JPH10218820A - Higher secondary alcohol alkoxylate, and detergent and emulsifier containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new higher secondary alcohol alkoxylate having low pour point, capable of being readily treated, good in osmotic force, capable of allowing the foam to be easily removed and excellent in detergency and emulsifying ability. SOLUTION: This higher secondary alcohol alkoxylate is represented by the formula [R<1> and R<2> are each an alkyl, with the proviso that 7<= (the total of the number the carbon atoms of the R<1> and that of the R<2> ) <=29 and (the number of the carbon atoms of the R<1> ) <= (that of the R<2> ); A is a lower alkylene; (n) is 1-50 in average] and comprises 30-90mol% higher secondary alcohol alkoxylate in which R<1> is methyl, and 70-10mol% higher secondary alcohol alkoxylate in which R<1> is an >=2C alkyl. The objective compound is obtained by reacting an 8-30C long chain olefin (e.g. octene) with a (poly) alkylene glycol (e.g. monoethylene glycol) in the presence of an acid catalyst (e.g. BEA zeolite).

Description

Description: TECHNICAL FIELD The present invention relates to a higher secondary alcohol alkoxylate and a detergent and an emulsifier containing the same. [0002] Nonionic surfactants include alkylphenol ethoxylates, higher primary alcohol ethoxylates, fatty acid ethoxylates and the like. [0003] Of these, alkylphenol ethoxylates, especially nonylphenol ethoxylate, are in the direction of being regulated because they are poor in biodegradability and thus have an adverse effect on the environment. [0004] Higher primary alcohol ethoxylates have a high pour point and not only solidify at room temperature,
The surface activity such as osmotic power is insufficient, and the detergency and emulsifying power are not sufficient. [0005] Other nonionic surfactants also include
For example, fatty acid ethoxylates hydrolyze,
Some of them are restricted in use, such as being unusable due to alkalinity, and none of them have sufficient performance. [0006] Accordingly, an object of the present invention is to provide a novel higher secondary alcohol alkoxylate and a detergent and an emulsifier containing the same. Another object of the present invention is to provide a higher secondary alcohol alkoxylate which has a low pour point, is easy to handle, has good penetrating power, has good defoaming, and has excellent detergency and emulsifying power, and a cleaning agent containing the same. It is to provide an emulsifier and an emulsifier. As a result of various studies, the present inventors have found that a specific higher secondary alcohol alkoxylate has a low pour point, is easy to handle, has a good penetrating power, and has a low foaming property. The present inventors have found that a surfactant excellent in detergency and emulsifying power can be obtained, and completed the present invention. That is, the object of the present invention is to provide (i) a compound represented by the following general formula (1): [Wherein R ¹ and R ² are alkyl groups, and the total number of carbon atoms of R ¹ and R ² is 7 to
29, and number of carbon atoms in R ² is greater than the number of carbon atoms of R ¹ (the number of carbon atoms of the carbon atoms ≦ R ² of R ^1), A represents a lower alkylene group, n represents 1 in average 50.
However, when n is 2 or more, the kind of oxyalkylene group represented by AO may be one kind or two kinds or more, and when there are two or more kinds of oxyalkylene groups, various oxyalkylene groups are used. Indicates that there are an average of n groups in total. A higher secondary alcohol alkoxylate represented by the formula (I), wherein R ¹ is a methyl group: 30 to 90 mol% of a higher secondary alcohol alkoxylate (X);
R ¹ is an alkyl group having 2 or more carbon atoms, higher secondary alcohol alkoxylate (Y) 70 to 10 m
ol% of the secondary alcohol alkoxylate. Another object of the present invention is attained by (ii) a detergent containing the above (i) higher secondary alcohol alkoxylate. Still another object of the present invention is to provide (iii)
This is achieved by an emulsifier characterized in that it contains the higher secondary alcohol alkoxylate of the above (i). DETAILED DESCRIPTION OF THE INVENTION The higher secondary alcohol alkoxylate according to the present invention has the general formula (1): ## STR3 ## [Wherein R ¹ and R ² are alkyl groups, and the total number of carbon atoms of R ¹ and R ² is 7 to
29, and number of carbon atoms in R ² is greater than the number of carbon atoms of R ¹ (the number of carbon atoms of the carbon atoms ≦ R ² of R ^1), A represents a lower alkylene group, n represents 1 in average 50.
