-185096.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The nonionic surfactant of the present invention comprises
A higher secondary alcohol alkoxylate adduct represented by the general formula (1), which satisfies the following requirements.

(1) Component (A) 3 wherein R ¹ is a methyl group
0 to 90 mol% and 70 to 10 mol% of component (B) in which R ¹ is an alkyl group having 2 or more carbon atoms. Above all,
It is preferable that the component (A) comprises 40 to 80 mol% and the component (B) 60 to 20 mol%.

(2) The alcohol in which m and n are 0 is 2% by weight or less. Of these, those having an alcohol content of 1% by weight or less are preferable, and those having no residual alcohol are particularly preferable.

(3) The narrow value is 55% by weight or more.
Above all, the narrow value is more than 60% by weight, especially 80% by weight
The above are preferred.

The above-mentioned nonionic surfactant of the present invention further comprises a higher secondary alcohol alkoxylate obtained by an addition reaction of an olefin having 8 to 30 carbon atoms with a (poly) alkylene glycol, and further having a higher secondary alcohol alkoxylate having 2 to 4 carbon atoms. Obtained by reacting with an alkylene oxide. The olefin having 8 to 30 carbon atoms has one double bond and has 8 to 30 carbon atoms.
It is preferably an aliphatic hydrocarbon having 10 to 20 and may be linear or branched. The position of the double bond is not particularly limited, and may be at the α-position or the inner position. Representative examples of the olefin having 8 to 30 carbon atoms (hereinafter, simply referred to as “olefin”) include octene,
Decene, dodecene, tetradecene, hexadecene, octadecene, eicosene and the like can be mentioned. These can be used alone or in combination of two or more.

As the olefin raw material, an ethylenically unsaturated hydrocarbon having a double bond at the α-position (α-olefin)
Is generally used, but since the inner olefin is generally more thermodynamically stable than the α-olefin, isomerization of the α-olefin to the inner olefin occurs during the addition reaction. In addition, since this addition reaction is generally carried out by circulating unreacted olefins and the like,
The olefin component undergoes an addition reaction with the (poly) alkylene glycol as a mixture of the α-olefin and the inner olefin.

The (poly) alkylene glycol is
General formula (2): HO (MO) mH (2) (wherein M is an alkylene group having 2 to 6 carbon atoms and m is a number of 1 to 3) There are, as typical examples, monoethylene glycol, diethylene glycol, triethylene glycol, monopropylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol. , 1,4-butanediol, 1,6-hexanediol and the like. Of these, monoalkylene glycols such as monoethylene glycol and monopropylene glycol are preferably used.

The method of producing the corresponding higher secondary alcohol alkoxylate (hereinafter simply referred to as "alcohol alkoxylate") by subjecting the above-mentioned olefin and (poly) alkylene glycol to an addition reaction is not particularly limited. For example, it can be produced by the method described in JP-B-61-51570, JP-A-3-148233, JP-A-9-52856 and the like.
As the catalyst to be used, a known acidic catalyst such as a strongly acidic ion exchange resin, crystalline aluminosilicate, dodecylbenzenesulfonic acid, or the like can be used.

For example, according to the method described in JP-A-9-52856, a crystalline metallosilicate is used as a catalyst with an olefin and a (poly) alkylene glycol at 50 to 250 ° C. in the presence or absence of a solvent. It is preferably obtained by performing an addition reaction at 100 to 200 ° C. The pressure may be either normal pressure or pressurized, but is usually appropriately selected from the range of normal pressure to 20 kg / cm ² . As the solvent, nitromethane, nitroethane, nitrobenzene, dioxane, ethylene glycol dimethyl ether, sulfolane, benzene, toluene, xylene, hexane, cyclohexane, decane, paraffin, and the like can be used. The molar ratio of (poly) alkylene glycol to olefin (olefin / (poly) alkylene glycol) can be appropriately determined without particular limitation, but is usually 0.05 / 1 to 20/1, and is preferably 0.05 / 1 to 20/1. 0.1 / 1 to 10/1. The amount of the catalyst used is usually 0.1 to 10 of the starting olefin.
0% by weight, preferably 0.5 to 50% by weight.

