JP2007231176A - Low-foaming nonionic surfactant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nonionic surfactant compound in which an alkylene oxide is added to an aliphatic alcohol, in which low foaming property is attained and performances such as permeability, surface tension-lowering ability, detergency, emulsifying power and solubilization power can sufficiently be kept in high level. <P>SOLUTION: The low-foaming nonionic surfactant comprises a compound represented by general formula (1): R<SP>1</SP>-O-(AO<SP>1</SP>)<SB>n</SB>-H [wherein R<SP>1</SP>is an aliphatic hydrocarbon group represented by general formula (2): R<SP>2</SP>-CH(R<SP>3</SP>)-CH<SB>2</SB>- (wherein R<SP>2</SP>and R<SP>3</SP>are each a straight-chain aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group); AO<SP>1</SP>is a 2-4C oxyalkylene group; n is 1-100; addition form of AO<SP>1</SP>is random addition, block addition or mixed addition thereof]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a low-foaming nonionic surfactant comprising a compound obtained by adding an alkylene oxide to an aliphatic alcohol. This type of nonionic surfactant can be used not only as a cleaning agent but also as a penetrating agent, a wetting agent, an emulsifying agent, a solubilizing agent, or an antifoaming agent.

  Nonionic interface obtained by addition polymerization of ethylene oxide or the like to linear or branched, saturated or unsaturated, primary or secondary aliphatic alcohols derived from natural and synthetic carbon atoms of 8 to 20 carbon atoms. Activators are very useful surfactants with excellent performance.

  In particular, nonionic surfactants starting from branched synthetic alcohols with branches belong to those with excellent performance, and have excellent permeability and surface tension reducing ability, as well as mineral oil stains, vegetable oil stains and other Good detergency against various soils. Moreover, it has performances such as good emulsifying power for various oils.

  Among them, products that use Gerve alcohol as a starting material exhibit particularly excellent surface tension lowering ability and detergency compared with products that use starting alcohols having other chain lengths as the starting material. It can be used in a wide range not only for home use but also for business use and industrial use.

  However, these nonionic surfactants usually have a lot of foaming, and it has been difficult to use them in detergents for hard surfaces such as dishes, metals, and plastics, and circulation type cleaning devices such as dishwashers.

As a method for reducing the foam of a nonionic surfactant, there are a method of introducing propylene oxide, a method of blocking a terminal hydroxyl group, etc., but there are many methods by introducing propylene oxide from the viewpoint of cost and production equipment. It is disclosed and considered suitable. However, the improvement effect by the prior art is not sufficiently satisfactory for practical use (for example, Patent Document 1).
JP 2004-277651 A

  However, when propylene oxide is added to improve foaming properties, the basic properties of surfactants, such as penetrability and surface tension lowering ability, are greatly reduced. The practically important performance such as the solubilizing power is reduced.

  As a result of various studies in view of the above problems, the present inventor has found that a nonionic surfactant having a specific hydrophobic group, or a specific type and a specific range and a molar ratio of a specific range and 3 or 4 carbon atoms. By adding this alkylene oxide, it has been found that a low-foaming nonionic surfactant having excellent performance that cannot be obtained under conditions outside of this is obtained.

  That is, the present invention provides a nonionic surfactant composed of a compound obtained by adding an alkylene oxide to an aliphatic alcohol, and realizes low foaming, permeability, surface tension reducing ability, detergency and emulsifying ability. The present invention provides what can maintain sufficiently high performance such as solubilizing power.

  The low-foaming nonionic surfactant of the present invention is characterized by comprising a compound represented by the following general formula (1).