However, when n is 2 or more, the kind of oxyalkylene group represented by AO may be one kind or two kinds or more, and when there are two or more kinds of oxyalkylene groups, various oxyalkylene groups are used. Indicates that there are an average of n groups in total. A higher secondary alcohol alkoxylate represented by the formula (I), wherein R ¹ is a methyl group: 30 to 90 mol% of a higher secondary alcohol alkoxylate (X);
R ¹ is an alkyl group having 2 or more carbon atoms, higher secondary alcohol alkoxylate (Y) 70 to 10 m
ol%. In the above formula (1), the lower alkylene group represented by A is an alkylene group having 2 to 8 carbon atoms, preferably 2 to 4 carbon atoms. Accordingly, the oxyalkylene group represented by AO includes, for example, an ethoxy group, a propoxy group, a butoxy group, an isopropoxy group,
A pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and the like, preferably an ethoxy group, a propoxy group and a butoxy group. Also,
As defined by AO in the general formula (1), these oxyalkylene groups may be composed of only one kind, or may be composed of two or more kinds. When the oxyalkylene group is composed of two or more types, the two or more types of oxyalkylene groups may be randomly arranged, or each may be arranged in a block. For example, a configuration in which a part of the long chain of an ethoxy group is a propoxy group may be employed. In the general formula (1), the alkyl groups represented by R ¹ and R ² are preferably straight-chain alkyl groups.
The total number of carbon atoms of the carbon atoms and R ² of ^1, 7-2
9, preferably 9 to 19, and the number of carbon atoms of R ² is R
^{It is not} less than ¹ carbon atoms (the number of carbon atoms of R ¹ ≦ the number of carbon atoms of R ² ). N in the general formula (1) is 1 to 5 on average.
0, preferably 1 to 20. The higher secondary alcohol alkoxylate of the present invention is a higher secondary alcohol alkoxylate represented by the above general formula (1), wherein R ¹ is a methyl group. ) 30 ~
90 mol%, preferably 40 to 80 mol%, and R ¹
Is an alkyl group having 2 or more carbon atoms.
Grade alcohol alkoxylate (Y) 70 to 10 mol
%, Preferably 60 to 20 mol%. At this time, when the proportion of the higher secondary alcohol alkoxylate (X) exceeds 90 mol%, the pour point of the obtained higher secondary alcohol alkoxylate increases, and the detergency decreases. On the other hand, the second class
The ratio of the lower alcohol alkoxylate (X) is 30 mo
If it is less than 1%, the performance as a surfactant is the same, but the production cost becomes high and it is not economically advantageous. The higher secondary alcohol alkoxylate of the present invention having the above structure can be synthesized, for example, by the following reaction. That is, it is produced by reacting a long-chain olefin having 8 to 30 carbon atoms with a (poly) alkylene glycol in the presence of an acid catalyst, and separating the product by distillation, extraction or other methods. . Here, the long-chain olefin used as a raw material for obtaining the higher secondary alcohol alkoxylate of the present invention must be a hydrocarbon having 8 to 30 carbon atoms having an ethylenically unsaturated bond. And an acyclic hydrocarbon having an ethylenically unsaturated bond and having 10 to 20 carbon atoms is preferable. Specific examples of the long-chain olefin used in the present invention include octene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, dococene, tetracocene, hexacocene, octacocene, and triacocene, for example, 1-
Decene, 2-decene, 1-dodecene, 2-dodecene, 3
-Dodecene, 4-dodecene, 5-dodecene, 1-tetradecene, 2-tetradecene, 1-hexadecene and the like. Of these, decene, dodecene, tetradecene, hexadecene, octadecene, and eicosene are preferably used. These may be used alone or in the form of a mixture of two or more. These long-chain olefins may have an unsaturated bond at the α-position, an inner position, or a mixture of the α-position and the inner-position. It can be used without any particular limitation. Of course, two or more of these long-chain olefins having different unsaturated bond positions can be used in combination. Specific examples of the (poly) alkylene glycol used as a raw material for obtaining the higher secondary alcohol alkoxylate include monoethylene glycol, diethylene glycol, triethylene glycol,
Polyethylene glycol, monopropylene glycol,
Dipropylene glycol, tripropylene glycol,
Polypropylene glycol, 1,3-propanediol, 1,2-butanediol, 2,3-butanediol, 1,4-butanediol, 1,6-hexanediol, para-xylene glycol, 1,4-cyclohexanemethanediol, etc. Is mentioned. These may be used alone or in the form of a mixture of two or more. Here, the molar ratio of the (poly) alkylene glycol to the long-chain olefin is not particularly limited, but is preferably from 0.05 to 20, more preferably from 0.1 to 10. If the molar ratio is less than 0.05, the yield of the higher secondary alcohol alkoxylate decreases, while if it exceeds 20, the volume of the reactor becomes large, which is not preferable because it is not economical. . As the reaction conditions for adding the (poly) alkylene glycol to the unsaturated bond of the long-chain olefin, the reaction temperature is usually 50 to 250 ° C, preferably 100 to 200 ° C.
