JP2700293B2 - Surfactant - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to surfactants. More particularly, it relates to a surfactant used as a detergent component.

[0002]

2. Description of the Related Art Conventionally, detergents used for washing at home, for example, for dishwashing and clothing, generally include alkyl sulfates, fatty acid amides, alkali metal salts of inorganic acids, and polyoxyalkylated higher alcohols and alkylphenols. Such a surfactant is blended. In the case where the surfactant to be blended is a polyoxyalkylated higher alcohol, it is conventionally 1. 1. ethylene oxide adducts;
Block adducts of propylene oxide and ethylene oxide (for example, JP-A-53-58508 and JP-A-59-164743). 3. Block adducts of ethylene oxide followed by propylene oxide followed by ethylene oxide have been used (eg, US
No. 3,752,857, US Pat. No. 4,134,854).

[0003]

[Problems to be solved by the invention] In the case of (1), although the washing power is excellent and the number of manufacturing steps and the manufacturing time are shortened, the pour point is high and an operation of heating is required in handling, and there is a problem that odor is generated during heating.
2. Is insufficient in all of the detergency, the number of production steps, the production time and the pour point. Also, 3. In the case of (1), although the pour point is low and heating is not required, the number of steps in the production increases, and the detergency is insufficient. There is a demand for a balanced surfactant that has excellent detergency, low pour point, and does not require a long number of production steps and time.

[0004]

Means for Solving the Problems As a result of intensive studies to solve these problems, the present inventors have found that a surfactant obtained by adding ethylene oxide and propylene oxide to a higher alcohol by a specific addition method has a detergency. The present invention was found to be excellent, has a low pour point, does not require heating, does not generate odor, and does not increase the number of production steps and time. That is, the present invention is a surfactant represented by the following general formula (1). General formula R—O — [(C ₂ H ₄ O) _n / (C ₃ H ₆ O) _m ] — (C ₂ H ₄ O) _k H (1) An aliphatic hydrocarbon group, n is a number of 1 to 8, m is a number of 1 to 5, k is a number of 2 to 10, [(C ₂ H ₄ O) _n / (C ₃ H ₆ O ) _M ] indicates random addition. ｝

[0005] The surfactant represented by the general formula (1) is usually produced by adding ethylene oxide and propylene oxide to a higher alcohol by a specific addition method.

The aliphatic hydrocarbon alcohols having 8 to 18 carbon atoms include saturated or unsaturated, primary, secondary and tertiary alcohols. Preferred among these are aliphatic saturated primary alcohols. 10 to 1 carbon atoms
8 is preferred. The number of carbon atoms may be constant or a mixture.

Specific examples of the aliphatic saturated primary alcohol include decyl alcohol, lauryl alcohol, stearyl alcohol, and alcohol synthesized using a Ziegler catalyst [for example, ALFOL 1214 (COND).
EA)], alcohols produced by oxo synthesis [for example, Dovanol 23, 25, 45 (manufactured by Mitsubishi Yuka), tridecanol (manufactured by Kyowa Hakko), oxocols 1213, 1215, 1415 (manufactured by Nissan Chemical), Diamond Doll 115-L, 115H, 135 (Mitsubishi Chemical)
Is mentioned.

The surfactant represented by the general formula (1) is prepared by adding an alkali or acid catalyst to a higher alcohol having 8 to 18 carbon atoms and subjecting a mixture of ethylene oxide and propylene oxide to a random mixture under a nitrogen atmosphere as in a conventional method. And then block addition of ethylene oxide.

In the above random addition, the mixture is composed of 1 to 8 mol of ethylene oxide and 1 to 5 mol of propylene oxide.
Is a mole. Preferably, 3 to 8 mol of ethylene oxide and 1 to 3 mol of propylene oxide are used. If the amount of ethylene oxide is more than 8 mol, the pour point becomes high and handling during use becomes difficult. On the other hand, when the propylene oxide content is more than 5 mol, the detergency decreases. In the block addition, the number of moles of ethylene oxide added is 2 to 10 moles. Preferably, it is 3 to 8 mol of ethylene oxide. If the amount of ethylene oxide is less than 2 mol, the detergency decreases, and if it is more than 10 mol, the pour point becomes high and handling during use becomes difficult.

