JP2952472B2 - Surfactant and liquid detergent composition using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a nonionic surfactant used as a detergent component and a liquid detergent composition using the same. More specifically, the present invention relates to a non-ionic surfactant used as a detergent at home, for example, a detergent used for dishwashing and clothing, a detergent in the textile industry, and a liquid detergent composition using the same.

[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, polyoxyalkylated higher alcohols and alkyl phenols. Surfactants are blended. As a detergent composition used in the textile industry, it is common to use polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, or a higher alcohol sulfate ester alone or in combination. 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, then propylene oxide, then ethylene oxide (eg, US 3
No. 758857, US Pat. No. 4,134,854).
4. Block adducts of ethylene oxide and propylene oxide (for example, JP-B-63-12192).
5. A product obtained by adding ethylene oxide after random addition polymerization of ethylene oxide and propylene oxide has been used (for example, JP-A-7-126690).

[0003]

[Problems to be solved by the invention] In the case of (1), although excellent in detergency, foaming is intense, the pour point is high, and an operation of heating when dissolving in water is necessary, and there is a problem that odor is generated when heating. 2. In the case of 2, the detergency, pour point and low foaming property are insufficient, and In the case of, the pour point is low and there is no need for heating, but low foaming,
Insufficient detergency. 4. In the case of (1), foaming is small but the detergency and pour point are insufficient. Also, 5. In case (1), the detergency and pour point are excellent, but the low foaming property is insufficient. The above 1. ~ 5. The liquid detergent composition using a surfactant has a high viscosity at a high concentration or at a low temperature, and is not only difficult to handle, but also has poor solubility in water, such as alcohol and glycol solvents. It was necessary to lower the viscosity by using a large amount of, and to increase the solubility in water. Also, 1.2.3. And 5. The detergent composition using the above surfactant has a disadvantage that troubles such as foaming at the time of washing, rinsing, and drainage are likely to occur. There is a need for balanced surfactants and detergents that have excellent detergency, low pour points, and low foaming.

[0004]

The present inventors have conducted intensive studies to solve these problems, and as a result, it has been found that a surfactant obtained by adding ethylene oxide and propylene oxide to a higher alcohol by a specific addition method has less foaming. Excellent detergency, low pour point, no need for heating when dissolving in water, no odor is generated, high concentration aqueous solution also has low viscosity, low viscosity even at low temperature, dissolution in cold water Have also been found to be excellent, and have reached the present invention. That is, the present invention relates to a surfactant represented by the following general formula (1) and a detergent composition using the same. Formula _{R-O - [(C 2} H 4 O) n / C 3 H 6 O) m] - (C 2 H 4 O) k- (C 3 H 6 O) rH (1) { wherein, R Represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, n is an integer of 1 to 8, m is an integer of 1 to 6, and k is 2-1.
The integer of 5 and r show the integer of 1-15. [(C ₂ H ₄ O)
n / C ₃ H ₆ O) m] indicates random addition. ｝

[0005] The surfactant represented by the general formula (1) can be usually produced by adding ethylene oxide and propylene oxide to a higher alcohol by a specific addition method. For example, a mixture prepared by adding an alkali or acid catalyst to a higher alcohol having 8 to 18 carbon atoms, randomly adding a mixture of ethylene oxide and propylene oxide under a nitrogen atmosphere, then adding ethylene oxide in a block, and then adding propylene oxide in a block. I do.

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. Examples of the aliphatic secondary alcohol include those obtained by oxidizing n-paraffin, and those described in Oil Chemistry, Vol. 21, No. 5, pp. 233-242 (1972).

In the above random addition, the mixture is composed of 1 to 8 mol of ethylene oxide and 1 to 6 mol of propylene oxide.
Is a mole. Preferably, 3 to 8 mol of ethylene oxide and 1 to 4 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. If the amount of propylene oxide is more than 6 mol, the detergency will be reduced. In the block addition, the number of moles of ethylene oxide added is 2 to 15 moles. Preferably, it is 3 to 12 moles of ethylene oxide. If the amount of ethylene oxide is less than 2 moles, the detergency decreases, and if it is more than 15 moles, the pour point increases and handling during use becomes difficult. In the block addition of terminal propylene oxide, the number of moles of propylene oxide to be added is 1 to 15 mol. Preferably it is 3 to 10 moles of propylene oxide. If the propylene oxide is less than 1 mol, foaming is large, and if it is more than 15 mol, the detergency decreases.

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 dissolves in water due to less foaming, excellent detergency, and a low pour point. Since there is no need for heating, there is no odor generated, and the high-concentration aqueous solution also has low viscosity, low viscosity even at low temperature, and excellent dissolution in cold water.

The surfactant of the present invention is usually contained in the detergent composition in an amount of 1 to 100% by weight, and the concentration of the surfactant in the washing solution is usually in the range of 0.001 g / L to 5 g / L. You.