R ¹ —O— (AO ¹ ) n—H (1)
R ² —CH (R ³ ) —CH ₂ — (2)
[Wherein, R ¹ is a fatty acid represented by the above general formula (2) (in the formula (2), R ² and R ³ are a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group). Represents a group hydrocarbon group, AO ¹ represents an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 100. The addition form of AO ¹ is random addition, block addition, or a mixed addition thereof. ]
With the above configuration, the low-foaming nonionic surfactant of the present invention achieves low foaming and maintains sufficiently high performance such as permeability, surface tension reducing ability, detergency, emulsifying power, and solubilizing power. be able to.

In the low-foaming nonionic surfactant of the present invention, the (AO ¹ ) n portion of the compound represented by the general formula (1) is represented by the following general formula (3). preferable.
_{^{- (AO 2) p- (C}} 2 H 4 O) q - [(C 2 H 4 O) r / (AO 3) s] - ··· (3)
In the formula, p, q, r, and s are average added mole numbers (p = 0 to 5, q = 1 to 30, r = 0 to 30, s = 1 to 30), and AO ² has 3 or 4 carbon atoms. The oxyalkylene group, (C ₂ H ₄ O) r / (AO ³ ) s, is a random or block polymer chain of an oxyethylene group and an oxyalkylene group having 3 or 4 carbon atoms.

Furthermore, the compound represented by the general formula (1) is preferably a nonionic interface in which R ² and R ^{3 in} the general formula (2) are each an aliphatic hydrocarbon group having 2 to 24 carbon atoms. It is an activator, and more preferably, R ^{1 in the} general formula (1) is 2-propyl-1-heptanol, 2-propyl-4-methyl-1-hexanol, 2-propyl-5-methyl-1- Hexanol, or an aliphatic hydrocarbon group derived from a mixture thereof, and in this case, in particular, while realizing low foaming, permeability, surface tension reducing ability, foam resistance, detergency against oil stains, and Excellent emulsifying power and solubilizing power for various oils.

  The low-foaming nonionic surfactant of the present invention realizes low foaming and exhibits sufficiently high performance such as permeability, surface tension reducing ability, detergency, emulsifying power, and solubilizing power. Can solve conventional problems such as foam trouble, and is suitable as a component of detergents, penetrants, wetting agents, emulsifiers, solubilizers, or antifoaming agents by utilizing the low foaming property Can be used for

  The nonionic surfactant of the present invention is composed of a compound represented by the above general formula (1), in which an alkylene oxide is added to a higher alcohol, and conditions such as a specific molar ratio are selected for a specific hydrophobic group. Is.

The compound represented by the general formula (1) is a nonionic surfactant in which R ¹ in the formula (1) is an aliphatic hydrocarbon group represented by the general formula (2).

R ² —CH (R ³ ) —CH ₂ — (2)
R ² and R ³ are straight chain aliphatic hydrocarbon groups or branched aliphatic hydrocarbon groups, and preferably R ² and R ³ are aliphatic hydrocarbon groups having 2 to 24 carbon atoms.

More preferably, R ¹ of the general formula (1) is 2-propyl-1-heptanol, 2-propyl-4-methyl-1-hexanol, 2-propyl-5-methyl-1-hexanol, or these An aliphatic hydrocarbon group derived from a mixture.

  Examples of preferred higher alcohols include 2-propyl-1-heptanol, 2-propyl-4-methyl-1-hexanol, 2-propyl-5-methyl-1-hexanol and the like. It can also be used. In particular, 2-propyl-1-alkanol containing 80% by weight or more of 2-propyl-1-heptanol as a main component is preferable.

  In addition, there is a gel alcohol obtained by dimerization of nonyl alcohol, and as a commercial product, Diadol 18G-C made by Mitsubishi Chemical can be used, and a gel alcohol mixture having 12 to 14 carbon atoms obtained by dimerization of hexanol and heptanol is also suitable. Is an example of a branched higher alcohol that can be used in At this time, the side chain of Gerve alcohol may be linear or branched.

  In addition, 2-ethyl-1-hexanol, 2-butyl-1-octanol, and 2-hexyl-1-decanol are examples of branched higher alcohols that can be used in the present invention. Furthermore, it is also possible to mix and use two or more of the various alcohols.