When the surfactant of the present invention is prepared by adding ethylene oxide and propylene oxide to a higher alcohol by a specific addition method, the surfactant has excellent detergency, has a low pour point, and does not require heating, thereby generating odor. And the number of manufacturing steps and time are not long. The specific addition method referred to here is a method in which a mixture of ethylene oxide and propylene oxide is first added at random, and then ethylene oxide is added in a block manner. The pour point is lowered by random addition of propylene oxide together with ethylene oxide. Since the temperature is lower by about 15 ° C. or more than that obtained by adding only ethylene oxide to a higher alcohol, it is easy to handle when mixed with other components to form a detergent. Since there is no need for heating, there is no generation of odor due to heating. With regard to the number and time of the production steps, this addition method has an advantage that the number of steps is one step and the time is reduced by about 30% compared to the method of adding blocks in the order of ethylene oxide, propylene oxide and ethylene oxide.

The detergent containing the surfactant of the present invention generally contains mainly alkyl ether sulfates, fatty acid amides, alkali metal salts of inorganic acids, and the like. The surfactant of the present invention usually contains 1 to 45% by weight of a detergent.
Contained. Alkyl ether sulfates include C
12 to C15 higher alkyl ether sulfates and the like.
0 to 50% by weight is contained. Fatty acid amides include coconut oil fatty acid diethanolamide and the like, and are contained in an amount of 1 to 10% by weight. Sodium ,, sodium aluminosilicate paratoluenesulfonic acid as an alkali metal salt of an inorganic acid, potassium aluminosilicate, sodium metasilicate, sodium orthosilicate, sodium carbonate, Sekisu sodium carbonate, sodium sulfate, zeolite (Na ₂ · 2Si
O ₂ · 4.5H ₂ O).
９０90% by weight.

The detergent containing the surfactant of the present invention can contain a required amount of a metal ion scavenger, a fluorescent agent, a bleaching agent, an enzyme, a disinfectant, etc., if necessary.

The surfactant of the present invention can be used not only as a detergent for washing dishes and clothes, but also as an industrial detergent such as a refining agent for textiles, a deinking agent for collecting used paper, and a metal degreasing agent.

[0014]

EXAMPLES The present invention will be further described with reference to examples below, but the present invention is not limited to these examples.

Example 1 In a 1 L autoclave equipped with a stirrer, a thermometer, a pressure gauge, a pressure dropping funnel, a reduced pressure and a nitrogen introduction line, oxo alcohol (I) [molecular weight 202, saturation, trade name Tridecanol (manufactured by Kyowa Hakko) 198 g, potassium hydroxide 1.
3 g was added, stirring was started, nitrogen was sealed and the temperature was raised to 90 ° C., followed by stirring at a pressure of −76 cmHg for 1 hour. Then 150 ± 1
The temperature was raised to 0 ° C., and a mixture of 215 g of ethylene oxide and 114 g of propylene oxide was successively dropped at a pressure of −76 cmHg to 6 kg / cm ² . It took 1 hour to complete the dropping and 2 hours to completely reduce the pressure. Then, 172 g of ethylene oxide was sequentially dropped. It took 0.5 hour to complete the dropping and 0.5 hour to completely reduce the pressure. Thereafter, the mixture was cooled to 60 ° C. and taken out to obtain 700 g of an alkylene oxide adduct. This is designated as surfactant A1.

