JPH1036885A - Surfactant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an anionic surfactant which is excellent in detergency, has a low flow point, does not emit an odor, and can dispense with the use of a cheating agent in hard water by bonding an anionic group to an ethylene oxide/propylene oxide adduct of a higher alcohol, the adduct being formed by addition reacting in a specified manner. SOLUTION: This surfactant is represented by formula I wherein R is an 8-18C aliph. hydrocarbon group; n is 1-11; m is 1-5; k is 0-10; in (OC2 H4 )n /(OC3 H6 )m , ethylene oxide units and propylene oxide units are linked randomly; and A is -OSO3 X, -OCH2 COOX, or a group represented by formula II [wherein Q is R-[(OC4 H4 )n /(OC1 H4 )k - or X; R is an 8-18C aliph. hydrocarbon group; n is 1-11; m is 1-5; k is 0-10; in (C2 H4 O)n /(C3 H6 O)m , ethylene oxide units and propylene oxide units are linked randomly; and X is a cationic group]}. A mixture comprising 2-20mol of ethylene oxide and 1-3mol of propylene oxide (based on 1 mol of a higher alcohol) is subjected to random addition reaction and then 3-10mol of ethylene oxide is subjected to block addition reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a surfactant. More particularly, it relates to a surfactant used as a detergent component.

[0002]

2. Description of the Related Art Conventionally, detergent formulations used for washing at home, for example, for dishwashing and clothing, generally include alkyl sulfonates, alkyl sulfonate esters, fatty acid amides, alkali metal salts of inorganic acids, and polyamines. Components such as oxyalkylated higher alcohols and alkylphenols are blended. In the case where the surfactant to be blended is an anionic surfactant obtained by adding an anionic group to a polyoxyalkylated higher alcohol, a conventional anionic surfactant is used. 1. a higher alcohol to which ethylene oxide is added and an anion group is added thereto; 2. higher alcohols obtained by adding an anion group to a block adduct of propylene oxide and ethylene oxide; Those obtained by adding an anionic group to a higher alcohol, ethylene oxide, then propylene oxide, and then a block adduct of ethylene oxide have been used. For example, when used in detergents used for dishwashing and clothing, depending on the formulation, a chelating agent may be required when used in hard water.

[0003]

However, in the case of (1), there is a problem that an operation of heating is required at the time of handling at a high pour point and a low temperature, or an odor is generated at the time of heating. Also in the case of No. 2, there is a problem that the lowering of the pour point is insufficient. Further, the case 3 has the same problem as the case 2 and also has a drawback that the number of steps in the production is large. In addition, there is a disadvantage that a chelating agent is required when used in hard water when incorporated in a detergent. There is a need for a surfactant that has excellent detergency, low pour point, does not require a long number of production steps and time, and does not require the use of a chelating agent in hard water when incorporated into a detergent.

[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 an anionic group to a higher alcohol obtained by adding ethylene oxide and propylene oxide by a specific addition method. However, it has excellent detergency, low pour point, does not require heating when handled at low temperatures, does not generate odors, does not require a long number of manufacturing steps and time, and when formulated in detergents, is a chelating agent in hard water. The inventors have found that the surfactant is an excellent surfactant that does not need to be used, and arrived at the present invention. That is, the present invention is an anionic surfactant represented by the following general formula (1). _{R - [(OC 2 H 4} ) n / (OC 3 H 6) m] - (OC 2 H 4) k -A (1) { wherein, R an aliphatic hydrocarbon group having 8 to 18 carbon atoms N is a number of 1 to 11, m is a number of 1 to 5, k is a number of 0 to 10, and [(C ₂ H ₄ O) _n / (C ₃ H ₆ O) _m ] is a random addition Is shown. A is -OSO ₃ X, -OCH ₂ COOX or And Q is R-[(OC ₂ H ₄ ) _n / (OC ₃ H ₆ ) _m ].
— (OC ₂ H ₄ ) _k − or X, and R represents a carbon number of 8 to
18 represents an aliphatic hydrocarbon group, n represents a number of 1 to 11, m represents a number of 1 to 5, k represents a number of 0 to 10, and [(C ₂ H ₄ O) _n
/ (C ₃ H ₆ O) _m ] indicates random addition. X represents a cationic group. ｝

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The surfactant represented by the general formula (1) is usually produced by adding an anionic group to a higher alcohol obtained by adding ethylene oxide and propylene oxide by a specific addition method.

The higher alcohol to which the alkylene oxide is added is an aliphatic hydrocarbon alcohol having 8 to 18 carbon atoms and includes saturated, unsaturated, primary, secondary and tertiary alcohols. Preferred among these are aliphatic saturated primary alcohols. 10 carbon atoms
To 18 are 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 Chemical), tridecanol (manufactured by Kyowa Yuka), oxocols 1213, 1215, 1415 (manufactured by Nissan Chemical), Diamond Doll 115-L, 115H, 135 (Mitsubishi Chemical)
Is mentioned.