After the reaction, after separating the catalyst, the reaction solution is separated into an olefin phase and a (poly) alkylene glycol phase, and the olefin phase is distilled to distill off unreacted olefin and recover the alcohol alkoxylate. The alcohol alkoxylate from which the unreacted olefin has been separated may be used as it is in the next reaction, but it is usually preferable to rectify and use the recovered alcohol alkoxylate. Since the rectification conditions vary depending on the starting materials used and the like, they cannot be specified unconditionally, but it is preferable to remove at least impurities such as an olefin polymer by-produced during the reaction.

The addition reaction between the olefin and the (poly) alkylene glycol can be carried out according to a generally used method such as a batch reaction or a continuous reaction. When a batch reactor is used, after the reaction is completed, the catalyst is separated from the reaction solution by a method such as centrifugation or filtration, and then, after the above phase separation, the desired alcohol alkoxylate is recovered from the olefin phase by distillation or the like. . Unreacted raw materials can be used for the next reaction. When a continuous reactor is used, any of a fluidized bed type, a fixed bed type, and a stirred tank type may be used, and the reaction proceeds while appropriately circulating unreacted raw materials. Separation of the catalyst, recovery of the alcohol alkoxylate, and the like are the same as in the case of using a batch reactor.

The above-mentioned alcohol alkoxylate has the following general formula (3):

[0023]

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(Wherein R ¹ , R ² , M and m have the same meaning as defined in the general formula (1)). When two or more different (poly) alkylene glycols are used, the group represented by (MO) differs accordingly.

Next, the alcohol alkoxylate of the general formula (3) is further reacted with an alkylene oxide having 2 to 4 carbon atoms to form a higher secondary alcohol alkoxylate adduct (hereinafter simply referred to as "alcohol alkoxylate adduct"). ).

In the alcohol alkoxylate represented by the general formula (3), since the residual amount of the alcohol having m + n = 0 is small, the alcohol alkoxylate represented by the general formula (1) can be obtained by using this as a raw material. The alkoxylate adduct has a small residual amount of alcohol.

The alkylene oxide having 2 to 4 carbon atoms (hereinafter simply referred to as "alkylene oxide") is ethylene oxide, propylene oxide and butylene oxide. These can be used alone or in combination of two or more.

The reaction between the alcohol alkoxylate and the alkylene oxide can be easily carried out by using an alkali catalyst as a catalyst. The molar ratio of the alkylene oxide to the alcohol alkoxylate (alkylene oxide / alcohol alkoxylate) can be appropriately determined without any particular limitation, and is usually 1/1 to 20/1.

Examples of the alkali catalyst include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide; and oxidation of alkaline earth metals. For example, a metal ion-added magnesium oxide, an aluminum-magnesium composite oxide, a carbonate, or the like can be used. The amount of the alkali catalyst to be used is generally 0.01 to 2% by weight, preferably 0.02 to 0.5% by weight, based on the alcohol alkoxylate.
The alkali catalyst may be added in the form of a powder, granules, or an aqueous solution. When an oxide catalyst is used, after the reaction is completed, the catalyst is removed by an operation such as filtration or adsorption.

The reaction temperature is usually 50 to 250 ° C., preferably 100 to 200 ° C. The reaction pressure may be normal pressure or pressurization, and is usually appropriately selected from the range of normal pressure to 20 kg / cm ² . Note that the reaction is preferably performed in an inert gas, for example, a nitrogen atmosphere. Even if solvent is used,
Although it is not necessary to carry out the reaction, the reaction is usually carried out without using a solvent.

The reaction between the alcohol alkoxylate and the alkylene oxide can be carried out according to a generally used method such as a batch reaction or a continuous reaction, as in the case of the production of the alcohol alkoxylate.

The reaction mixture after completion of the reaction can be used as it is. The alkali catalyst in the alcohol alkoxylate adduct may be neutralized with acetic acid or the like before use.