  Needless to say, the C3 or C4 alkylene oxide used in the production of the nonionic surfactant of the present invention is propylene oxide. The alkylene oxide having 4 carbon atoms includes isobutylene oxide and tetrahydrane, and is preferably 1,2-butylene oxide or 2,3-butylene oxide.

In the low-foaming nonionic surfactant of the present invention, the (AO ¹ ) n portion of the compound represented by the general formula (1) is preferably represented by the following general formula (3).
_{^{- (AO 2) p- (C}} 2 H 4 O) q - [(C 2 H 4 O) r / (AO 3) s] - ··· (3)
In the formula, p, q, r, and s are average added mole numbers (p = 0 to 5, q = 1 to 30, r = 0 to 30, s = 1 to 30), and AO ² has 3 or 4 carbon atoms. The oxyalkylene group, (C ₂ H ₄ O) r / (AO ³ ) s, is a random or block polymer chain of an oxyethylene group and an oxyalkylene group having 3 or 4 carbon atoms.

More preferably, the (AO ¹ ) n part of the general formula (1) is a polyoxyalkylene chain containing 50 mol% or more of oxyethylene groups.

  When the nonionic surfactant composition of the present invention satisfies the conditional expression (3) in the above general formula (1), it is particularly excellent in low foaming property, and has permeability, surface tension lowering ability, foaming property, It is further excellent in cleaning power against oil stains and emulsifying power and solubilizing power in various oils.

  The average addition mole number p of the oxyalkylene group in the general formula (3), the average addition mole number q of the oxyethylene group, the average addition mole number r of the oxyethylene group in the random or block polymer chain, and 3 or 4 carbon atoms. Even if any of the average added mole number s of the oxyalkylene group is out of the above range, the effect of improving the low-foaming property is greatly reduced, or the permeability and surface tension reducing ability are greatly reduced, and the detergency and emulsifying power are also reduced. The solubilizing power will be reduced.

  The nonionic surfactant of the present invention can be suitably used as a household product, a commercial product, an industrial product, and a process chemical in various industrial fields. As a specific use example, it can be suitably used as a cleaning agent, a penetrating agent, a wetting agent, an emulsifying agent, a solubilizing agent, a dispersing agent, and an antifoaming agent, taking advantage of the characteristics of good penetrating power and excellent surface tension reducing ability. . In addition, the nonionic surfactant of the present invention is characterized by low foaming and good foaming properties, so that there are concerns about problems due to foaming, such as industrial products and process chemicals in various industrial fields. It can be suitably used. In this case, as in the prior art, as a surfactant component, other surfactants as necessary, for example, other types of nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric interfaces. One or more active agents can be used in appropriate amounts. Furthermore, various other compounding components can be used as in the prior art.

  Examples of the nonionic surfactant of the present invention that can be suitably used include household, commercial and industrial cleaning agents, and various industrial process chemicals such as fiber scouring agents, metal surface treatment agents, metals There are degreasing agents, metal parts, cleaning agents for electronic parts, pitch removing agents, deinking agents, and the like. The nonionic surfactant of the present invention exhibits good detergency against various soils such as mineral oils, vegetable oils, soils with inorganic substances, waxes, and resins. It is particularly effective against mineral oil stains. In addition, the nonionic surfactant of the present invention can be used alone or in combination with other types of drugs. As a compounding component when used as a cleaning agent, as in the prior art, in addition to various nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, various alkaline components, inorganic builders , Thickeners, chelating agents, hydrotropes, enzymes, disinfectants, fragrances, dyes, and the like.

  Specific examples and comparative examples of the present invention will be described below, but the present invention is not limited to these examples.

Table 1 shows raw alcohols, surfactant compositions (AO ² , p, q, r, AO ³ , s) of nonionic surfactants of Examples 1 to 12 and clouding points thereof according to the present invention.