Example 2 In a 1 L autoclave equipped with a stirrer, thermometer, pressure gauge, pressure dropping funnel, reduced pressure and nitrogen introduction line, 175 g of natural reduced alcohol [molecular weight: 186, saturation, trade name: Calcol 20 (manufactured by Kao)] Then, 1.3 g of potassium hydroxide was added, stirring was started, nitrogen was sealed and the temperature was raised to 100 ° C., followed by stirring at a pressure of −76 cmHg for 1 hour. Then, the temperature was raised to 150 ± 10 ° C., and a mixture of 248 g of ethylene oxide and 110 g of propylene oxide was sequentially dropped at a pressure of −76 cmHg to 6 kg / cm ² . It took 1 hour to complete the dropping and 2 hours to completely reduce the pressure. Then, 166 g of ethylene oxide was sequentially dropped. 0. by the end of dropping.
It took 5 hours and 0.5 hours for the pressure to drop completely.
Thereafter, the mixture was cooled to 60 ° C. and taken out to obtain 700 g of an alkylene oxide adduct. This is called surfactant A2
And

Example 3 In the same reactor as in Example 1, oxo alcohol (II)
[Molecular weight: 200, saturation, trade name: Diamond Doll 115H
(Manufactured by Mitsubishi Kasei)] and potassium hydroxide in the amounts shown in Table 1 (hereinafter all shown in Table 1), and reacted with a mixture of ethylene oxide and propylene oxide in the same manner as in Example 1, followed by reaction of ethylene oxide. The resulting alkylene oxide adduct is referred to as surfactant A3.

Example 4 The above oxo alcohol (II) and catalyst were added in the amounts shown in Table 1 (the same applies hereinafter), and a mixture of ethylene oxide and propylene oxide was reacted in the same manner as in Example 1, followed by reaction of ethylene oxide. The resulting adduct is referred to as surfactant A4.

Example 5 An oxo alcohol (III) [molecular weight: 195, saturation, trade name: Dovanol 23 (manufactured by Mitsubishi Yuka)] and a catalyst were added in the amounts shown in Table 1 (the same applies hereinafter), and ethylene oxide was prepared in the same manner as in Example 1. And a mixture of propylene oxide,
Next, the adduct obtained by reacting ethylene oxide is referred to as surfactant A5.

Comparative Example 1 Only the ethylene oxide was added to the oxo alcohol (I) in the amounts shown in Table 2. This is designated as surfactant B.

Comparative Example 2 Propylene oxide was first added to the above oxo alcohol (I) in the amount shown in Table 2, and then ethylene oxide was added in a block form to obtain surfactant C.

Comparative Example 3 Ethylene oxide was first added to the oxo alcohol (I) in the amount shown in Table 2, then propylene oxide was added, and finally ethylene oxide was added. This is designated as surfactant D.

Tables 1 and 2 show the pour point of the surfactant, the number of production steps and the production time. From the results in Tables 1 and 2, the surfactants A1, A2, A3, A
4. It is found that the pour point of A5 is low and is preferable, and the number of steps of the production is small and the production time is not long. Comparative Example 1
Surfactant B obtained from ethylene oxide alone
Although the number of manufacturing steps is small and the manufacturing time is short, the pour point is high, and heating is required during handling, and odor is generated.

[0024]

[Table 1] The symbols in Tables 1 and 2 mean the following. Note 1) EO is ethylene oxide, PO is propylene oxide, and (EO / PO) is a mixture of ethylene oxide and propylene oxide. Note 2) Pour point: (Measurement is carried out using a pour point / cloud point measuring device of ISL.) ；; -15 to 5 ° C, Δ to ×; 10 to 15 ° C., ×;
20 ° C Note 3) Time required ○: 2 hours, △: 4 hours,
×; 6 hours Number of steps ○; 1, △;
×; 3

[0025]

[Table 2]

Evaluation Example 1 A detergent composition (a) was prepared at the following ratio, and the cleaning power was evaluated together with the surfactant alone. Surfactant 6 C12-C15 higher alkyl ether sulfate 44 (trade name, Sandet END, manufactured by Sanyo Chemical Industries) Palm oil fatty acid diethanolamide 3 (trade name, Prophan 128 Extra, manufactured by Sanyo Chemical Industries) Water 47

The evaluation of the detergency was carried out by the Linatu method (JIS K3).
370). Renauts method test: (1) Cleaning, model stained glass pieces (6
Stain is adhered to one set of sheets), put into 700 ml of a sample solution, and washed at 30 ° C. for 3 minutes using a Linatu improved detergency tester (250 rpm). (2) The rinsed and washed model stained glass pieces are placed in 700 ml of water, and washed at 30 ° C. for 1 minute using a Renauts improved detergency tester. Detergency% = {(B−C) / (B−A)} × 100 A: Weight before attaching dirt to model stained glass pieces (one set of six) B: Weight after attaching dirt C: 〃 The sample solution used was a single product and a 0.15% aqueous solution of the detergent composition (a).

