JP4323249B2 - Nonionic surfactant and nonionic surfactant composition containing the same - Google Patents

Description

  The present invention relates to a nonionic surfactant and a nonionic surfactant composition containing the same.

  Conventionally, nonionic surfactants obtained by addition polymerization of alkylphenols with ethylene oxide (hereinafter also simply referred to as “EO”) have exhibited extremely excellent surface activity and have been widely used in a wide range of application fields. .

  However, in recent years, due to concerns about the negative impact of the nonionic surfactants on the environment and ecosystems, aliphatic alcohols are used as starting materials in application fields that require consideration for the environment and ecosystems, such as detergents. The resulting non-alkylphenol type nonionic surfactant is being converted, and addition polymerization of aliphatic oxide with ethylene oxide and / or C3-4 alkylene oxide in the presence of an alkali catalyst or acid catalyst Alkylene oxide adducts of aliphatic alcohols obtained as above are already used in various fields of application as various detergents, emulsifiers, emulsion polymerization emulsifiers, dispersants, solubilizers, wetting and penetrating agents, antifoaming agents, etc. ing.

As conventional nonionic surfactants, conventional techniques relating to addition forms of propylene oxide (hereinafter also simply referred to as “PO”) include, for example, aliphatic alcohol as a starting material, and (1) random addition of ethylene oxide and propylene oxide. An alkylene oxide adduct in which ethylene oxide is further introduced into the body (see, for example, Patent Document 1), or (2) an alkylene oxide adduct in which propylene oxide is further introduced into a random adduct of ethylene oxide and propylene oxide (for example, Various alkylene oxide adducts such as Patent Document 2) have been proposed.
JP 7-126690 A Japanese Patent Laid-Open No. 10-461189

  The above-mentioned conventional aliphatic alcohol-based nonionic surfactants are practically unsatisfactory due to insufficient performance, and are often limited in application fields and use conditions that can be used. There was a problem that high performance and wide versatility were not exhibited like nonionic surfactants. In particular, the emulsifying power, solubilizing power, and cleaning power are not sufficiently satisfactory in terms of performance, and further development has been awaited.

[Object of invention]
The present invention has been made in view of the above circumstances, and its purpose is to have an excellent surface activity comparable to an alkylphenol-based nonionic surfactant obtained by addition polymerization of ethylene oxide to an alkylphenol. It is an object of the present invention to provide a fatty alcohol-based nonionic surfactant that can be used in various application fields and a composition containing the same.

  As a result of intensive studies, the present inventor has found that the presence of unreacted alcohol in the production (synthesis) process adversely affects various performances of the finally obtained nonionic surfactant, and specific aliphatic alcohols. It is found that good results can be obtained only when using as a starting material, and an alkylene oxide adduct of an aliphatic alcohol obtained by setting these conditions in a balanced manner is comparable to an alkylphenol-based nonionic surfactant. It has been found that it has such an excellent surface activity and can be used in a wide range of application fields, and has led to the present invention.

That is, non-ionic surface active agent according to claim 1, wherein the content of the alcohol of 12 to 14 carbon atoms is synthesized from 80 wt% or more der Luer alcohol mixtures, non-represented by the following general formula (1) It is an ionic surfactant and is characterized by using a compound represented by the following general formula (2) having an unreacted alcohol content of 4% by weight or less.

RO- (AO) n- (EO) m-H (1)
RO- (AO) n-H (2)
[Where, R is an aliphatic hydrocarbon group content of hydrocarbon group of 12 to 14 carbon atoms is 80 wt% or more, - (AO) n- is a single also 3 carbon atoms of the alkylene oxide having 4 carbon atoms German heavy Gokusari, - (EO) m- denotes a homopolymer chain of ethylene oxide. In the formula, n and m represent the average number of added moles of alkylene oxide, n is 3 to 4 when AO is an alkylene oxide having 3 carbon atoms, 2.5 when m is an alkylene oxide having 4 carbon atoms , and m is 0 to 0. A range of 100. ]

  The nonionic surfactant according to claim 2 is the saturated non-ionic surfactant according to claim 1, wherein the aliphatic alcohol represented by the general formula (2) has a linear primary ratio of 70% or more. It is synthesized from alcohol and / or linear saturated primary alcohol.