° C, and the reaction pressure may be any of reduced pressure, normal pressure or increased pressure, but is preferably in the range of normal pressure to 20 kg / cm ² . When the reaction temperature is lower than 50 ° C., the reaction rate is too slow. On the other hand, when the reaction temperature is higher than 250 ° C., polymerization of a long-chain olefin, decomposition of (poly) alkylene glycol, polycondensation, etc. occur, resulting in a selectivity. Is unfavorable. Specific examples of the acid catalyst used in the reaction between the long-chain olefin and the (poly) alkylene glycol include:
Strong acid ion exchange resins, crystalline aluminosilicates such as BEA zeolite, dodecylbenzenesulfonic acid, etc. may be mentioned, but from the viewpoint of reactivity, preferably crystalline aluminosilicate, and among them, BEA zeolite is particularly desirable. . The amount of the acid catalyst is 1 to 50% by weight, preferably 2 to 30% by weight, based on the long-chain olefin. When the amount of the catalyst is less than 1% by weight, sufficient catalytic activity cannot be obtained and the addition reaction cannot be promoted.
If the amount exceeds 10% by weight, it is not preferable because effects equivalent to the further addition cannot be obtained and uneconomical. [0029] The higher secondary alcohol alkoxylate of the present invention, besides the product obtained in the above reaction step,
An alkylene oxide such as ethylene oxide, propylene oxide, butylene oxide, or styrene oxide may be added to the product. The higher secondary alcohol alkoxylate to which the alkylene oxide has been added can be obtained, for example, by adding an alkylene oxide to the above product and reacting the product in the presence of an alkali catalyst. Here, the number of moles of alkylene oxide added to the above product is not particularly limited, but is preferably 1 to 30, more preferably 4 to 20. Also,
As the reaction conditions for further adding an alkylene oxide to the above product, the reaction temperature is usually 50 to 250 ° C, preferably 100 to 200 ° C, and the reaction pressure may be either normal pressure or pressurized. Pressure to 20 kg / cm ²
Is desirable. When the reaction temperature is lower than 50 ° C., the reaction rate is slow. On the other hand, when the reaction temperature is higher than 250 ° C., decomposition and increase of by-products occur, which is not preferable. Examples of the alkali catalyst include hydroxides of elements belonging to alkali metals or alkaline earth metals, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, magnesium hydroxide, calcium hydroxide,
Barium hydroxide and the like can be mentioned. From the viewpoint of availability and reactivity, preferred are sodium hydroxide and potassium hydroxide. These may be powdered, granular, or added as an aqueous solution to perform dehydration. The amount of the alkali catalyst used is preferably from 0.01 to 2.0% by weight, and more preferably from 0.02 to 0.5% by weight, based on the starting alkoxylate. The higher secondary alcohol alkoxylate of the present invention can be used, for example, as a nonionic surfactant, or as a raw material for producing anionic or cationic surfactants. Since it has a pour point, is easy to handle, has good penetrating power, has good defoaming, and has excellent detergency and emulsifying power, it is desirable to use it as a detergent and emulsifier. Therefore, another aspect of the present invention is a cleaning agent containing the above-mentioned higher secondary alcohol alkoxylate. In the detergent of the present invention, the above-mentioned higher secondary alcohol alkoxylate may be used alone, or a conventionally known detergent surfactant may be used in combination. Examples of such surfactants include alkyl benzene sulfonate, alkyl sulfate, α-olefin sulfonate, alkyl sulfonate, aliphatic amide sulfonate, dialkyl sulfosuccinate, and alkyl ether sulfate. And the like, anionic surfactants such as an alkylamine salt and a quaternary ammonium salt, and amphoteric surfactants such as an alkyl betaine. Conventional nonionic surfactants, for example,
For higher primary alcohol ethoxylate, etc.