The polyoxyalkylated higher alcohol used for 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 in a nitrogen atmosphere as in a usual method. , A mixture of ethylene oxide and propylene oxide can be added at random, and then a predetermined amount of ethylene oxide can be added in a block to produce the mixture.

In the above random addition, the mixture is composed of 1 to 11 mol of ethylene oxide and 1 to 1 mol of propylene oxide.
5 moles. If the amount of ethylene oxide is more than 11 mol, the pour point will be high, and it will be difficult to handle when used at low temperatures. On the other hand, when propylene oxide is more than 5 mol, the detergency decreases when it is blended with a detergent. In the block addition, the number of moles of ethylene oxide added is 0 to 10 moles. If it is larger than 10 mol, the pour point will be high, and it will be difficult to handle at a low temperature because it is blended into a detergent. In the random addition, the mixture is preferably 2 to 10 moles of ethylene oxide, 1 to 3 propylene oxides.
Is a mole. In the block addition, the number of moles of ethylene oxide added is preferably 3 to 10 moles.

In the production of the polyoxyalkylated higher alcohol used in the surfactant of the present invention, ethylene oxide and propylene oxide are added to the higher alcohol by a specific addition method. 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 at a low temperature during the preparation in the anionization step. In addition, since the anionized surfactant of the general formula (1) also has a low pour point,
It is easy to handle when it is mixed with other components at low temperature in winter to make a detergent. Since there is no need for heating, there is an advantage that no odor is generated due to heating. In addition, since it is not necessary to use a chelating agent in hard water when incorporated into a detergent, there is also an advantage that a compact detergent formulation having a high active ingredient acting on washing can be obtained.

In the production of the surfactant of the present invention, a higher alcohol to which ethylene oxide and propylene oxide are added by a specific addition method is used. General formula (1)
An example of a method for inserting an anion group of A in the following is as follows.

When A is —OSO ₃ X, the cationic group X is N
H ₄ , Na, K and the like. When X is NH _4, an approximately equivalent amount of sulfamic acid is added dropwise while stirring the polyoxyalkyl higher alcohol at about 50 ° C., and the mixture is reacted at about 100 ° C. to obtain a sulfate.

When X is Na or K, an approximately equivalent amount of chlorosulfonic acid is added dropwise while stirring the polyoxyalkyl higher alcohol and reacted at about 100 ° C. to form a sulfate ester, followed by NaOH or KOH in a conventional manner. Obtained by neutralization.

When A is --OCH ₂ COOX, X is an alkali metal, alkaline earth metal, ammonium or alkanolamine. In the case of an alkali metal or alkaline earth metal, a polyoxyalkyl higher alcohol is converted into an alcoholate, and monochloroacetic acid is added dropwise with stirring.
It is obtained by reacting with alcoholoxyacetic acid and neutralizing with NaOH, KOH or Mg (OH) ₂ .

When X is ammonium or alkanolamine, alcoholoxyacetic acid is formed in the same manner as described above, and ammonia,
It is obtained by neutralization with mono-, di- or tri-ethanolamine.

[0016] X includes Na, K and the like. When Q is X, ie, -OPO ₃ Na ₂ or -OPO ₃ K ₂ , phosphoric acid (H ₃ PO ₄ ) is added dropwise while stirring a polyoxyalkyl higher alcohol and reacted to form a phosphate ester. NaOH or K
Obtained by neutralizing with OH.

Q is R-[(OC ₂ H ₄ ) _n / (OC
_{3 H 6) m] - (} OC 2 H 4) k - where stirring polyoxyalkylated higher alcohol was added dropwise phosphorus pentoxide (P ₂ O _5), and a phosphoric acid ester is reacted, NaOH or KO
Obtained by neutralizing with H.

As described above, when the surfactant of the present invention is used for a detergent, it is generally used as an alkyl sulfonate, an alkyl sulfonate, a polyoxyalkyl higher alcohol, a fatty acid amide, an alkali metal salt of an inorganic acid, or the like. Formulated with At that time, the surfactant of the present invention is usually contained in the detergent in an amount of 10 to 50% by weight. Examples of the polyoxyalkyl higher alcohol include an adduct of lauryl alcohol and ethylene oxide, an adduct of ethylene oxide of an alcohol produced by oxo synthesis (for example, Dovanol 23), and 1 to 10% by weight. Fatty acid amides include coconut oil fatty acid diethanolamide and the like, and are contained in an amount of 1 to 10% by weight. Examples of the alkali metal salt of an inorganic acid include sodium paratoluenesulfonate and the like, which is contained in an amount of 1 to 10% by weight.

