JP4699726B2 - Surfactant composition - Google Patents

Description

  The present invention relates to a surfactant composition comprising, as an essential component, a surfactant composed of a phenolic compound, excellent in biodegradability and excellent in surface activity, and a cleaning composition using the same. .

  The surfactant has a wide range of properties such as emulsification, dispersion, washing, wetting, and foaming. Utilizing these performances, it has been used in various fields such as fiber, paper, rubber, plastic, metal, paint, pigment, civil engineering and construction. Among the surfactants used in these industries, the alkylene oxide adduct of nonylphenol is one of the most used surfactants at present because of its high performance and low cost. However, since nonylphenol is a substance with poor biodegradability, each industry has been searching for alternative surfactants to replace alkylene oxide of nonylphenol.

  Then, the method of using the surfactant using the aliphatic alcohol represented by the natural alcohol derived from natural fats and oils is known. For example, Patent Document 1 discloses an unsaturated alcohol used as a surfactant raw material having an iodine value of more than 110 and 140 or less, and a cloud point of 15 ° C. or less (Claim 1). The unsaturated alcohol raw material fat is at least one plant oil selected from the group consisting of soybean oil, rapeseed oil, safflower oil, corn oil, cottonseed oil, sunflower oil, rice bran oil and linseed oil. Of unsaturated alcohols (claim 2).

  Further, Patent Document 2 contains an alkylene oxide adduct (A) of an unsaturated alcohol having an iodine value of 40 to 140 as an essential component (Claim 1); unsaturated The alcohol is at least one selected from palm oil, palm kernel oil, palm oil, olive oil, soybean oil, rapeseed oil, safflower oil, corn oil, cottonseed oil, sunflower oil, rice bran oil and linseed oil. A surfactant for polymerization (claim 5) is disclosed.

JP, 2003-335714, A Claims JP, 2004-002644, A Claims

  However, surfactants using such aliphatic alcohols have better biodegradability than nonylphenol, but the basic performance as a surfactant, such as emulsifying power, dispersing power, detergency, wetting, etc. There was a problem that it was inferior in power and foaming power.

  Therefore, the problem to be solved by the present invention is to provide a surfactant composition excellent in biodegradability and surface activity.

（式中、Ｒ^１は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）で表される化合物７０質量％、
一般式（２）

（式中、Ｒ^２は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）で表される化合物２０質量％、及び
一般式（３）

（式中、Ｒ^３は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）で表される化合物１０質量％の混合物よりなるカシューナッツ殻液のアルキレンオキシド付加物であって、アルキレンオキシド中のエチレンオキシドが５０モル％以上である界面活性剤を必須成分として含有することを特徴とする界面活性剤組成物である。 As a result of intensive studies, the present inventors have found that an alkylene oxide adduct of a compound having a specific structure is excellent in biodegradability and surface activity, and has completed the present invention.
That is, the present invention provides the following general formula (1)

(Wherein R ¹ represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group) 70% by mass,
General formula (2)

(Wherein R ² represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group), and the general formula (3)

(In the formula, R ^3, mixture represents. Alkyl and alkenyl groups having 15 carbon atoms) a cashew nut shell liquid alkylene oxide adducts of consisting of the compounds a mixture of 10 wt%, represented by, in the alkylene oxide A surfactant composition comprising a surfactant having an ethylene oxide content of 50 mol% or more as an essential component.

  The effect of the present invention is to provide a surfactant composition having a surface active ability equivalent to that of an alkylene oxide adduct of nonylphenol and having good biodegradability.

The surfactant composition of the present invention contains an alkylene oxide adduct of cashew nut shell liquid composed of a mixture of compounds represented by the following general formula (1), general formula (2) and general formula (3) as an essential component. contains.

（式中、Ｒ^１は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）

(In the formula, R ¹ represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group.)