The detergent composition containing the surfactant of the present invention may contain other nonionic surfactants (polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, fatty acid amide, etc.) if necessary. Anionic surfactants (such as alkyl ether sulfates, sulfated or carboxymethylated ethylene oxide adducts of fatty alcohols), builders (caustic soda,
Alkaline builders such as soda ash, ammonia, triethanolamine, sodium tripolyphosphate, EDTA, N
A chelating agent such as TA or polycarboxylic acid), a fluorescent agent, a bleaching agent, a softening agent, an enzyme, a disinfectant, a fragrance, a coloring agent and the like can be contained in necessary amounts. In addition, hydrophilic solvents (methanol,
Ethanol, isopropyl alcohol, ethylene glycol, propylene glycol, etc.), defoamers (silicone defoamers, pluronic defoamers, mineral oil defoamers, etc.) may be mixed or used in combination.

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

The detergent composition of the present invention is particularly useful for cleaning natural fibers, synthetic fibers, and blended and woven fibers thereof. Natural fibers include cotton, hemp, wool, etc., and synthetic fibers include regenerated cellulose fibers such as rayon and acetate, polyester, polyamide fibers, acrylic,
And synthetic fibers such as spandex. These blended interwoven fibers include cotton and hemp and other fibers (wool,
Polyester, polyamide, acrylic, etc.), wool and other fibers (polyester, polyamide, acrylic, etc.),
Polyester fiber and other fibers (rayon, acetate,
Polyamide fibers, acrylics, spandex, etc.) and polyamide fibers and other fibers (rayon, acetate, acrylic, spandex, etc.).

In the case of washing using the detergent composition of the present invention, there is no particular limitation on the washing method, and ordinary methods (hand washing in homes, washing machines, and industrial use with a winch or jet dyeing machine). Batch processing, continuous processing by a continuous scouring device, etc.) can be used. In the case of batch processing, the bath ratio is not particularly limited, but is usually 1: 4 to 1:40, preferably 1: 6 to 1:30.

The washing temperature can be arbitrarily selected depending on the type of the fiber to be applied, but is usually 5 to 140 ° C., preferably 20 to 130 ° C. The detergent composition of the present invention can be used in a desizing step and a bleaching step other than the washing step.

[0016]

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: 195, saturation, trade name: Dovanol 23 (manufactured by Mitsubishi Chemical Corporation) )] 155 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 140 g of ethylene oxide and 92 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, 175 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. Then, 138 g of propylene oxide was successively added dropwise. It took 1.5 hours to complete the dropping and 2 hours to completely reduce the pressure. Thereafter, the mixture was cooled to 60 ° C. and taken out to obtain 701 g of an alkylene oxide adduct. This is designated as surfactant A1.

Example 2 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, 111 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 200 g of ethylene oxide and 66 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. Next, 125 g of ethylene oxide was successively added dropwise. 0.5 by the end of dropping
It took 0.5 hours for the time and pressure to completely decrease. Next, 198 g of propylene oxide was successively added dropwise. It took 1.5 hours to complete the dropping and 2 hours to completely reduce the pressure. Then, cool to 60 ° C and take out.
01 g of an alkylene oxide adduct was obtained. This is designated as surfactant A2.

Example 3 Oxoalcohol (II) was placed in the same reaction vessel as in Example 1.
[Molecular weight 202, saturation, trade name: tridecanol (manufactured by Kyowa Hakko)] and potassium hydroxide were added in the amounts shown in Table 1 (hereinafter, all of the amounts in Table 1), and ethylene oxide and propylene oxide were added in the same manner as in Example 1. React the mixture,
Next, ethylene oxide was reacted, and then propylene oxide was reacted. Let the obtained alkylene oxide adduct be A3.

Example 4 In the same reaction vessel as in Example 1, oxo alcohol (II)
I) [Molecular weight 200, saturated, trade name Diamond Doll 11]
5H (manufactured by Mitsubishi Chemical Corporation)] and potassium hydroxide in the amounts shown in Table 1 (hereinafter, all of the amounts shown in Table 1) were added, and in the same manner as in Example 1,
A mixture of ethylene oxide and propylene oxide was reacted, then ethylene oxide was reacted, and then propylene oxide was reacted. Let the obtained alkylene oxide adduct be A4.

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

Comparative Example 2 Surfactant C was obtained by first adding propylene oxide to the oxo alcohol (II) in the amount shown in Table 2 and then adding ethylene oxide to the oxo alcohol (II).

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

Comparative Example 4 Ethylene oxide was first added to the oxo alcohol (II) in the amount shown in Table 2, and then propylene oxide was added. This is designated as surfactant E.

Comparative Example 5 Ethylene oxide and propylene oxide were first added to the oxo alcohol (II) in the amounts shown in Table 2 at random, and then ethylene oxide was added in blocks.
This is designated as surfactant F.

The pour points of the surfactants are shown in Tables 1 and 2. From the results in Tables 1 and 2, it can be seen that surfactants A1, A2, A3, and A4 of the present invention and surfactant F of Comparative Example 5 have low pour points and are preferable. Surfactant B obtained from ethylene oxide alone in Comparative Example 1 has a high pour point, requires heating during handling, and generates odor.