The nonionic surfactant according to claim 3 is the nonionic surfactant according to claim 1, wherein the aliphatic alcohol represented by the general formula (2) is a branched saturated primary having 12 to 13 carbon atoms. It is synthesized from a mixture of branched saturated primary alcohols having an alcohol content of 80% by weight or more.

  The nonionic surfactant according to claim 4 is used as a cleaning agent in the nonionic surfactant according to any one of claims 1 to 3.

  The nonionic surfactant according to claim 5 is used as an emulsifier in the nonionic surfactant according to any one of claims 1 to 3.

  The nonionic surfactant according to claim 6 is used as an emulsifier for emulsion polymerization in the nonionic surfactant according to any one of claims 1 to 3.

  The nonionic surfactant according to claim 7 is characterized in that, in the nonionic surfactant according to any one of claims 1 to 3, the nonionic surfactant is used as a fragrance solubilizer or an essential oil solubilizer. To do.

  The nonionic surfactant according to claim 8 is used as a surfactant for dry cleaning in the nonionic surfactant according to any one of claims 1 to 3.

  The nonionic surfactant composition according to claim 9 contains 70 to 95% by weight of the nonionic surfactant according to any one of claims 1 to 8 and 5 to 30% by weight of water. It is characterized by.

  According to the nonionic surfactant of the present invention, emulsifying power for various oils such as mineral oil and vegetable oil, various solvents, and various synthetic resins is remarkably improved. In addition, it exhibits extremely excellent performance as a cleaning agent, and can be used as various industrial and household cleaning agents, various industrial process chemicals, various commercial cleaning agents, dry cleaning bases, and the like. Further, it has excellent surface activity comparable to alkylphenol-based nonionic surfactants, and can be used as a solubilizer for various fragrances or as an emulsifier for emulsion polymerization of various synthetic polymers. Sulfate ester type and ether carboxylate type anionic surfactants derived from the nonionic surfactant of the present invention can also be suitably used as emulsifiers for emulsion polymerization.

  When the number of carbon atoms of the starting aliphatic alcohol is not within the limited range (12-14) of the present invention, or when the content is less than 80% by weight even if it is within C12-14, the fatty acid alcohol When the nonionic surfactant of the invention is produced, the nonionic surfactant is induced on the condition that the content of unreacted alcohol in the intermediate compound represented by the general formula (2) exceeds 4% by weight. In the case of surface activity, a significant decrease in surface activity such as a decrease in surface tension reduction performance, an increase in critical micelle concentration (cmc), and a decrease in osmotic power is observed. The performance important in terms of practicality such as compatibility and mixed state is deteriorated or the properties are remarkably deteriorated. In particular, in order to make very important performances such as emulsifying power and solubilizing power good, it is necessary to be 4% by weight or less, and preferably 1% by weight or less.

  In the nonionic surfactant of the present invention, preferably n in the compounds represented by the general formulas (1) and (2), that is, an alkylene oxide having 3 and / or 4 carbon atoms (specifically, propylene) The preferred average added mole number of oxide and / or 1,2-butylene oxide is 2-8. When the average number of added moles (n) is less than 2 or more than 8, the surface tension lowering ability is lowered, the penetrating power is lowered, the detergency, the emulsifying power, the solubilizing power, the compatibility, etc. , Practical performance may be degraded or properties may be deteriorated.

  In the nonionic surfactant of the present invention, m in the compound represented by the general formula (1), that is, the average added mole number of ethylene oxide is 0 to 100, the surface tension lowering ability is lowered, the penetrating power is lowered, Moreover, 2-50 are preferable at the point which is excellent in the balance of physical properties, such as detergency, emulsification power, solubilization power, and compatibility.