Table 3 shows the detergency test results of the single product and the detergent composition (a). The results in Table 3 show that the surfactants A1, A2, A3, A4, and A5 of the present invention had good detergency for the detergent alone and the detergency of the detergent composition, and were equivalent to Comparative Example 1. It is superior to Examples 2 and 3.

[0029]

[Table 3] Note: Detergency% is 70% or more, ○, 60% or more, and 70%
Less than% is represented by Δ.

Evaluation Example 2 A detergent composition (b) was prepared at the following ratio, and the detergency was evaluated together with the surfactant alone. Surfactant 20 Sodium carbonate 58 Sodium metasilicate 7 Zeolite 15

The evaluation of the detergency was carried out according to the method recommended by the Japan Oil Chemistry Association committee. Carbon black contaminated cloth method: (1) Cleaning and cleaning equipment is Terg-O-tomete of UUTesting
Using r, put 10 pieces of carbon black-contaminated cloth and 3 pieces of sepam cloth with 60 mg of organic stain per sheet,
The bath ratio was adjusted to 30 times with a knitted cloth and washed at 120 ° C. for 10 minutes at 30 ° C. The washing solution is 900ml. 30
Uses 0 ppm hard water. (2) Rinse. Performed twice for 3 minutes. _{Detergency% = {(R W -R S} ) / (R I -R S)} × 100 R I: reflectance of clean cloth, R _W: reflectance of the cleaning cloth, R _S: reflectance of soiled cloth Using a Hunter whiteness meter As a sample solution, a single product and a 0.025% aqueous solution of the cleaning composition (b) were used.

Table 4 shows the detergency test results of the single product and the detergent composition (b). The results in Table 4 show that the surfactants A1, A2, A3, A4, and A5 of the present invention had good detergency for the detergent alone and the detergency of the detergent composition, and were equivalent to Comparative Example 1. It is superior to Examples 2 and 3.

[0033]

[Table 4] Note) Detergency% is 32% or more, ○, 20% or more, and 32
Less than% is represented by Δ.

[0034]

The surfactant of the present invention is excellent in detergency, has a low pour point, does not need to be heated at the time of blending into a detergent composition, and does not generate odor. It is not long and is a well-balanced surfactant.

 ────────────────────────────────────────────────── ─── Continuation of the front page Examiner Yoshihisa Seki (56) References JP-A-53-113805 (JP, A) JP-A-57-108198 (JP, A) JP-A-58-217598 (JP, A) JP-A-60-255898 (JP, A) JP-A-61-293541 (JP, A) JP-A-63-159500 (JP, A) JP-A-3-503168 (JP, A) JP-A 33-2798 (JP, B1) JP-B-63-20567 (JP, B2) JP-B-63-19558 (JP, B2) JP-B 2-16956 (JP, B2)

Claims (3)

(57) [Claims] 1. A surfactant represented by the following general formula (1). General formula R—O — [(C ₂ H ₄ O) _n / (C ₃ H ₆ O) _m ] — (C ₂ H ₄
O) _k H (1) In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, n is a number of 1 to 8, m is a number of 1 to 5,
k represents a number of 2 to 10, and [(C ₂ H ₄ O) _n / (C ₃ H
₆ O) _m ] indicates random addition. ｝ 2. In the general formula (1), n is a number of 3 to 8, m
Is a number of 1 to 3, and k is a number of 3 to 8. 3. The surfactant represented by the general formula (1):
3. The surfactant according to claim 1, which is derived from an aliphatic saturated primary alcohol having 8 to 18 carbon atoms.