According to the above-mentioned method, the reaction conditions are strictly adjusted as necessary, and an alkylene oxide is added to the alcohol alkoxylate represented by the general formula (3), whereby an alcohol alkoxylate having a narrow value of 55% by weight or more is added. You can get things. Further, the narrowness of the alcohol alkoxylate adduct obtained as described above may be adjusted to 55% by weight or more by rectification or the like.

The nonionic surfactant of the present invention in which the component (A) and the component (B) are within the above range is an alcohol alkoxylate represented by the general formula (3), wherein R ¹ is An alcohol alkoxylate comprising 30 to 90 mol% of an alcohol alkoxylate which is a methyl group and 70 to 10 mol% of an alcohol alkoxylate wherein R ¹ is an alkyl group having 2 or more carbon atoms is prepared. And obtained by reacting

In the preparation of the above-mentioned alcohol alkoxylate of the general formula (3), for example, when 1-dodecene is used as a starting olefin,
Heat treatment of dodecene in the presence of an acid or base catalyst to convert a part of 1-dodecene to innerdodecene, and to obtain a mixture of 1-dodecene and innerdodecene (for example, 25:75 (mol%) )) May be used to carry out the addition reaction. In addition, an α-olefin may be used as a raw material, an unreacted inner olefin may be recovered and circulated, and reacted as a mixture of the α-olefin and the inner olefin.

In the general formula (1), when M = N, the nonionic surfactant of the present invention is represented by the following general formula (4):

[0037]

Embedded image

(Each symbol in the formula is the same as defined in the general formula (1)).

The cleaning composition of the present invention contains the above-mentioned nonionic surfactant in an effective amount, usually at a concentration of 3 to 60% by weight. The nonionic surfactant of the present invention can be used in combination with other known surfactants, for example, primary alcohol alkoxylate, secondary alcohol alkoxylate, anionic surfactant, cationic surfactant, alkanolamine and the like. it can.

Examples of the primary alcohol alkoxylate include, for example, a higher primary alcohol alkoxylate obtained by adding ethylene oxide or ethylene oxide and propylene oxide in an average of 5 to 30 mol to a primary alcohol having 8 to 20 carbon atoms. Can be mentioned. These can be used alone or in combination of two or more.

Examples of the higher secondary alcohol alkoxylate include a secondary alcohol having 8 to 20 carbon atoms, ethylene oxide or ethylene oxide and propylene oxide having an average of 3 to 20 moles added, and a secondary alcohol having 8 to 30 carbon atoms. After addition of an alkylene glycol to the olefin of the above, there may be further mentioned ethylene oxide or an alkoxylate obtained by adding 3 to 20 mol of ethylene oxide and propylene oxide. These can be used alone or in combination of two or more.

Examples of the anionic surfactant include an alkyl sulfate having 10 to 18 carbon atoms, an alkane sulfonate having 10 to 18 carbon atoms, an olefin sulfonate having 10 to 18 carbon atoms, and an alkyl group having 10 to 18 carbon atoms. And alkylbenzenesulfonic acid having an alkyl group or alkenyl group of 10 to 18 carbon atoms (average number of moles of ethylene oxide added: 2 to 7). In addition, the above-mentioned salt means an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an alkanolamine salt and the like. These can be used alone or in combination of two or more.

As the cationic surfactant, for example,
Examples thereof include quaternary ammonium salts and imidazolium salts, and more specifically, monoalkyl (C6 to C24) trimethylammonium salts. These alone,
Two or more kinds can be used in combination.

Examples of the alcohol amine include alkanolamines such as monoethanolamine, diethanolamine, triethanolamine, monopropanolamine, dipropanolamine, and tripropanolamine, and fatty acid amides of these alkanolamines. These can be used alone or in combination of two or more.

The detergent composition of the present invention may contain various additives generally used in the detergent composition, depending on the use and purpose. Representative examples of these additives include polyoxyethylene alkyl ether,
Foaming agents such as fatty acid alkanolamides; hydrotropes such as lower alcohols, polyhydric alcohols, polyethylene glycol and lower aryl sulfonates; sequestering of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, citric acid and metal salts thereof. Agents, fungicides such as benzoic acid, pigments, fragrances, alkaline agents, polishing agents, bleaching agents, enzymes and the like.