Starting alcohol nonionic surfactants of Comparative Examples 1 to 12 in Table 2 (ROH), a surfactant composition ^{(AO 2, p, q,} r, AO 3, s) and shows the cloud point.

  Regarding the aqueous solutions of the nonionic surfactants described in Tables 1 and 2, the basic physical properties (surface tension, penetrating power, foaming property) and detergency were evaluated by the following test methods, and further comprehensive evaluation was performed. .

[surface tension]
Based on the Wilhelmy method, the surface tension of a 0.5% nonionic surfactant aqueous solution was measured at 25 ° C. using a Wilhelmy type surface tension meter.

[Penetration power]
In accordance with the canvas disk method (ISO-8022-11990), the penetrating power of a 0.1% aqueous solution of a nonionic surfactant at 25 ° C. (seconds until the canvas disk starts to settle after being immersed in the surfactant aqueous solution) Number).

[Foaming power]
According to the Ross Miles method (JIS K3362-1990), the foaming power (bubble height (mm)) of a nonionic surfactant 0.1% aqueous solution at 25 ° C. was measured immediately after sample preparation and after 5 minutes. It was measured.

[Cleaning power (cleaning performance of mineral oil stains)]
The oil removal rate (%) was calculated from the change in weight before and after the washing with respect to the mineral oil stain adhered to the test piece, and the oil removal rate was defined as the detergency (%) and evaluated.

<Preparation of cleaning composition>
The cleaning composition is composed of 10.0 g of a nonionic surfactant (surfactant concentration of 2.0%), 1.7 g of sodium metasilicate (pentahydrate) (0.2% in terms of anhydride), distilled water It was set to 488.3 g (total) 500 g.
<Cleaning test>
A test piece of known weight (100 mesh SUS wire mesh, test piece size 100 mm × 50 mm) was dipped in refined mineral oil (Idemitsu Kosan Co., Ltd., Daphne Super Ace Bag), then allowed to stand at 105 ° C. for 30 minutes. The weight was measured. Next, 500 g of the cleaning composition was prepared in a 500 ml beaker, and the liquid temperature was adjusted to 30 ° C. Next, the test piece was fixed with a clip and immersed in an aqueous solution, and then the test piece was treated (washed) by stirring at 200 rpm for 2 minutes with a propeller-type stirring blade having a blade diameter of 50 mm. Subsequently, 500 ml of 30 ° C. distilled water was taken into another 500 ml beaker and rinsed for 1 minute in the same manner as the washing operation. After rinsing, the test piece was taken out of the water and left in a constant temperature bath at 60 ° C. overnight to dry.

<Calculation and evaluation of cleaning power>
The detergency was calculated according to the following formula.
Detergency (%) = (A−B) × 100 / (A−C)
However, A: test piece weight (g) after oil immersion and before washing, B: dry weight (g) of test piece after washing, C: dry weight (g) of test piece before oil immersion. Based on the calculated value of the detergency, evaluation was performed according to the following criteria.
○: 85.0-94.9%, Δ: 70.0-84.9%, X: 0-69.9%
Table 3 shows the evaluation results of basic physical properties and properties of Examples 1 to 12, and Table 4 shows the evaluation results of basic physical properties and properties of Comparative Examples 1 to 12.

  As shown in Tables 3 and 4, for the low-foaming nonionic surfactant of the present invention, good results were obtained for each evaluation item, whereas the nonionic surfactant of the comparative example was obtained. Then, it became a very inferior result in either evaluation item.

  The surfactant compounds of the examples were satisfactory in detergency. Further, by using the surfactant compound of the example as an antifoaming agent, it is possible to reduce the foam without reducing the surface tension reducing ability, penetrating power, and cleaning power.

  Next, the emulsifying power of the nonionic surfactant was evaluated based on the following method. Liquid paraffin, kerosene, toluene, olive oil, and silicon oil were used as the oil to be emulsified. Table 5 summarizes the results of the nonionic surfactants of Examples and Comparative Examples.