  The nonionic surfactant of the present invention can be derived from a fatty acid alcohol using various known catalysts such as an alkali catalyst and an acid catalyst, because the distribution of the alkylene oxide adduct becomes relatively wide. It is preferable to use an alkali catalyst. Examples of the alkali catalyst that can be used include hydroxides of alkali metals such as KOH and NaOH, and various amine compounds including triethylamine.

Field of Use The nonionic surfactant of the present invention exhibits very excellent performance as an emulsifier for various oils and solvents, like the alkylphenol nonionic surfactant. Particularly, it is suitable as an emulsifier for various mineral oils, various vegetable oils, aliphatic and alicyclic hydrocarbon solvents, and aromatic solvents.

  Various silicones, modified silicones, polyolefins, polyesters, diene polymers such as polybutadiene, and other synthetic resins as emulsifiers and dispersants, and essential oils, perfumes emulsifiers and solubilizers It is suitable as.

  It is also suitably used as an emulsifier for emulsion polymerization of various monomers such as acrylate, styrene, diene and vinyl.

  In addition, the nonionic surfactant of the present invention exhibits very excellent performance as a cleaning agent, like the alkylphenol nonionic surfactant, and can be widely used in various fields of application. For example, various industrial and commercial cleaning agents, automotive cleaning agents, and various industrial process chemicals such as fiber scouring agents, metal surface treatment agents, metal degreasing agents, metal component cleaners, electronic component cleaners In addition to agents, leather cleaners, pitch removers, linen supply related cleaners, kitchen cleaners, fingertip cleaners, dry cleaning additives, and the like. In particular, the nonionic surfactant of the present invention exhibits a very good detergency over a wide range of soils such as mineral oil stains, vegetable oil stains, soils with inorganic substances, waxes, and resins attached thereto. .

The aliphatic alcohol aliphatic alcohol is a higher alcohol having an aliphatic hydrocarbon group having 12 to 14 carbon atoms of 80% by weight or more, and the content of 12 to 14 carbon atoms being 80% by weight or more. The use of straight-chain saturated primary alcohols leads to a marked improvement in emulsifying power, solubilizing power, and detergency, and exhibits performance comparable to alkylphenol-based nonionic surfactants and wide versatility in practical use. This is preferable. Specific examples include Conol (made by Nippon Nippon Chemical Co., Ltd.) and Calcoal (made by Kao Corporation), which mainly contain lauryl alcohol.

  A saturated primary alcohol having a straight chain ratio of 70% or more can also be suitably used. Examples of the saturated primary alcohol having a straight chain ratio of 70% or more include Dovanol 23, 25 (manufactured by Shell Chemical Co., Ltd.).

  In addition, the use of a branched saturated primary alcohol having a content of 12 to 13 carbon atoms of 80% or more has good surface tension reducing ability and penetrating ability, and practically sufficient surface active ability in a dynamic state. The detergency, emulsification power, and solubilization power are preferable because they have performance comparable to that of alkylphenol nonionic surfactants and a wide range of practical versatility. As a specific example, a branched saturated primary alcohol produced by an oxo method via a higher olefin derived from propylene, butene, or a mixture thereof is preferable. In addition, the isotridecanol manufactured by this manufacturing method is marketed, and can be used conveniently for this invention. In addition, a single composition of Guerbet Alchol having a 2-alkyl-1-alkanol type chemical structure or a mixture thereof is an example of a branched aliphatic alcohol that can be suitably used.

  Furthermore, the aliphatic alcohol used may be a single carbon number or a mixture of aliphatic alcohols having different carbon numbers as long as it is within the limited range of the nonionic surfactant of the present invention. The chemical structure of the aliphatic alcohol may be a single composition or a mixture of a plurality of isomers. Moreover, it is also possible to mix | blend and use 2 or more types of the said various alcohol within the limited range of this invention.