The cleaning agent of the present invention can be used in combination without impairing the original performance. Further, various additives used in ordinary cleaning agents can be added to the cleaning agent of the present invention. Such additives include, for example, alkaline agents,
Examples include builders, fragrances, optical brighteners, coloring agents, foaming agents, foam stabilizers, polishing agents, bactericides, bleaching agents, enzymes, preservatives, dyes, solvents, and the like. The detergent of the present invention can be used for clothing, textiles, tableware, containers, sundries, foods, building maintenance products,
Cleaning agents for houses, furniture, cars, aircraft, metal products, etc.
It can be used effectively as shampoo, body shampoo and the like. Another aspect of the present invention is an emulsifier comprising the above-mentioned higher secondary alcohol alkoxylate. In the emulsifier of the present invention, the above-mentioned higher secondary alcohol alkoxylate may be used alone, or may contain a conventionally known emulsifier. For example, an anionic surfactant, a cationic surfactant, a nonionic surfactant or a zwitterionic surfactant generally used as an emulsifier can be used in combination. The oily substance in which the emulsifier of the present invention can be used is not particularly limited, and includes mineral oil, animal and vegetable oil,
Synthetic oils and the like can be used. These can be used alone or in combination of two or more.
Examples of mineral oils include, for example, spindle oil, machine oil, liquid paraffin oil, and the like. Examples of animal and vegetable oils include beef tallow, lard, fish oil, whale oil, rapeseed oil, sesame oil, coconut oil, soybean oil, palm oil, camellia oil, castor oil and the like. The emulsifier of the present invention can be used in agricultural chemicals, metal working oils, paints, emulsifiers for emulsion polymerization, and the like. EXAMPLES Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. In the following examples, those in which n in the general formula (1) is 1 are called higher secondary alcohol monoalkoxylates, and those in which n is 2 or more are higher secondary alcohol polyalkoxylates. Called. (Synthesis Method) Example 1 Secondary dodecanol monoethoxylate 1-dodecene was converted to a BEA type zeolite (trade name: manufactured by PQ).
VALFOR CP811BL-25) at 5% by weight,
A dodecene isomer mixture (1-dodecene 25 mol) obtained by reacting in a liquid phase at 150 ° C. for 10 hours.
%, And 75 mol% of innerdodecene) 810
g (4.82 mol), monoethylene glycol 90
0g (14.52 mol) and BEA type zeolite manufactured by PQ (trade name: VALFOR CP 8) as a catalyst
11BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, the gas phase was replaced with nitrogen, and then kept in a nitrogen atmosphere at normal pressure.
Next, while stirring at a rotation speed of 600 rpm, 1
After the temperature was raised to 50 ° C., and the reaction was carried out at the same temperature for 3 hours, the reaction solution was cooled to room temperature, the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, the pressure was reduced to 2 mmH.