  The compound represented by the general formula (1) is preferably obtained from a natural product from the viewpoint of biodegradability. The best known of these natural products are the liquid components contained in cashew nut shells. The seeds of cashew tree, a plant of the Urushi family, are covered with a hard shell, and the soft portion of the shell is used as a cashew nut. It is known that these shells contain a liquid mainly composed of the compound represented by the general formula (1). These liquids contained in the cashew nut shell are called cashew nut shell liquid and are located at the bottom of the cashew nut shell and are released as soon as the shell is opened.

（式中、Ｒ^２は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）

（式中、Ｒ^３は、炭素数１５のアルキル基及びアルケニル基の混合物を表す。）
The cashew nut shell liquid is a mixture of about 70% by mass of the compound represented by the general formula (1) and about 20% by mass and about 10% by mass of the general formulas (2) and (3), respectively. Are known. R ¹ , R ² and R ³ of these three kinds of compounds are a mixture of an alkyl group having 15 carbon atoms and an alkenyl group.

(In the formula, R ² represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group.)

(In the formula, R ³ represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group.)

When adding an alkylene oxide to the cashew nut shell liquid which is a mixture of the general formulas ( 1 ), ( 2 ) and ( 3 ), it is added as it is .

  In the surfactant composition of the present invention, the alkylene oxide adduct of the compound represented by the general formula (1) is preferably 50% by mass or more, more preferably 60% by mass or more of the entire surfactant composition. Preferably, 70% by mass or more is more preferable, and 80% by mass or more is most preferable. When the alkylene oxide adduct of the compound represented by the general formula (1) is less than 50% by mass of the whole surfactant composition, the basic function as a surfactant is compared with the alkylene oxide adduct of nonylphenol. Since it may be inferior, it is not preferable.

  Examples of the alkylene oxide added to the compound represented by the general formula (1) include ethylene oxide, propylene oxide, and butylene oxide. The polymerization form of the alkylene oxide to be added is not limited, and homopolymerization of one kind of alkylene oxide or the like. Random copolymerization, block copolymerization, random / block copolymerization, or the like of two or more types of alkylene oxides may be used. The alkylene oxide is added to the —OH group and / or —COOH group of the compound represented by the general formula (1).

  The type of these alkylene oxides and the number of added moles thereof may be appropriately selected depending on the application. For example, when used in an aqueous medium such as a cleaning agent, an emulsifier, and a dispersing agent, ethylene oxide is mainly used. The addition amount of ethylene oxide in the alkylene oxide to be added is preferably 50 mol% or more, more preferably 60 mol% or more, particularly preferably 70 mol% or more, and most preferably 80 mol% or more. Moreover, when using for non-aqueous media, such as lubricating oil, it is preferable to use propylene oxide, butylene oxide, etc.

  The number of moles of alkylene oxide added is preferably 5 to 20 moles, more preferably 6 to 18 moles, and most preferably 8 to 15 moles in applications such as cleaning agents. Is preferably 10 to 100 mol, more preferably 15 to 80 mol, and most preferably 20 to 50 mol.

  Any known method can be used to add the alkylene oxide. The most common method is, for example, a method of reacting at 50 ° C. to 180 ° C. under a pressure of 0.03 MPa to 1 MPa in the presence of a catalyst, but the reaction temperature is preferably 70 ° C. to 160 ° C., 80 ° C. More preferably, ˜150 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate may be slow, so the reaction may not be terminated. When the reaction temperature exceeds 180 ° C., problems such as coloring may occur. Also, if the pressure is lower than 0.03 MPa, the amount of alkylene oxide that can be put in the reactor is too small, and reaction time may be required. If it exceeds 1 MPa, the amount of alkylene oxide in the reactor will be increased. This is not preferable because the amount becomes large and it may be difficult to control the reaction.