The surfactant of the present invention can be used not only as a dishwashing and clothing detergent, but also as an industrial detergent such as a refining agent, a deinking agent, a metal degreasing agent, and a wet emulsifier for the textile industry.

[0020]

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 A stirrer, a thermometer, a dropping funnel and a nitrogen introduction line were provided.
In a 1 L autoclave, polyoxy higher alcohol C ₁₂
613 g of O- (EO _4.5 / PO ₂ )-(EO) _2.5 -H is charged, stirring is started, and the temperature is raised to 50 ° C. at room temperature while bubbling nitrogen from the liquid. While dropping 98 g of sulfamic acid at the same temperature, the temperature was raised to 100 ° C. in 0.5 hours, and the dropping was completed. Thereafter, the reaction is performed at 100 ± 5 ° C. for 5 hours. Sulfation rate of 711 g 9
4.3% of a pale yellow liquid was obtained. This is designated as polyoxy alcohol anionized product (A).

Example 2 As in Example 1, polyoxy higher alcohol C ₁₂ O- (EO ₇
613 g of / PO ₂ ) -H are reacted with 98 g of sulfamic acid. 711 g of a pale yellow liquid having a sulfation rate of 93.2% were obtained. This is designated as polyoxyalcohol anionized compound (a).

Comparative Example 1 In the same manner as in Example 1, polyoxy higher alcohol C ₁₂ O- (E
O) 497 g of _7- H was charged and 98 g of sulfamic acid was added dropwise to react. 595 g of a pale yellow liquid having a sulfation ratio of 95.6% were obtained. This is designated as polyoxy alcohol anionized product (C).

Comparative Example 2 In the same manner as in Example 1, polyoxy higher alcohol C ₁₂ O- (P
O) 305 g of _2- H and 98 g of sulfamic acid are reacted. 403 g of a pale yellow liquid having a sulfation rate of 99.8% were obtained. This is designated as polyoxy alcohol anionized compound (d).

Comparative Example 3 As in Example 1, polyoxy higher alcohol C ₁₂ O- (P
393 g of O ₂ EO ₂ ) -H was reacted with 98 g of sulfamic acid to obtain 491 g of a pale yellow liquid. This is designated as polyoxy alcohol anionized compound (e).

Comparative Example 4 Polyoxy higher alcohol C ₁₂ O- (EO) _3-
After adding 118 g of chlorosulfonic acid dropwise to 321 g of H and stirring for 1 hour, 42.1 g of caustic soda (95% product) was added.
And neutralized. 443.5 g of a pale yellow liquid were obtained. This is designated as polyoxy alcohol anionized compound (f).

The viscosities and pour points of the polyoxy higher alcohols and polyoxyalcohol anionates are shown in Examples 1 and 2 and Comparative Examples 1 to 4 in Table 1.

[0028]

[Table 1] A: C ₁₂ O- (EO _4.5 / PO ₂ )-(EO) _2.5 -H A: C ₁₂ O- (EO ₇ / PO ₂ ) -H C: C ₁₂ O- (EO) ₇ -H D: C ₁₂ O- (PO) ₂ -H O: C ₁₂ O- (PO) ₂ (EO) ₂ -H F: C ₁₂ O- (EO) ₃ -H (A): C ₁₂ O- (EO _4.5 / PO ₂ )-(EO) _2.5 -SO ₃ NH ₄ (A): C ₁₂ O- (EO ₇ / PO ₂ ) -SO ₃ NH ₄ (C): C ₁₂ O- (EO) ₇ -SO ₃ NH ₄ ( D): C ₁₂ O- (PO) ₂ -SO ₃ NH ₄ (o): C ₁₂ O- (PO) ₂ (EO) ₂ -SO ₃ NH ₄ (f): C ₁₂ O- (EO) _3- SO ₃ Na Viscosity ^{* 1} : 5 ° C, B-type viscometer, CPS. Viscosity * ² : 25 ° C ○ 8,200-8,500 CPS., △ ～ × Semi-solid, × Solid

As can be seen from Table 1, Examples 1 and 2
In C ₁₂ higher alcohol - despite the addition molar number of EO that EO7 mol Le is large, viscosity ^{* 1,} viscosity ^{* 2} both low and easy to handle since less pour point. On the other hand, in Comparative Examples 1 to 4, the viscosity ^{* 1} was low because the number of moles of added PO or EO was small, but the viscosity * ² was semi-solid or solid and had a high pour point, requiring a lot of trouble in handling.

Examples 3 and 4, Comparative Examples 5 to 8 Using the polyoxyalcohol anionized products prepared in Table 1, a detergent composition was formulated according to the following formulation, and the performance was evaluated. The results are shown in Table 2. .