[0027]

[Table 1]

The symbols in Tables 1 and 2 mean the following. Note 1) EO is ethylene oxide, PO is propylene oxide, random is an addition reaction of a mixture of ethylene oxide and propylene oxide, and block is a single addition reaction of ethylene oxide or 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 ×;
20 ° C

[0029]

[Table 2]

Evaluation Example 1 A cleaning composition (a) was prepared at the following ratio, and the cleaning power was evaluated together with the surfactant alone. Surfactant 12 EDTA-2 sodium salt 0.03 Coconut oil fatty acid diethanolamide 8 (trade name Prophan 128 Extra manufactured by Sanyo Chemical Industries) Ethanol 1 Urea 5 Water 74

The detergency was evaluated by the Lenatsu method (JIS K3).
370). Rinatsu method test: (1) Washing / modeling Dirt adhered to glass dirt pieces (one set of 6 pieces), put this in 700 ml of sample solution, and used Rinatsu improved detergency tester (250 rpm) Wash at 30 ° C. for 3 minutes. (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, and A4 of the present invention have good detergency for the detergent alone and the detergency of the detergent composition, and are equivalent to Comparative Examples 1 and 5. , And Comparative Examples 2, 3, and 4.

[0033]

[Table 3]

Note) The detergency% is indicated by ○ when it is 70% or more, and Δ when it is 60% or more and less than 70%.

Evaluation Example 2 A cleaning composition (b) was prepared at the following ratio, and the cleaning power was evaluated together with the surfactant alone. Surfactant 40 Citric acid 1 Triethanolamine 5 Propylene glycol 5 Alcalase 2.5L 0.4 Water 48.6

The evaluation of the detergency was carried out according to the method recommended by the Japan Oil Chemists' Society 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 rpm for 10 minutes at 25 ° 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, and A4 of the present invention had good detergency for the detergent alone and the detergency of the detergent composition, and were equivalent to Comparative Examples 1 and 5. It is superior to Examples 2, 3 and 4.

[0038]

[Table 4]

Note) Detergency% is indicated by ○ when it is 32% or more, and Δ when it is 20% or more and less than 32%.

The detergent composition (b) was cooled to 5 ° C., and the results of measuring the viscosity and solubility in cold water (8 ° C. water) are shown in Table 5. The results in Table 5 show that the detergent composition using the surfactant of the present invention has a low viscosity even at a low temperature and has excellent solubility in cold water.

[0041]

[Table 5]

Note) Those having a viscosity of 500 cP or less
Those with a value of 100 to 1000 cP were represented by Δ, and those with 1000 cP or more were represented by x. Also, 5 g of the detergent composition (b) cooled to 5 ° C is taken into a 200 mL beaker, and 100 mL of ion-exchanged water at 8 ° C is gently poured from above, and the detergent composition (b) dissolves in 20 seconds or less. The sample was represented by ○, the sample dissolved in 20 to 60 seconds was indicated by Δ, and the sample dissolved by 60 seconds or more was indicated by ×.

Evaluation Example 3 A detergent composition (c) was prepared in the following ratio, and 1.5 L of a 0.1% aqueous solution thereof was used with a high-pressure jet liquid flow foaming tester (manufactured by Tsujii Dyeing Machine Co., Ltd.). , 50 ° C and 90 ° C were evaluated. Surfactant 20 Potassium oleate 8 Sodium salt of carboxymethylated product of lauryl alcohol ethylene oxide 2 mol adduct 5 EDTA-4 sodium salt 1 Isopropyl alcohol 1 Water 65 From the results in Table 6, the surfactant of the present invention was used. It can be seen that the foaming of the cleaning composition was low as in Comparative Example 4.

[0044]

[Table 6]

Note) ○: Bubble height of 20 mm or less
Those of 20 to 50 mm were represented by Δ, and those of 50 mm or more were represented by X.

[0046]

The surfactant of the present invention has low foaming,
Excellent detergency, low pour point, no need for heating when dissolved in water, no odor.Highly concentrated aqueous solution also has low viscosity, low viscosity even at low temperature, solubility in cold water Are well-balanced surfactants that also have the advantage of being excellent.

──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. ⁶ , DB name) C11D 1/72-1/722 B01F 17/42 CA (STN)

Claims (5)

(57) [Claims] 1. A nonionic surfactant (A) represented by the following general formula (1). Formula _{R-O - [(C 2} H 4 O) n / C 3 H 6 O) m] - (C 2 H 4 O) k- (C 3 H 6 O) rH (1) { wherein, R Represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, n is an integer of 1 to 8, m is an integer of 1 to 6, and k is 2-1.
The integer of 5 and r show the integer of 1-15. [(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,
The surfactant according to claim 1, wherein m is a number of 1 to 4, k is 3 to 12, and r is a number of 3 to 10. 3. R in the general formula (1) is a compound having 8 to 8 carbon atoms.
18. A residue of an aliphatic saturated primary alcohol of 18
Or the surfactant according to 2. 4. A liquid detergent composition comprising the nonionic surfactant (A) according to claim 1. 5. The liquid detergent composition according to claim 4, which is used for cleaning a knitted or woven fabric containing cellulose fibers, synthetic fibers, wool, silk or acetate fibers.