  Examples of catalysts that can be used include strong acids such as sulfuric acid and toluenesulfonic acid; metal halides such as titanium tetrachloride, hafnium chloride, zirconium chloride, aluminum chloride, gallium chloride, indium chloride, iron chloride, tin chloride, and boron fluoride. ; Hydroxides, alcoholates and carbonates of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, sodium methylate and sodium carbonate; aluminum oxide, calcium oxide, barium oxide, sodium oxide, etc. Metal oxides: Organic metal compounds such as tetraisopropyl titanate, dibutyltin dichloride, and dibutyltin oxide are listed.

  Surfactant compositions of the present invention include, for example, clothing cleaners, dish cleaners, residential cleaners, toilet cleaners, human cleaners, industrial cleaners, emulsifying dispersants for various resins, reactions It can be used in applications such as a basic emulsifying dispersant, an asphalt emulsifier, an inorganic powder dispersant, and a lubricant, but can be used in combination with other components within a range not impairing the effects of the present invention. Examples of other components include other surfactants, alkali agents, builders, solvents, antioxidants, and bactericides.

  Other surfactants include, for example, alkyl sulfates, polyoxyethylene alkyl sulfates, fatty acid salts, alkyl sulfonates, α-olefin sulfonates, α-sulfo fatty acid ester salts, mono-, di- or tri -Alkyl phosphate ester salts, alkyl or hydroxyalkyl ether carboxylates, alkylamide ether sulfates, N-alkylamide alkanol sulfates, acyl sarcosinates, N-acyl taurides, N-acyl-N-methyl tau Ride, fatty acid monoglyceride sulfate, acylamino acid salt, alkyliminodicarboxylate, secondary amide type N-acylamino acid salt, tartaric acid alkylamide, malic acid alkylamide, citric acid alkylamide and other anionic surfactants; higher alcohols Etoki Sylate, sucrose fatty acid ester, alkyl (poly) glucooxide, alkyl (poly) glyceryl ether, polyglycerin fatty acid mono- or di-alkanolamide, fatty acid 2,3-dihydroxypropylamide, fatty acid polyoxyethyleneamide, alkylamine oxide, alkyl Nonionic surfactants such as amidoamine oxide, polyoxyethylene fatty acid ester, methyl or ethyl glucooxide fatty acid ester, acylglucamide; mono- or dialkyl quaternary ammonium salt, mono- or dialkyl quaternary containing ether group, ester group or amide group Cationic surfactants such as ammonium salts or their hydrochlorides, sulfates, organic acid salts; carboxybetaines, sulfobetaines, phosphobetaines, amide amino acids, Amphoteric surfactants such as da sledding betaine-based surfactants. From the viewpoint of biodegradability, these other surfactants are preferably those using natural raw materials as much as possible, and the amount used is based on 100 parts by mass of the surfactant represented by the general formula (1). Less than 100 parts by mass, preferably less than 70 parts by mass. If the amount exceeds 100 parts by mass, the effect of the present invention, that is, the surface activity equivalent to that of the alkylene oxide adduct of nonylphenol, may not appear.

  Examples of the alkali agent include hydroxide compounds such as sodium hydroxide and potassium hydroxide; sodium silicates such as sodium orthosilicate and sodium metasilicate; potassium silicates such as potassium orthosilicate and potassium metasilicate; orthophosphoric acid Examples thereof include sodium phosphates such as sodium and sodium tripolyphosphate; potassium phosphates such as potassium orthophosphate and potassium tripolyphosphate; zeolite, sodium carbonate, aqueous ammonia and the like. These alkali agents can be added to the surfactant composition of the present invention in an amount of 0.1 to 40% by mass, preferably 0.2 to 30% by mass.

  Furthermore, examples of the builder include polycarboxylic acids such as alkali metal salts such as polyacrylic acid and polymaleic acid or lower amine salts; alkali metal salts such as nitrilotriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminediacetic acid and triethylenetetraminehexaacetic acid Alternatively, aminocarboxylic acids such as lower amine salts; alkali metal salts such as malic acid, citric acid, glyconic acid, and glucoheptonic acid; or oxycarboxylic acids such as lower amine salts. These builders can be added to the surfactant composition of the present invention in an amount of 0.1 to 40% by mass, preferably 0.2 to 30% by mass.

