JPH073290A - Detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition containing a specific tetrazole compound in combination with a surfactant, having excellent detergent power, exhibiting excellent rust-proofing effect in the cleaning of metal, having extremely excellent oil-water separation property and generating waste water having remarkably low COD and BOD. CONSTITUTION:This detergent composition contains (A) a tetrazole compound of the formula I and the formula II (X is H, alkyl, amino or hydroxy) or its salt and (B) a surfactant as active components. The amounts of the component A and the component B are preferably 0.01-1wt.% and 0.1-1wt.% based on the total composition, respectively. The compound of the formula I used as the component A is e.g. 5-phenyl-1,2,3,4-tetrazole. The component B is preferably an anionic surfactant in the case of using the composition for domestic use such as washing of tableware and is preferably cationic, nonionic or ampholytic surfactant for industrial use.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a detergent composition. Specifically, the present invention exhibits excellent detergency, exhibits an excellent rust preventive effect when the object to be washed is a metal, has extremely good oil-water separability, and has significantly low COD and BOD of wastewater. In particular, the present invention relates to a cleaning composition that does not require drainage measures.

[0002]

2. Description of the Related Art Freon 113 and 1, which have been widely used for cleaning various industrial products including metal products.
With the decision to abolish 1,1-trichloroethane (hereinafter simply referred to as “ethane”) at the end of 1995, the development of alternative cleaning agents has become remarkable.

At present, non-aqueous (organic solvent-based), quasi-water-based and water-based alternative cleaning agents are known.

As the non-aqueous detergent, hydrocarbons such as petroleum hydrocarbons, lower alcohols such as isopropanol and ethanol, chlorinated hydrocarbons such as methylene chloride and trichloroethylene, N-methylpyrrolidone and the like are used. There is. These non-aqueous cleaning agents are advantageous in that they can be used as they are for CFC and ethane cleaners, but most of them are dangerous substances with high flammability and flammability, so facilities that ensure safety Or
There is a problem that it is highly toxic to the human body, or that wastewater treatment is difficult and pollution of rivers and groundwater occurs.

As the semi-aqueous detergent, for example, those containing a higher alcohol, an aliphatic hydrocarbon, a terpene, etc. as a main component are used, but they are flammable like the non-aqueous detergent. However, wastewater treatment is also difficult.

Further, as the water-based cleaning agent, water containing an alkaline agent, a surfactant and the like is used. Such water-based cleaning agents have no danger of being flammable or flammable and are not toxic to the human body, but there remains a problem from the viewpoint of wastewater treatment. That is, since the current water-based detergents have insufficient oil-water separability, stains (oils and fats) adhering to the object to be washed are emulsified in the detergent, making it impossible to separate and remove only the stains. . Therefore, as a result, both the cleaning agent and the cleaning agent must be treated as wastewater, and the amount of water-based cleaning agent used is higher than that of non-aqueous or semi-aqueous systems, which increases COD and BOD of wastewater. It is the cause.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems of the prior art, the present inventors have found that when a specific tetrazole compound and a surfactant are used in combination,
(1) It has the same excellent detergency as CFCs and ethane against dirt such as fats and oils. (2) After cleaning, it can be subjected to chemical conversion treatment and coating without washing with water. When is a metal, it can also be rustproof.
(3) The oil-water separability is very good, so after cleaning the dirt such as fats and oils, only the dirt can be separated and removed, and can be repeatedly used as it is. (4) COD and BO of waste water
It was found that there is no need to take special drainage measures because D is extremely low. The present invention has been completed based on these findings.

That is, the present invention has the general formula

[0009]

[Chemical 3]

[In the formula, X represents a hydrogen atom, an alkyl group, an amino group or a hydroxy group. ] The tetrazole compound represented by these, its salt, and general formula

[0011]

[Chemical 4]

[Wherein X is the same as above. ] A detergent composition comprising as an active ingredient at least one compound selected from the tetrazole compound represented by the formula and a salt thereof and a surfactant.