Polyoxyalcohol anionized product 18 Coconut oil fatty acid diethanolamide 2 (trade name Prophan 128 Extra, manufactured by Sanyo Chemical Industries) Water Remaining ------------------------------- −−−−−−−−−−−−−−−−−− Total 100

The evaluation of the detergency (1) is based on the Linatu method (JIS).
K3370), the foaming power was tested by the Ross Miles method,
The results are shown in Table 2. Renauts method test: (1) Cleaning, model stained glass pieces (6
Stains on each sheet). This is the sample solution 700m
l, and a Rinatsu improved detergency tester (250 r.p.
m.) and 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 weight of the sample after washing after washing was 0.1% aqueous solution of the detergent composition.

[0033]

[Table 2] Viscosity ^{* 2} (same as Table 1 viscosity ^{* 2} ) Foaming force (immediately) seconds: 159 to 152, 〜 151 to 139, × 138 to 88 〃 (after 5 minutes) seconds: 157 to 148, △ 147 to 134, × 133 to 65 Detergency (1): ○ 98% or more, △ Less than 98% to 90%

In Table 2, the polyoxyalcohol anionized products of Examples 3 and 4 were prepared by using
Foaming power (immediately), (after 5 minutes), and detergency are all good. In Comparative Examples 5 and 8, the foaming power (immediately) and (after 5 minutes) and the detergency were good, but the viscosity was slightly poor or poor. Comparative Examples 6 and 7 are inferior in viscosity, foaming power (immediately), (after 5 minutes), and detergency.

Example 5, Comparative Examples 9 to 11 Detergent compositions were prepared at the ratios shown in Table 3, and the foaming power and detergency in water having high hardness were measured.

[0036]

[Table 3] (A): Polyoxy alcohol anionate (A) C ₁₂ O- (EO _4.5 / PO ₂ )-(EO) _2.5 -SO ₃ NH ₄ LAS: Sodium dodecylbenzenesulfonic acid chelating agent: Tripolyphosphoric acid The test of soda foaming power and detergency used a 0.04% calcium chloride aqueous solution. Foaming power (immediately) seconds: 151 151-140, △ 139-129, × 128 or less 〃 (after 5 minutes) seconds: ○ 144-131, △ 130-100, × 99 or less Detergency (2): ○ 98 % Or more, △ less than 98% to 90%

The detergency (2) was evaluated by the following method, and the foaming power was tested by the Ross-Miles method. Detergency: Using a Terg-O-Tometer, an artificially stained cloth (manufactured by Washing Science Association) was washed under the following conditions. Washing condition: 30 ° C., 10 minutes; Rinse condition: 3 minutes, twice Bath ratio: 1:30; Bath concentration: 0.15% The reflectance of the cloth was measured, and the washing power was determined from the following equation. Detergency% = {(CB) / (AB)} × 100 A: reflectance of white cloth before cleaning B: reflectance of cloth before cleaning C: reflectance of cloth after cleaning

As can be seen from Table 3, Example 5 shows good foaming power and detergency in calcium ion water without using a chelating agent. Comparative Examples 9 and 10 are formulations mainly composed of an alkyl sulfonate salt. A comparison between a formulation containing a chelating agent and a formulation containing no chelating agent shows that Comparative Example 10 without a chelating agent has significantly reduced foaming power and detergency. I have. Example 5 using anionized (A) is superior in foaming power and detergency to Comparative Example 11 in which anionization is not performed.

[0039]

The surfactant of the present invention is excellent in detergency, has a low pour point, does not need to be heated when compounded in the detergent composition, and does not generate odor. It is an excellent surfactant that does not require the use of a chelating agent.

Claims (5)

[Claims] 1. An anionic surfactant represented by the following general formula (1). _{R - [(OC 2 H 4} ) n / (OC 3 H 6) m] - (OC 2 H 4) k -A (1) { wherein, R an aliphatic hydrocarbon group having 8 to 18 carbon atoms N is a number of 1 to 11, m is a number of 1 to 5, k is a number of 0 to 10, and [(C ₂ H ₄ O) _n / (C ₃ H ₆ O) _m ] is a random addition Is shown. A is -OSO ₃ X, -OCH ₂ COOX or Q is R-[(OC ₂ H ₄ ) _n / (OC ₃ H ₆ ) _m ]-(OC
₂ H ₄ ) _k − or X, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, n is a number of 1 to 11, m is a number of 1 to 5, k is a number of 0 to 10 And [(C ₂ H ₄ O) _n / (C ₃
H ₆ O) _m ] indicates random addition. X represents a cationic group. ｝ 2. The surfactant according to claim 1, wherein 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 1 to 7. 3. In the general formula (1), A represents —OSO ₃
Surfactants according to claim 1 or 2, wherein the NH _4. 4. In the general formula (1), R is a group having 8 to 8 carbon atoms.
The surfactant according to any one of claims 1 to 3, which is an aliphatic saturated primary alkyl group of 18. 5. A detergent comprising the surfactant according to claim 1 or a surfactant comprising the surfactant and another surfactant.