Catalyst As the catalyst used in the alkylene oxide addition reaction for obtaining the nonionic surfactant of the present invention, known catalysts such as a base catalyst and an acid catalyst can be used, but in order to achieve the object of the present invention, it is more preferable. It is preferable to use an alkali catalyst characterized by relatively wide distribution of the alkylene oxide adduct. Examples of the alkali catalyst that can be used include hydroxides of alkali metals such as potassium hydroxide and sodium hydroxide, and various amine compounds including triethylamine. Moreover, these catalysts are advantageous from the viewpoint of commercial production from the viewpoints of reaction rate, production cost, amount of by-products and the like. Furthermore, in the present invention, potassium hydroxide and sodium hydroxide are preferred, and a suitable catalyst amount is 0.005 to 1.0% (converted to solid content) per reaction crude product (total charge), more preferably It is 0.03 to 0.4% (in terms of solid content).

The production conditions in the case of using potassium hydroxide and / or sodium hydroxide as the alkylene oxide addition catalyst such as the production conditions are shown below, but the production conditions for obtaining the nonionic surfactant of the present invention are limited thereto. Is not to be done.

  Heating, cooling operation, depressurization, pressurization operation are possible, and the above-listed reactors are equipped with a raw material inlet, a product outlet, an alkylene oxide and nitrogen inlet tube, a stirrer, a thermometer, and a pressure gauge. A predetermined amount of an aliphatic alcohol that can be suitably used in the invention is charged, and then solid potassium hydroxide or sodium hydroxide, or an aqueous solution thereof is charged, and then purged with nitrogen, and the pressure is reduced in a temperature range from room temperature to 110 ° C. Dehydrate. Next, a predetermined amount of alkylene oxide is introduced and added at 80 to 180 ° C. When the alkylene oxide is ethylene oxide, the introduction temperature, that is, the reaction temperature is more preferably 100 to 180 ° C. In addition, when alkylene oxide is propylene oxide, when propylene oxide and ethylene oxide coexist, or when reacted with butylene oxide and ethylene oxide, or when propylene oxide and butylene oxide coexist In this case, the reaction temperature is more preferably 100 to 150 ° C. In the alkylene oxide addition reaction operation, after introducing a predetermined amount of alkylene oxide, it is more preferable to perform an operation (aging operation) for continuing the reaction until the pressure decreases and becomes constant. Furthermore, the target non-ionic surfactant of the present invention can be obtained by adding an appropriate amount of a known acid to the obtained reaction crude product to neutralize the catalyst. In the neutralization operation, it is also possible to remove the catalyst using an alkali adsorbent.

Composition The nonionic surfactant of the present invention may be used in combination with water (that is, as a composition with water) for the purpose of improving the appearance and uniformity of the product. The mixing ratio in this case is 70 to 95% by weight of nonionic surfactant and 5 to 30% by weight of water.

  One embodiment of the present invention will be described below, but the present invention is not limited thereto.

Examples 1, 3-4, and Examples 6-7
A 5-liter autoclave was charged with 800 g (4.1 mol) of lauryl alcohol [Conol 1275; manufactured by Shin Nippon Chemical Co., Ltd., molecular weight 196] and 3.49 g of potassium hydroxide (solid content), and the inside of the autoclave was purged with nitrogen. The pressure was reduced at 100 ° C. while stirring, and after the internal pressure in the reactor reached 2.7 KPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after raising the temperature to 120 ° C., 947 g (16.3 mol) of propylene oxide was introduced at 120 ± 5 ° C. and a reaction pressure of 0.25 MPa. After the introduction of propylene oxide, the reaction temperature was maintained and the reaction was continued until the internal pressure decreased and became constant to obtain a PO adduct.

  Next, 1796 g (40.8 mol) of ethylene oxide was introduced at 130 ± 5 ° C. and a reaction pressure of 0.25 MPa. Subsequently, after the introduction of ethylene oxide, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 70 ° C., neutralized with 6.92 g of 85% lactic acid, and the nonionic surfactant (1) of the present invention [in the general formula (I), AO = PO, n = 4, m = 10].