The tetrazole compounds of the general formulas (1) and (2) used as the active ingredient in the present invention are known compounds. Specific examples of the tetrazole compound represented by the general formula (1) include 5-phenyl-
1,2,3,4-tetrazole, 5- (2-methylphenyl) -1,2,3,4-tetrazole, 5- (3-methylphenyl) -1,2,3,4-tetrazole, 5-
(4-methylphenyl) -1,2,3,4-tetrazole, 5- (4-ethylphenyl) -1,2,3,4-tetrazole, 5- (2-aminophenyl) -1,2,
3,4-tetrazole, 5- (3-aminophenyl)-
1,2,3,4-tetrazole, 5- (4-aminophenyl) -1,2,3,4-tetrazole, 5- (4-hydroxy) -1,2,3,4-tetrazole and the like. You can Specific examples of the tetrazole compound represented by the general formula (2) include 1-phenyl-1,2,
3,4-tetrazole, 1- (2-methylphenyl)-
1,2,3,4-tetrazole, 1- (3-methylphenyl) -1,2,3,4-tetrazole, 1- (4-methylphenyl) -1,2,3,4-tetrazole, 1-
(3-Ethylphenyl) -1,2,3,4-tetrazole, 1- (2-aminophenyl) -1,2,3,4-tetrazole, 1- (3-aminophenyl) -1,2,
3,4-tetrazole, 1- (4-aminophenyl)-
1,2,3,4-tetrazole, 1- (4-hydroxyphenyl) -1,2,3,4-tetrazole and the like can be mentioned. The salts of the above general formulas (1) and (2) are not particularly limited and known ones can be used, and examples thereof include salts with an inorganic alkaline compound and salts with an organic alkaline compound. Specific examples of the salt with an inorganic alkaline compound include salts with an alkali metal such as Na salt and K salt. Specific examples of the salt with an organic alkaline compound include salts with amines. These tetrazole compounds are 1
The seeds may be used alone or in combination of two or more.

As the surfactant which is another active ingredient in the present invention, conventionally known ones can be widely used,
For example, anionic surfactant, cationic surfactant,
Examples thereof include nonionic surfactants and amphoteric surfactants. When the cleaning agent of the present invention is used for industrial purposes such as metal cleaning, cationic surfactants, nonionic surfactants and amphoteric surfactants are preferable, and dishwashing,
Anionic surfactants are preferred when used for household purposes such as cleaning.

The anionic surfactant is not particularly limited and can be widely used conventionally known ones, specifically, fatty acid salt, alkyl sulfate ester salt, alkyl sulfonate, alkyl aryl sulfonate, alkyl naphthalene sulfone. Examples thereof include acid salts, alkyl sulfosuccinates, alkyl diphenyl ether disulfonates, alkyl phosphates, polyoxyethylene alkyl sulfate ester salts, and sulfosuccinate ester salts. The cationic surfactant is not particularly limited, and conventionally known ones can be widely used. Specific examples thereof include higher amine halogen acid salts, halogenated alkylpyridinium salts, and quaternary ammonium salts. The nonionic surfactant is not particularly limited, and conventionally known ones can be widely used. Specifically, polyoxyethylene glycol such as polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether, etc. Alkyl ethers, polyethylene glycol fatty acid esters such as polyethylene glycol monostearate,
Sorbitan monolaurate, sorbitan fatty acid esters such as polyoxyethylene sorbitan monolaurate,
Examples thereof include glycol fatty acid esters such as glycol monostearate and fatty acid monoglycerides. The amphoteric surfactant is not particularly limited and widely known ones can be widely used, for example, the general formula RNHR'COOH.
[Wherein R and R'are the same or different and have 8 to 1 carbon atoms]
6 shows an aliphatic hydrocarbon group of 6. ] Amino acids and the like represented by

Among the above-mentioned surfactants, in consideration of detergency, oil-water separability, etc., sulfosuccinic acid ester or the like is used as the anionic surfactant, and higher amine halogenate or quaternary ammonium salt is used as the cationic surfactant. Among the nonionic surfactants, polyoxyethylene lauryl ether, polyoxyethylene higher alcohol ether, polyoxyethylene octyl phenyl ether (each HL
B13 to 15)) and the like, and as the amphoteric surfactant, aminopropionic acid, betaine and the like are preferable.

As the above-mentioned surfactants, anionic, cationic, nonionic or amphoteric surfactants may be used alone or in combination of two or more. Furthermore, two or more kinds of compounds different from each other (for example, only an anionic surfactant) may be mixed and used.

The composition of the present invention is prepared by dissolving or dispersing at least one of the above tetrazole compounds and at least one of the surfactants in water or an aqueous solvent. The concentration of the tetrazole compound and the surfactant is not particularly limited and may be appropriately selected from a wide range according to the object to be washed, etc., but the tetrazole compound is usually about 0.001 to 10 wt% of the total amount of the composition, preferably 0.01
It may be about 1 to 1% by weight, and the surfactant is usually 0.01 to 10% by weight of the total amount of the composition, preferably 0.1.
It may be about 1 to 1% by weight. If the concentration of the tetrazole compound is significantly lower than 0.001% by weight, the cleaning effect and the oil-water separability may decrease, while the concentration of 10% by weight
Even if it exceeds the above range, no further remarkable improvement in the cleaning effect is observed, which is economically unfavorable. Further, if the concentration of the surfactant is significantly lower than 0.01% by weight, the cleaning effect and oil-water separability may be deteriorated. On the other hand, if it exceeds 10% by weight, the cleaning effect and the like are further significantly improved. Because it is not possible, it is not economically preferable.