155 g of secondary dodecanol monoethoxylate were obtained in a boiling point range of 129 to 131 ° C. The position of addition of the alkyl chain carbon to the ethoxylate site of the obtained secondary dodecanol monoethoxylate was determined by ¹ H-NMR analysis (FIG. 1) from the proton ratio of the alkyl terminal methyl group. Secondary dodecanol monoethoxylate in which position 2 is ethoxylated (an ethoxylate wherein R ¹ in the general formula (1) is a methyl group; corresponding to the higher secondary alcohol alkoxylate (X) in claim 1) (The same applies hereinafter; the same applies hereinafter) was 71 mol%. When the pour point of the obtained secondary dodecanol monoethoxylate was measured based on JIS K-2269, it was -20 ° C. or less. The integral value of double lines near · 1.15 ppm <calculation method of the position of ethoxylation> (protons of the methyl group of R ¹ when R ¹ is a methyl group): near a · 0.9 ppm integral value of the triplet (R ¹ is and terminal methyl group of R ¹ when it is 2 or more alkyl groups carbon atoms, protons of methyl group at the end of all R ^2):
b-Ratio of those corresponding to higher secondary alcohol alkoxylate (X): c c = 2a / (a + b) <NMR measurement method> Model: Varian Unity Plus400 (4)
00 MHz) Solvent: CDCl ₃ + 0.03% TMS: SAMPLE =
99: 1 The number of times of integration: The conditions displayed after 16 ¹ H-NMR measurement were as follows. FREQUENCY 399.958MH
z SPECIAL WIDTH 7998.4 Hz ACQUISITION TIME 4.001 sec RELAXATION DELAY 3.000 sec PULSE WIDTH 10.0 usec AMBIENT TEMPERATURE NO. REPETITIONS16 DOUBLE PRECISION ACQUISIT
ION DATA PROCESSING FT SIZE 65536 TOTAL ACQUISITION TIME 1m
inutes. . Example 2 Secondary dodecanol polyethoxylate 155 g (0.67 mol) of the secondary dodecanol monoethoxylate obtained in Example 1 and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave. After replacing with nitrogen, the pressure in the reactor was increased to 1.
After adjusting the pressure to 0 kg / cm ² G and increasing the temperature to 150 ° C., 217 g (4.93 mol) of ethylene oxide was introduced into the autoclave in 3 hours. After the introduction, further 1 hour at 150 ° C
After cooling to room temperature and purging the internal pressure, a secondary dodecanol polyethoxylate of the general formula (1) having an average of 8.4 was obtained. The carbon addition position of the alkyl chain at the ethoxylate site of the obtained secondary dodecanol polyethoxylate was determined by ¹ H-NMR analysis (FIG. 2) from the proton ratio of the alkyl terminal methyl group. The secondary dodecanol polyethoxylate in which the position 2 was ethoxylated was 72 mol%. The method of calculating the position of ethoxylation and the method of NMR measurement were performed in the same manner as in Example 1. Example 3 Secondary tetradecanol monoethoxylate 1-tetradecene was mixed with 5% by weight of BEA type zeolite (trade name: VALFOR CP 811BL-25) manufactured by PQ.
At 150 ° C. for 13 hours in a liquid phase to obtain a tetradecene isomer mixture (1-tetradecene 20 mol%, inner tetradecene 80 mol%)
810 g (4.13 mol), 900 g (14.52 mol) of monoethylene glycol, and BEA type zeolite manufactured by PQ (trade name: VAL) as a catalyst.
100 g of FOR CP 811BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser, and the gas phase was replaced with nitrogen. Subsequently, the temperature was raised to 150 ° C. while stirring at a rotation speed of 600 rpm, and the reaction was carried out at the same temperature for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and the upper tetradecene phase was separated and distilled. After distilling off unreacted tetradecene, 102 g of secondary tetradecanol monoethoxylate was obtained at a reduced pressure of 5 mmHg and a boiling point of 170 to 174 ° C. The position of the alkyl chain carbon addition at the ethoxylate site of the obtained secondary tetradecanol monoethoxylate was determined by ¹ H-NMR analysis (FIG. 3) from the proton ratio of the alkyl terminal methyl group. The ratio of the secondary tetradecanol monoethoxylate in which the position 2 was ethoxylated was 69 mol%. The method of calculating the position of ethoxylation and the method of NMR measurement were performed in the same manner as in Example 1. The pour point of the obtained secondary tetradecanol monoethoxylate was measured at -10 ° C. based on JIS K-2269. Example 4 Secondary tetradecanol polyethoxylate A stainless steel autoclave was charged with 102 g (0.40 mol) of the secondary tetradecanol monoethoxylate obtained in Example 3 and 0.2 g of sodium hydroxide as a catalyst. , And the pressure in the reactor was adjusted to 1.0 kg / cm ² G with nitrogen. After the temperature was raised to 150 ° C, 150 g (3.42 mol) of ethylene oxide was introduced into the autoclave over 3 hours. 1 hour after introduction, 15 hours