  Solvents include alcohols such as methanol, ethanol, propanol and butanol; polyhydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, glycerin, sorbitol and mannitol; ethylene glycol monoethyl ether and ethylene glycol monopropyl ether. , Ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether , Dipropylene Glycol ethers such as recall monobutyl ether: toluene, aromatic solvents such as xylene, acetone, diethyl ketone, ketones such as methyl isobutyl ketone. Among these, it is preferable to use highly safe alcohols. These solvents can be added to the surfactant composition of the present invention in an amount of 0.5 to 40% by mass, preferably 1 to 30% by mass.

  Furthermore, examples of the antioxidant include phosphorus antioxidants, phenol antioxidants, sulfur antioxidants, and amine antioxidants. These antioxidants can be added to the surfactant composition of the present invention in an amount of 0.01 to 5% by mass, preferably 0.05 to 3% by mass.

  Examples of bactericides include quaternary ammonium salts mentioned in the above surfactants; parabens such as methylparaben, ethylparaben, propylparaben, and benzylparaben; phenols such as phenol, cresol, and salicylic acid; monoglycerin alkyl ester And diols such as monoglycerin alkyl ether, octanediol and decanediol. These fungicides can be added to the surfactant composition of the present invention so as to be 0.01 to 10% by mass, preferably 0.05 to 5% by mass.

  Next, the cleaning composition of the present invention comprises the above surfactant composition of the present invention and the above alkaline agent. These alkali agents are preferably added in an amount of 0.1 to 40% by mass in the surfactant composition of the present invention, more preferably 0.2 to 30 parts by mass, and 0.2 to It is more preferable to add 10 parts by mass.

  The cleaning composition of the present invention can be used for applications such as garment cleaning, tableware cleaning, residential cleaning, toilet cleaning, human body cleaning, industrial cleaning, etc. Use as a cleaning agent is most preferred. Although it does not restrict | limit especially as articles | goods to be cleaned as an industrial cleaning agent, For example, it can use suitably for washing | cleaning of a metal part, a nonmetallic part, an electronic component, a precision instrument part, a glass product, a lens etc., for example.

Hereinafter, the present invention will be described more specifically with reference to examples. In the following examples, “part” and “%” are based on mass unless otherwise specified. EO represents an oxyethylene group, PO represents an oxypropylene group, and the number of added moles of alkylene oxide is a value per mole of raw material components.
The surfactant compositions of Examples 1 to 4 and Comparative Examples 1 to 8 were synthesized by a conventional method and used for the following experiments. The structure of each surfactant composition is shown in Table 1.

Table 2-1 shows the test results of surface tension, biodegradability, and permeability for these products of the present invention and comparative products. Moreover, the emulsification test was implemented about this invention product 2 and the comparative products 2 and 5, and the obtained result is shown to Table 2-2. The experimental method is as follows.
The surface tension was measured by a Wilhelmi method for a 25% 0.1% aqueous solution.
-Biodegradability measured BOD5 based on JISK0102. As a seeding solution, a commercially available mixed bacterium (SYBRON CHEMICALS INC. BI-CHEM BOD Seed) was dissolved in 500 ml of diluted water to obtain a seeding solution. The dilution water used was adjusted to pH 7.2 by adding 1 ml each of 4 types of adjustment reagent A solution, B solution, C solution and D solution commercially available from SYBRON CHEMICALS INC. For 1 liter of water. It is adjusted. In addition, ND shows that it is less than 10 ppm of a measurement limit, and biodegradability is so good that a numerical value is high.
-Permeability is controlled by inverting a canvas punched out to 1 inch (2.54 cm) in diameter into a 0.1% by weight surfactant solution with a gout funnel without a filter plate upside down. Hold. As the canvas wets and sinks off the funnel, the time until that time was measured. The earlier the time, the better the permeability.
In the emulsification test, the emulsified state was shown when 3% by mass of surfactant, 0.5% by mass of calcium chloride, and 40% by mass of asphalt with a penetration of 80/100 (the balance was tap water) were emulsified with a colloid mill. . In addition, the stability of the emulsion was visually observed after the emulsion was placed in a high-temperature bath at 40 ° C. for 1 week.