The nonionic surfactant of the present invention is used as an active ingredient in industrial detergents, household clothing detergents, kitchen detergents, shampoos, etc., and further as an emulsifier, a suspending agent, etc. can do. Further, the detergent composition of the present invention can be used as an industrial or household detergent.

The cleaning composition containing the nonionic surfactant of the present invention can be used in the form of powder, paste, liquid, and the like.

[0048]

The main effects of the nonionic surfactant of the present invention are listed below.

(A) The nonionic surfactant of the present invention has a narrow addition molar distribution of alkylene oxide, a low odor, and a low irritation.

(B) The nonionic surfactant of the present invention has a low pour point, a low viscosity even at a low temperature, and is excellent in handleability.

(C) The nonionic surfactant of the present invention has excellent penetrating power, and has good foam removal during rinsing.

(D) By using the nonionic surfactant of the present invention, a nongel transparent solution can be obtained in a wide range of aqueous solution concentrations.

[0053]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples.

Example 1 (Preparation of alcohol alkoxylate) 1-dodecene was converted to BEA type zeolite manufactured by PQ (trade name: VALFO)
R CP811 BL-25) at 150 ° C at 5% by weight
For 10 hours in the liquid phase to obtain a dodecene isomer mixture consisting of 25 mol% of 1-dodecene and 75 mol% of innerdodecene.

810 g of this dodecene isomer mixture, 900 g of monoethylene glycol and BEA zeolite (trade name: VALFOR CP 811BL-25, P
100 g) (provided with a stirrer and a reflux condenser)
2,000 ml glass reactor, under nitrogen atmosphere,
The reaction was performed at 150 ° C. for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and the upper separated dodecene phase was separated.
Distilled. After distilling off unreacted dodecene, the pressure was reduced to 2
155 g of secondary dodecanol monoethoxylate (alcohol alkoxylate) was obtained in a boiling point range of 129 to 131 ° C. at mmHg.

In the secondary dodecanol ethoxylate, the proportion of the ethoxylate in which R ¹ is a methyl group in the general formula (3) is 71 mol%, and the remainder is R ¹
Was an ethoxylate having an ethyl group or more. This ratio was determined by NMR analysis.

(Preparation of alcohol alkoxylate adduct) 155 g of the above secondary dodecanol ethoxylate
(0.67 mol) and 0.15 g of sodium hydroxide in a stainless steel autoclave,
The temperature was raised to 60 ° C., and 236 g (5.36 mol) of ethylene oxide were introduced in 3 hours.
After holding at 0 ° C., cooling and purging the internal gas,
Polyethoxylate (alcohol alkoxylate adduct) was obtained as a reaction product. The ethylene oxide addition molar distribution of this polyethoxylate was determined by liquid chromatography. The results are shown in FIG.

Table 1 shows the ratio of component (A) to component (B), the amount of alcohol and the narrow value of this alcohol alkoxylate adduct.

(Performance Evaluation) Penetration wool: 2 according to JIS K-3362-1955
Nippon Woolen 20 oz roller piece 90mm x 10m at 5 ° C
It was measured at an activator concentration of 0.1% by weight using m.

2. Detergency With reference to JIS K-3362, a test was conducted under the following conditions using a stirring type detergency tester (Terg-O-tometer).

Soiled cloth: size 5 cm × 5 cm Soil (weight%): oleic acid 28.3, triolein 15.6, cholesterol oleate 12.2, liquid paraffin 2.5, squalene 2.5, cholesterol 1 0.6, gelatin 7.0, red-yellow earth 29.8, carbon black 0.5 water: tap water temperature: 25 ° C. washing time: washing 5 minutes / rinsing 5 minutes bath ratio: 3 sheets / 1 pot (1 liter) Activator concentration: 0.03% by weight (Detergency evaluation method)
The reflectance of the contaminated cloth and the cleaned cloth after cleaning was measured at three points for each test cloth, and the detergency (%) was calculated from the average value by the following formula.