After maintaining at 0 ° C., the mixture was cooled to room temperature, and after purging the internal pressure, a secondary tetradecanol polyethoxylate of the general formula (1) having an average of 9.6 was obtained. The position of the alkyl chain carbon addition at the ethoxylate site of the obtained secondary tetradecanol polyethoxylate was determined by ¹ H-NMR analysis (FIG. 4) from the proton ratio of the alkyl terminal methyl group. The secondary tetradecanol polyethoxylate in which the position 2 was ethoxylated was 66 mol%. The method of calculating the position of ethoxylation and the method of NMR measurement were performed in the same manner as in Example 1. Comparative Example 1 Primary dodecanol polyethoxylate 320 g (1.7 mol) of n-dodecanol and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave, and after replacing with nitrogen, the pressure in the reactor was reduced to nitrogen. at a 1.0 kg / cm ² G, it was introduced into the autoclave in 3 hours After the heating, ethylene oxide 680 g (15.5 mol) in 0.99 ° C.. One hour after introduction,
After maintaining at 150 ° C., the mixture was cooled to room temperature, and the internal pressure was purged, to obtain a primary dodecanol polyethoxylate having a general formula (1) wherein n was 9.0 on average. Comparative Example 2 810 g (4.82 mol) of secondary dodecanol monoethoxylate 1-dodecene, 900 g (14.52 mol) of monoethylene glycol, and BEA type zeolite manufactured by PQ (trade name: VA) as a catalyst
100 g of LFOR CP 811 BL-25) was charged into a 3000 ml glass reactor equipped with a stirring blade and a reflux condenser. After the gas phase was replaced with nitrogen, the atmosphere was kept under a nitrogen atmosphere at normal pressure. Subsequently, the temperature was raised to 150 ° C. while stirring at a rotation speed of 600 rpm, and the reaction was carried out at the same temperature for 3 hours. Thereafter, the reaction solution was cooled to room temperature, and the upper layer of the dodecene phase was separated and distilled. After distilling off unreacted dodecene, 255 g of secondary dodecanol monoethoxylate was obtained at a reduced pressure of 2 mmHg in a boiling range of 129 to 131 ° C. The alkyl chain carbon addition position of the ethoxylate site of the obtained secondary dodecanol monoethoxylate was determined by ¹ H-NMR analysis (FIG. 5) from the proton ratio of the alkyl terminal methyl group. The ratio of secondary dodecanol monoethoxylate in which position 2 was ethoxylated was 94 mol%. The method of calculating the position of ethoxylation and the method of NMR measurement were performed in the same manner as in Example 1. Comparative Example 3 Secondary dodecanol polyethoxylate 255 g (1.1 mol) of the secondary dodecanol monoethoxylate obtained in Comparative Example 2 and 0.2 g of sodium hydroxide as a catalyst were charged into a stainless steel autoclave. After replacing with nitrogen, the pressure in the reactor was increased to 1.0 with nitrogen.
and kg / cm ² G, it was introduced into the autoclave in 3 hours After the heating, ethylene oxide 358g (8.14mol) in 0.99 ° C.. After the introduction, the temperature was further maintained at 150 ° C. for 1 hour, cooled to room temperature, and the internal pressure was purged. Was. The carbon addition position of the alkyl chain at the ethoxylate site of the obtained secondary dodecanol polyethoxylate was determined by ¹ H-NMR analysis (FIG. 6) from the proton ratio of the alkyl terminal methyl group. The secondary dodecanol polyethoxylate in which the position 2 was ethoxylated was 93 mol%. The method of calculating the position of ethoxylation and the method of NMR measurement were performed in the same manner as in Example 1. Examples 5 and 6 and Comparative Examples 4 and 5 The following physical properties and interface properties of the substances obtained in Examples 2 and 4 were measured. (Examples 5 and 6) The same measurement was performed for the substances obtained in Comparative Examples 1 and 3. (Comparative Examples 4 and 5) The measurement results are shown in Table 1 below. Measurement method (1) Pour point Measured in accordance with JIS K-2269 (Petroleum product pour point test method). (2) Penetration wool: 2 in accordance with JIS K-3362-1955
Nippon woolen 20 oz roller cross wool piece at 5 ° C 9
It measured using 0x10mm. (Activator concentration: 0.1
Cotton): Canvas 6 at 25 ° C by the campus disk method.