In the same way,
Nonionic surfactant (3) [in general formula (I), AO = PO, n = 4, m = 3]
Nonionic surfactant (4) [in general formula (I), AO = PO, n = 4, m = 4]
Nonionic surfactant (6) [in general formula (I), AO = BO, n = 2.5, m = 4]
Nonionic surfactant (7) [In general formula (I), AO = BO, n = 2.5, m = 8] was obtained.

Example 2 and Example 5
A 5-liter autoclave was charged with 800 g (4.0 mol) of tridecyl alcohol [Tridecanol BT; manufactured by Kyowa Hakko Co., Ltd., molecular weight 200] and 2.99 g of potassium hydroxide (solid content), and the inside of the autoclave was purged with nitrogen. The pressure was reduced at 100 ° C. while stirring, and after the internal pressure in the reactor reached 2.7 KPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after the temperature was raised to 120 ° C., 698 g (12.0 mol) of propylene oxide was introduced at 120 ± 5 ° C. and a reaction pressure of 0.25 MPa. After the introduction of propylene oxide, the reaction temperature was maintained and the reaction was continued until the internal pressure decreased and became constant to obtain a PO adduct.

  Next, 1584 g (36.0 mol) of ethylene oxide was introduced at 130 ± 5 ° C. and a reaction pressure of 0.25 MPa. Subsequently, after the introduction of ethylene oxide, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Thereafter, the reaction solution was cooled to 70 ° C., neutralized with 5.93 g of 85% lactic acid, and the nonionic surfactant (2) of the present invention [in the general formula (I), AO = PO, n = 3, m = 9].

  By the same operation, the nonionic surfactant (5) of the present invention [in general formula (I), AO = PO, n = 3, m = 4] was obtained.

Comparative Examples 1, 3, 5 and Comparative Example 10
After charging 1400 g (7.1 mol) of lauryl alcohol [Conol 1275; made by Shin Nippon Rika Co., Ltd., molecular weight 196] and 1.80 g of potassium hydroxide (solid content) into a 5 liter autoclave, the inside of the autoclave was purged with nitrogen The pressure was reduced at 100 ° C. while stirring, and after the internal pressure in the reactor reached 2.7 KPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after the temperature was raised to 130 ° C., 2200 g (50.0 mol) of ethylene oxide was introduced at 130 ± 5 ° C. and a reaction pressure of 0.25 MPa. Subsequently, after the introduction of ethylene oxide, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Then, after cooling a reaction liquid to 70 degreeC, it neutralized with 3.57g of 85% lactic acid, and the nonionic surfactant of the comparative example (1) was obtained. By the same operation, the nonionic surfactant (3), (5), (10) of the comparative example was obtained.

Comparative Examples 2, 6-7, and Comparative Example 13
By the same operation as Example 1, the nonionic surfactants (2), (6), (7), and (13) of Comparative Examples having different addition mole numbers of the starting material and alkylene oxide were obtained.

Comparative Example 4 and Comparative Example 12
A 5-liter autoclave was charged with 800 g (4.1 mol) of lauryl alcohol [Conol 1275; manufactured by Shin Nippon Chemical Co., Ltd., molecular weight 196] and 3.54 g of potassium hydroxide (solid content), and the interior of the autoclave was purged with nitrogen. The pressure was reduced at 100 ° C. while stirring, and after the internal pressure in the reactor reached 2.7 KPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after the temperature was raised to 120 ° C., an alkylene oxide mixture in which 1796 g (40.8 mol) of ethylene oxide and 947 g (16.3 mol) of propylene oxide were mixed at 125 ± 5 ° C. and a reaction pressure of 0.20 MPa was introduced. The reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Then, after cooling a reaction liquid to 70 degreeC, it neutralized with 7.02g of 85% lactic acid, and the nonionic surfactant of the comparative example (4) was obtained. By the same operation, the nonionic surfactant (12) of the comparative example was obtained.