  The surfactant composition of the present invention exhibits the same surface activity as other aromatic nonionic surfactants, and is biodegradable equivalent to natural alcohol nonionic surfactants with good biodegradability. Showing gender. Furthermore, when used as an emulsifier, it showed better performance than other aromatic nonionic surfactants and natural alcohol nonionic surfactants.

Next, using the surfactant compositions of the present invention products 1 to 4 and comparative products 1 to 8, a cleaning composition having the following composition was prepared, and the cleaning power was evaluated. The results are shown in Table 4.
<Detergency test 1: Immersion test>
Alkaline detergent formulation 9% surfactant composition of the present invention or comparative product
Trisodium citrate 3%
Sodium hydroxide (40% aqueous solution) 4%
Water balance

About the alkali cleaning composition of the said prescription, it tested by the following method.
(1) About 1 g of the artificial stain shown below was uniformly applied to a 10 cm square glass plate and allowed to stand for 24 hours.
Artificial dirt: 50 parts of margarine / 52 parts of wheat flour / 2 parts of oleic acid (2) Prepare a 0.2% aqueous solution of the above alkaline detergent, soak the glass plate with the dirt attached, and clean it ultrasonically after 5 minutes. For 30 seconds.
(3) The glass plate was taken out and rinsed several times with stored water, then the water was drained and air-dried to observe the surface state.
Evaluation was performed in five stages as follows.
5: Clean surface with no residue remaining.
4: Almost no dirt remains, but poor rinsing properties.
3: Dirt of less than 5% of the total area remains.
2: Stain of 5 to 10% of the entire area remains.
1: Almost no cleaning was possible.

<Detergency test 2: Metal cleaning test>
Detergent formulation Surfactant composition of the present invention or comparative product 0.02%
Sodium metasilicate 0.18%
Water balance

About the said cleaning composition, about 100 mg of machine oil was made to adhere to the stainless steel test piece of length 10cm, width 10cm, and thickness 2mm, and the detergency test was done in the following ways as a contamination test piece. The contamination test piece was immersed in the cleaning composition at 25 ° C. for 3 minutes and then dried at 105 ° C. for 2 hours. The washing rate of machine oil was calculated by the following formula.
Washing rate (%) = 100 × (Ms−Mw) / (Ms−M ₀ )
Mo: Mass of test piece Ms: Mass before cleaning of contaminated test piece Mw: Mass after cleaning of contaminated test piece

  A detergent formulated with the surfactant composition of the present invention exhibits a detergency equivalent to that of an aromatic nonionic surfactant having poor biodegradability, and a natural alcohol nonionic interface having good biodegradability. Detergency was better than the activator.

  Surfactant compositions of the present invention include, for example, clothing cleaners, dish cleaners, residential cleaners, toilet cleaners, human cleaners, industrial cleaners, emulsifying dispersants for various resins, reactions Can be used for applications such as a basic emulsifying dispersant, an asphalt emulsifier, an inorganic powder dispersant, and a lubricant.

Claims (2)

The following general formula (1)

(Wherein R ¹ represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group) 70% by mass,
General formula (2)

(Wherein R ² represents a mixture of an alkyl group having 15 carbon atoms and an alkenyl group), and the general formula (3)

(In the formula, R ^3, mixture represents. Alkyl and alkenyl groups having 15 carbon atoms) a cashew nut shell liquid alkylene oxide adducts of consisting of the compounds a mixture of 10 wt%, represented by, in the alkylene oxide A surfactant composition comprising a surfactant having an ethylene oxide content of 50 mol% or more as an essential component. Detergent composition characterized by comprising a combination of surfactant composition of claim 1 Symbol placement and alkaline agents.