[Emulsification test]
Take 8 g of the oil to be emulsified and 0.8 g of the nonionic surfactant in a graduated test tube, stir for 30 seconds with a touch mixer for test tube, add 11.2 g of distilled water and stir for 1 minute with a touch mixer. The emulsifying power was evaluated by measuring the height of the emulsified phase and the water-separated phase after standing for 2 hours.

<Evaluation of emulsifying power>
The emulsifying power was calculated by the following formula.
Emulsifying power (%) = (amount of water charged-amount of water separation) (ml) x 100 / amount of water charged (ml)
Based on the evaluation value of the obtained emulsifying power, evaluation was performed according to the following criteria.
○: 85.0 to 100.0%, Δ: 60.0 to 84.9%, ×: 0 to 59.9%

  The nonionic surfactant of the present invention showed good emulsifying power, whereas the surfactant of the comparative example was very inferior.

  Next, the solubilizing power of the nonionic surfactant was evaluated based on the following method. Limonene, Eugel, and benzyl acetate were used as the soluble emulsion. Table 6 summarizes the results of the nonionic surfactants of Examples and Comparative Examples.

[Solubilization test]
0.1 to 0.3 g of the solubilized product and 1.0 g of the nonionic surfactant are placed in a container and stirred. 99 g of distilled water was added thereto and stirred, and the state of the solution after standing for 2 hours was visually evaluated. The obtained solubilized solution was evaluated as follows.
○: transparent and uniform, Δ: slightly turbid, ×: cloudy or separated.

  The nonionic surfactant of the present invention showed a good solubilizing power, whereas the surfactant of the comparative example resulted in very poor solubilizing power.

  In addition, in the nonionic surfactant compound of the example in which an alkylene oxide is added to an aliphatic alcohol, while realizing low foaming properties, performance such as permeability, surface tension reducing ability, detergency, emulsifying ability, and solubilizing ability Was kept high enough.

The nonionic surfactants of the present invention can be suitably used as process products in household products, commercial products, industrial products, and various industrial fields. For example, detergents, penetrants, wetting agents, emulsifiers, It can be suitably used as a solubilizer and antifoaming agent. Furthermore, it can be suitably used for industrial and various industrial process chemicals such as fiber scouring agents, metal surface treatment agents, metal degreasing agents, metal parts, electronic parts cleaning agents, depitching agents, deinking agents, and the like. .

Claims (3)

A low-foaming nonionic surfactant characterized by comprising a compound represented by the following general formula (1).
R ¹ —O— (AO ¹ ) n—H (1)
R ² —CH (R ³ ) —CH ₂ — (2)
[Wherein, R ¹ is a fatty acid represented by the above general formula (2) (in the formula (2), R ² and R ³ are a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group). Represents a group hydrocarbon group, AO ¹ represents an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 100. The addition form of AO ¹ is random addition, block addition, or a mixed addition thereof. ] The low-foaming nonionic surfactant according to claim 1, wherein the (AO ¹ ) n portion of the general formula (1) is represented by the following general formula (3).
_{^{- (AO 2) p- (C}} 2 H 4 O) q - [(C 2 H 4 O) r / (AO 3) s] - ··· (3)
[Wherein, p, q, r, and s are average added mole numbers (p = 0 to 5, q = 1 to 30, r = 0 to 30, s = 1 to 30), and AO ² has 3 or 4 carbon atoms. The oxyalkylene group, (C ₂ H ₄ O) r / (AO ³ ) s, is a random or block polymer chain of an oxyethylene group and an oxyalkylene group having 3 or 4 carbon atoms. ] A cleaning agent, a penetrating agent, a wetting agent, an emulsifying agent, a solubilizing agent or an antifoaming agent comprising the low-foaming nonionic surfactant according to claim 1 or 2.