Comparative Example 8 and Comparative Example 11
1700 g (4. containing 3% potassium acetate, containing 3% potassium acetate, 5% tridecyl alcohol (unreacted alcohol)) in a 5 liter autoclave with tridecyl alcohol [Tridecanol BT; Kyowa Hakko Kogyo Co., Ltd., molecular weight 200]. 7 mol) was charged, and the inside of the autoclave was purged with nitrogen, and then the pressure was reduced at 100 ° C. with stirring. After the internal pressure in the reactor reached 2.7 KPa, dehydration under reduced pressure was continued for 30 minutes. Subsequently, after the temperature was raised to 130 ° C., 1843 g (31.8 mol) of ethylene oxide was introduced at 130 ± 5 ° C. and a reaction pressure of 0.25 MPa. Subsequently, after the introduction of ethylene oxide, the reaction temperature was maintained and aging was performed until the internal pressure decreased and became constant. Then, after cooling a reaction liquid to 70 degreeC, it neutralized with 5.73 g of 85% lactic acid, and the nonionic surfactant of the comparative example (8) was obtained. By the same operation, the nonionic surfactant (11) of the comparative example was obtained.

Comparative Example 9
“Neugen EA-130” (nonylphenol-10EO) manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. was used as a nonionic surfactant in Comparative Example (9).

Comparative Example 14
Nonylphenol-3PO-4EO was used as it was as the nonionic surfactant of Comparative Example (14).

Comparative Example 15
Nonylphenol-3PO-9EO was used as it was as the nonionic surfactant of Comparative Example (15).

The nonionic surfactants of Examples 1 to 7 and Comparative Examples 1 to 15 obtained as described above are summarized in the following [Table 1].

Detergency test (1)
The nonionic surfactants obtained in Examples and Comparative Examples were mixed with the components shown in the following [Table 2] in the proportions described in the same table to prepare clothing cleaning agents.

  A cleaning test on the garment cleaning agent was performed under the following conditions. That is, the washing power evaluation of the detergent for clothes was performed using a targo-meter (Terg-O-Tometer) using a wet-contaminated cloth manufactured by the Laundry Association as a test cloth (based on JIS K3362).

<Terg-O-Tometer / Color difference meter method, washing test for clothing>
Contaminated cloth ... Commercial wet artificially contaminated cloth, detergent manufactured by the Laundry Science Association ... detergent concentration for the above-prepared clothes detergent ... active ingredient equivalent of surfactant component (component A + component B) 0.02%
Washing conditions [during washing]: aqueous detergent solution, 30 ° C., 120 rpm, 10 minutes × 1 time, bath ratio 1:30
[When rinsing]: tap water, 30 ° C., 120 rpm, 3 minutes × twice, bath ratio 1:30
[Used hard water]: CaCl ₂ · 2H ₂ O (270 mg / liter).

  In addition, the cleaning power (cleaning rate%) in this test was calculated based on the following formula from the surface reflectance (%) change before and after cleaning of the model-contaminated cloth obtained with a surface reflectometer.

Detergency = Washing rate (%) = (Test cloth reflectance after washing−Test cloth reflectance before washing) / (White cloth (unstained cloth) reflectance before washing−Test cloth reflectance before washing) × 100
Relative detergency (%) = (cleaning rate of each test nonionic surfactant) / (cleaning rate of lauryl alcohol-7EO) × 100
The results are shown in [Table 3] below.

Detergency test (2)
The detergency test for the model dirt shown in [Table 4] below was carried out under the following operating methods and conditions, and the detergency performance of the nonionic surfactants of Examples and Comparative Examples was evaluated. In addition, the cleaning power was evaluated by visually observing the degree of cleaning (removal of dirt) of the test cloth after cleaning in four stages of ◎, ○, Δ, and ×.

  Preparation of test cloth: A woven cloth made of 65% polyester and 35% cotton is immersed in model dirt having the above composition and then left for 12 hours in a state of being fixed to a clip in a constant temperature bath at 40 ° C. The cloth was cut into a size of 5 cm × 5 cm, and a test cloth to be used for this test was prepared.