Detergency (%) = (Rw-Rs) / (Ro-
Rs) (× 100) Here, Rw represents the reflectance of the washed cloth after cleaning, Rs represents the reflectance of the contaminated cloth, and Ro represents the reflectance of the original cloth before the contamination.

3. Skin irritation Soak hands up to wrist for 30 minutes a day in 1% aqueous solution of active agent, 3
After repeating for one day, self-scoring was performed in the next evaluation and the average of five testers was taken.

(Irritation scoring method) Notably rough: 1 point Rough: 3 points No skin roughness: 5 points (Results) Table 2 shows the results.

[0065]

[Table 1]

[0066]

[Table 2]

Example 2 (Preparation of Alcohol Alkoxylate) Dodecene (mixture of 25 mol% of 1-dodecene and 75 mol% of innerdodecene obtained in the same manner as in Example 1) 810
g, monoethylene glycol 900 g and BEA type zeolite (trade name: VALFOR CP 811BL-
25, manufactured by PQ) was charged into a 3000 ml glass reactor equipped with a stirrer and a reflux condenser, and reacted at 150 ° C. for 3 hours under a nitrogen atmosphere. After the completion of the reaction, the reaction solution was cooled to room temperature, and the upper layer of the separated dodecene phase was separated and distilled. After distilling off unreacted dodecene,
Second pressure range of 129 to 131 ° C at a reduced pressure of 2 mmHg
155 g of grade dodecanol monoethoxylate (alcohol alkoxylate) was obtained.

This secondary dodecanol ethoxylate was analyzed by H-NMR to find that the above-mentioned general formula (3)
In the above, the proportion of the ethoxylate in which R ¹ was a methyl group was 71 mol%, and the remainder was an ethoxylate in which R ¹ was an ethyl group or more.

(Preparation of alcohol alkoxylate adduct) As a catalyst, Kyoward 500 (Mg ₆ Al ₂ (O
H) What was calcined at 600 ° C. for 3 hours in a nitrogen atmosphere using ₁₆ CO ₃ .4H ₂ O) was used.

The above secondary dodecanol ethoxylate 1
55 g (0.67 mol) and 0.15 g of the above catalyst were charged into a stainless steel autoclave, and after replacing with nitrogen, 16 g.
The temperature was raised to 0 ° C, and 192 g (4.36 mol) of ethylene oxide
Was introduced in 6 hours, and then for another 1.5 hours at 160 ° C.
After cooling, and purging of the internal gas, polyethoxylate (alcohol alkoxylate adduct) was obtained as a reaction product. The ethylene oxide addition molar distribution of this polyethoxylate was determined by liquid chromatography. The results are shown in FIG.

Table 1 shows the ratio of component (A) to component (B), the amount of alcohol and the narrow value of this alcohol alkoxylate adduct.

(Evaluation of Performance) Evaluation was performed in the same manner as in Example 1.

(Results) Table 2 shows the results.

[Brief description of the drawings]

FIG. 1 is a graph showing the distribution of the number of moles of ethylene oxide added to the alcohol alkoxylate adduct obtained in Examples 1 and 2.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Yoshiyuki Onda 5-8 Nishiburi-cho, Suita-shi, Osaka Nippon Shokubai Co., Ltd.

Claims (2)

[Claims] 1. General formula (1): (Wherein, R ¹ and R ² are alkyl groups, the total number of carbon atoms is 7 to 29, and R ¹ ≦ R ² , M is an alkylene group having 2 to 6 carbon atoms, and m is A number of 1 to 3, N is an alkylene group having 2 to 4 carbon atoms, n represents the number of moles of alkylene oxide added, and is a number of 1 to 20). So, (1) R
30 to 90 mol% of component (A) in which ¹ is a methyl group and 70 to 10 component (B) in which R ¹ is an alkyl group having 2 or more carbon atoms.
(2) the alcohol in which m and n are 0 is 2% by weight or less and (3) the addition mole number with the largest weight% is (m + n) max, the following formula: (Equation 1) (Wherein, Yi is a ratio (% by weight) of i moles of (m + n) added). 2. A detergent composition comprising the nonionic surfactant according to claim 1.