No. was measured. (Activator concentration: 0.25% by weight) (3) Foam property According to JIS K-3362 (Rosmiles method), 2
It was measured at 5 ° C. (Activator concentration: 0.1% by weight) Examples 7 and 8 and Comparative Example 6 The substances obtained in Examples 2 and 4 were evaluated for the following detergency. (Examples 7 and 8) The substances obtained in Comparative Example 3 were similarly evaluated.
(Comparative Example 6) The results are shown in Table 2 below. (Evaluation method) Referring to JIS K-3362, a stirring type detergency tester (Terg-O-tom) was used.
eter) under the following conditions. <Washing conditions> Soiled cloth: Size 5 × 5 cm Soil (%) Oleic acid 28.3 Triolein 15.6 Cholesterol oleate 12.2 Liquid paraffin 2.5 Squalene 2.5 Cholesterol 1.6 Gelatin 7.0 Red Yellow soil 29.8 Carbon black 0.5 Water used: Water temperature: 25 ° C Time: Washing 5 minutes / Rinse 5 minutes Bath ratio: 3 sheets / 1 pot (1 L) Activator concentration: 0.03% Evaluation method> Using a reflectometer, the reflectance of the original cloth, the artificially-contaminated cloth, and the cleaning cloth after cleaning were measured at three locations for each cloth of each test piece, and the average value was used to perform cleaning according to the following formula. Force (%) was calculated. ## EQU1 ## [Table 2] Examples 9 and 10 The substances obtained in Examples 2 and 4 were evaluated for the following emulsifying power. The results are shown in Table 3 below. (Evaluation method) 5 ml of the synthesized sample was added to a mixture of 55 ml of water and 40 ml of oil, mixed well, and allowed to stand. After 5 minutes, the state of separation of the water or oil layer is observed. Evaluation was made as follows according to the emulsified state. ：: Good emulsified state △: Slightly separated ×: Completely separated Table 3 The higher secondary alcohol alkoxylate of the present invention has a particularly low pour point, is easy to handle, has good penetrating power, has good defoaming, and has excellent detergency and emulsifying power. Has advantages.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of an ethoxylate site of the secondary dodecanol monoethoxylate obtained in Example 1. FIG. 2 shows ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of an ethoxylate site of the secondary dodecanol polyethoxylate obtained in Example 2. FIG. 3 is ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of an ethoxylate site of the secondary tetradecanol monoethoxylate obtained in Example 3. FIG. 4 is ¹ H-NMR analysis data used to calculate the alkyl chain carbon addition position of the ethoxylate site of the secondary tetradecanol polyethoxylate obtained in Example 4. FIG. 5 is ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of an ethoxylate site of the secondary dodecanol monoethoxylate obtained in Comparative Example 2. FIG. 6 shows ¹ H-NMR analysis data used for calculating an alkyl chain carbon addition position of an ethoxylate site of the secondary dodecanol polyethoxylate obtained in Comparative Example 3.

Continuation of front page    (72) Inventor Yoshiyuki Onda             5-8 Nishiburi-cho, Suita-shi, Osaka             Nippon Shokubai

Claims (1)

Claims: General formula (1) [Wherein R ¹ and R ² are alkyl groups, the total number of carbon atoms of R ¹ and R ² is 7 to 29, and R 1
² carbon atoms is greater than the number of carbon atoms of R ¹ (the number of carbon atoms of the carbon atoms ≦ R ² R ^1), A represents a lower alkylene group, n represents 1 to 50 on average. Where n is 2
In the above cases, the type of the oxyalkylene group represented by AO may be one or more, and when the number of the oxyalkylene groups is two or more, the various oxyalkylene groups are averaged as a whole. Indicates that there are n. A higher secondary alcohol alkoxylate represented by the formula: wherein R ¹ is a methyl group, 30 to 90 mol% of a higher secondary alcohol alkoxylate (X), and R ¹ has 2 or more carbon atoms. Alkyl higher alcohol secondary alkoxylate (Y) 70 to 10 m
ol%, a higher secondary alcohol alkoxylate comprising: 2. A detergent comprising the higher secondary alcohol alkoxylate according to claim 1. 3. An emulsifier comprising the higher secondary alcohol alkoxylate according to claim 1.