  Cleaning test conditions: 1 liter of a 1% aqueous solution of the nonionic surfactant of the present invention was adjusted to 30 ° C, and then the above three test cloths were put in, and the temperature was maintained at 60 ° C with a tartometer (Terg-O-Tometer). Washing at 100 rpm for 15 minutes. Thereafter, a 3-minute rinse was performed three times in the same manner. The water used in this test was tap water for both washing and rinsing. After rinsing, the test cloth was taken out of the water, dehydrated and dried overnight in a hot air dryer at 40 ° C., and the detergency was evaluated. In addition, the same treatment was performed only with water without being immersed in model dirt, and a test cloth was obtained as a blank for cleaning evaluation.

  Evaluation of detergency and foaming at the time of detergency: In the detergency test performed on the nonionic surfactant of the present invention, detergency was determined according to the following evaluation criteria.

Detergency rating:
Evaluation: State of the test cloth after washing ◎ ... Good cleaning power, no white color unevenness with whiteness equivalent to a blank ○ ... Whiteness equivalent to a blank but color unevenness is observed Δ ... White against a blank Degree is inferior x: Whiteness is inferior to blank and uneven color is observed. The results are shown in [Table 5] below.

Detergency test (3)
The nonionic surfactants obtained in Examples and Comparative Examples were mixed with the components shown in [Table 6] below in the proportions shown in the table, thereby preparing a kitchen cleaner (pH adjustment: 7 0.0 ± 0.5). Detergency evaluation of this kitchen detergent was performed according to JIS K3362 (Leanut method). The cleaning power in this test was the cleaning power (%), which was the dirt removal rate (%) determined by the following formula. Further, the cleaning power of each system was relatively compared with the cleaning power of the lauryl alcohol 7EO adduct being 100.

<Leanut cleaning test>
Dirt ... Edible oil model dirt (beef tallow, soybean oil, monoolein, oil red)
Cleaning substrate… Glass preparation cleaner… Concentration of cleaning agent for kitchen as above… 0.02% as cleaning agent for kitchen
Washing conditions [during washing] ... Aqueous detergent solution, 30 ° C., 250 rpm, 3 minutes × 1 time [during rinsing] ... 30 ° C., 250 rpm, 1 minute × 1 time [use hard water] ... CaCl ₂ .2H ₂ O 59.0 mg /liter,
MgCl ₂ · 6H ₂ O 27.2 mg / liter,
Detergency: Soil removal rate (%) = [(BC) / (BA)] × 100
A = Weight before adhering dirt to the glass plate for testing (a set of 6 sheets) (g)
B = Weight (g) after attaching dirt to a glass plate for testing (1 set of 6)
C = Weight (g) after cleaning of a test glass plate (a set of 6 sheets) with dirt attached
The results are shown in [Table 7] below.

Emulsifying power test An emulsifying test of oils with the nonionic surfactant obtained in the examples and comparative examples was carried out under the following operating methods and conditions to evaluate the emulsifying performance.

Emulsification test conditions: Liquid paraffin, silicon oil (dimethylpolysiloxane, kinematic viscosity 1000 mm ² / s (25 ° C.)), kerosene and olive oil 8.0 g and emulsifier 0.8 g as an oil to be emulsified in a graduated test tube, Stir with a test tube touch mixer for 30 seconds, then add 11.2 g of distilled water and further stir with a touch mixer for 1 minute, and then measure the water separation layer of the emulsion after standing for 2 hours. The emulsification performance of the ionic surfactant was evaluated.

  Emulsifying power evaluation: Under the above conditions, the emulsifying power was evaluated by the following formula from the water separation after 2 hours of the emulsion. Moreover, the versatility as an emulsifier was evaluated by defining the total of the four types of emulsification power (%) tested as emulsification performance.

Emulsifying power (%) = (amount of charged water−amount of water separation) (ml) / amount of charged water (ml) × 100
Emulsification performance = emulsification power of liquid paraffin (%) + emulsification power of silicone oil (%) + emulsification power of kerosene (%) + emulsification power of olive oil (%)
The results are shown in [Table 8] below.

Solubilization test The perfume solubilization test of the nonionic surfactants obtained in Examples and Comparative Examples was performed under the following operating methods and conditions, and the solubilization performance was evaluated.

  Solubilization test conditions: 0.6 g of orange oil and 0.6 g of emulsifier were placed in a graduated test tube, stirred for 30 seconds with a test tube touch mixer, then 28.8 g of distilled water was added, and further stirred for 2 minutes with a touch mixer. Thereafter, the state of the perfumed liquid after standing for 1 hour was observed. Further, a similar solubilization test was performed in place of orange oil instead of rose oil, and the solubilization performance of the nonionic surfactant of the present invention was evaluated.

Evaluation of solubilizing power:
Evaluation: State of perfumed liquid ○: Appearance is transparent, no separation of perfume is observed Δ: Appearance is turbid, or non-uniform layer is observed in upper layer ×: Perfume separation is observed [Table 9] Shown in

  The nonionic surfactant of the present invention has extremely excellent emulsifying power for various oils such as mineral oil and vegetable oil, various solvents, and various synthetic resins. It can be used as various industrial and household cleaning agents, various industrial process chemicals, various commercial cleaning agents, and dry cleaning bases. Further, it has excellent surface activity comparable to alkylphenol-based nonionic surfactants, and can be used as a solubilizer for various fragrances or as an emulsifier for emulsion polymerization of various synthetic polymers. Sulfate ester type and ether carboxylate type anionic surfactants derived from the nonionic surfactant of the present invention can also be suitably used as emulsifiers for emulsion polymerization.

Claims (9)

Alcohol content of 12 to 14 carbon atoms are synthesized from Der Rua alcohol mixture 80 wt% or more, a non-ionic surfactant represented by the following general formula (1),
Nonionic surfactants characterized by comprising using the compound represented by the unreacted alcohol content of 4 wt% or less of the following general formula (2).
RO- (AO) n- (EO) m-H (1)
RO- (AO) n-H (2)
[Where, R is an aliphatic hydrocarbon group content of hydrocarbon group of 12 to 14 carbon atoms is 80 wt% or more, - (AO) n- is a single also 3 carbon atoms of the alkylene oxide having 4 carbon atoms German heavy Gokusari, - (EO) m- denotes a homopolymer chain of ethylene oxide. In the formula, n and m represent the average number of added moles of alkylene oxide, n is 3 to 4 when AO is alkylene oxide having 3 carbon atoms, 2.5 when alkylene oxide having 4 carbon atoms , m is 0 to A range of 100. ]   The aliphatic alcohol represented by the general formula (2) is synthesized from a saturated primary alcohol and / or a linear saturated primary alcohol having a straight chain ratio of 70% or more. Nonionic surfactant. Aliphatic alcohols represented by the general formula (2) is to be synthesized from a mixture of branched saturated primary alcohol branched saturated primary alcohols content of 12 to 13 carbon atoms is 80 wt% or more The nonionic surfactant according to claim 1, wherein   The nonionic surfactant according to any one of claims 1 to 3, wherein the nonionic surfactant is used as a cleaning agent.   The nonionic surfactant according to any one of claims 1 to 3, wherein the nonionic surfactant is used for an emulsifier.   It uses for the emulsifier for emulsion polymerization, The nonionic surfactant of any one of Claims 1-3 characterized by the above-mentioned.   The nonionic surfactant according to any one of claims 1 to 3, wherein the nonionic surfactant is used as a perfume solubilizer or a solubilizer for essential oils.   The nonionic surfactant according to any one of claims 1 to 3, wherein the nonionic surfactant is used as a surfactant for dry cleaning.   A nonionic surfactant composition comprising 70 to 95% by weight of the nonionic surfactant according to any one of claims 1 to 8 and 5 to 30% by weight of water.