By adjusting the pH of the composition of the present invention to about 7 to 10, more remarkable cleaning effect, oil-water separability and rust prevention effect can be exhibited. The pH is adjusted by a known method, for example, the addition of an alkaline agent.
A wide variety of known compounds can be used as the alkaline agent, for example, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, aqueous ammonia, hydrazine, monoethanolamine, monoisopropanolamine, diethanolamine, diisopropanolamine, and triamine. Alkanolamines such as ethanolamine and cyclohexylamine, polyvalent amines such as morpholine and ethylenediamine,
1,8-diazabicyclo [5,4,0] -7-undecene (DBU), 1,5-diazabicyclo [4,3,0]
Examples thereof include polycyclic amidines such as -5-nonene (DBN). These alkaline agents may be used alone or in combination of two or more.

In the composition of the present invention, the tetrazole compound, which is the active ingredient compound, is chemically stable against known rust preventives and anticorrosion agents, so that it can be used in combination with known rust preventives and anticorrosive agents. Is. Specific examples thereof include nitrite, molybdate, tungstate, tert-butylbenzoate, azelaate, which are effective for iron.
Examples thereof include benzotriazole, tolyltriazole, 2-mercaptobenzothiazole, and 1,2,4-triazole which are effective for copper and copper alloys such as hydroxybenzotriazole salt. Commercially available rust preventives and anticorrosives can also be added.

Further, the composition of the present invention may be added with conventionally used additives for detergents, for example, antifoaming agents such as silicone type and surfactant type.

In washing with the composition of the present invention, conventionally known methods can be widely adopted, and examples thereof include spraying, showering, dipping, ultrasonic waves and brushing. In the immersion cleaning, ultrasonic waves may be used together, or the immersion tank may be shaken or stirred. The use concentration of the composition of the present invention is not particularly limited and may be appropriately selected depending on the degree of stains on the article to be washed, but usually sufficient effect is exhibited even if it is diluted with water about 10 to 20 times. It The washing temperature and the washing time can be appropriately determined within a wide range according to the washing method, but the washing temperature is usually room temperature to about 90 ° C., preferably about 60 to 80 ° C., and the washing time is usually about 30.
It may be about 10 seconds, preferably about 2 to 5 minutes.

The composition of the present invention is effective for removing the contaminants adhering to, for example, metal, ceramics, plastics, rubber or molded products thereof. The stain content is not particularly limited, and examples thereof include rust preventive oil, metal working oil (cutting oil, grinding oil, press oil, rolling oil, drawing oil, heat treatment oil, etc.), lubricating oil, grease, flux, fingerprints, etc. Oils and fats, chips / grinding grains, plastic grains, dust, dust and the like. Furthermore, the composition of the present invention can be used in virtually all industrial fields. Specifically, ferrous and non-ferrous metal industries (steel pipes, steel plates, castings, rolled products, copper products, etc.), metal processing industry (can manufacturing, building materials, screws, springs, bearings, shafts, tools, etc.), machinery industry ( Metalworking / processing machine products, dies, machine tools, general machine parts, turbines, etc.), automobile industry (automobile parts such as engines, pistons, pumps, valves, bolts, nuts, industrial vehicle parts, etc.), precision machinery industry ( Precision parts such as molds, bearings and gears, die castings, springs, precision castings, optical machines and their parts), electrical machinery industry (electric motor parts, printed circuit boards, communication / electronic parts such as hoop materials), plastic manufacturing Examples include industries (precision resin processed parts, automobile parts, etc.). Further, the composition of the present invention,
For example, it is preferably used for washing household items such as clothes, tableware, bathtubs, sanitary items and the like.

[0024]

The composition of the present invention exhibits the following remarkable effects.

(1) It has an excellent detergency equivalent to that of Freon and ethane with respect to dirt such as oil and fat.

(2) After washing, it can be subjected to chemical conversion treatment or coating without washing with water, and when the object to be washed is metal, it can also be provided with rust preventive properties.

(3) Since the oil-water separation property is extremely good,
After the dirt such as fats and oils is washed, only the dirt is separated and removed and can be repeatedly used as it is.

(4) Since the COD and BOD of the wastewater are extremely low, it is not necessary to take any special measures against the wastewater.

[0029]

EXAMPLES The present invention will be further clarified with reference to the following examples and comparative examples. In the following, "%" simply means "% by weight".

Examples 1 to 5 Each of the components shown in Table 1 below was dissolved in water to obtain a cleaning composition of the present invention.

[0031]

[Table 1]

Test Example 1 The compositions of the present invention of Examples 1 to 5 were each diluted with deionized water.
Diluted 0 times. Cutting oil [trade name: Bakumaru B2, manufactured by Cast Roll Co., Ltd.] is uniformly applied to the surface of an iron piece having a size of 70 × 150 × 0.8 mm, and this is applied at a temperature of 50 ° C. for 2 times with the above dilution. Immersion cleaning (ultrasonic wave: 39KH)
z) or after spray cleaning, it was dried to prepare a test piece. The test piece was analyzed according to the following method to evaluate the cleaning performance, rust prevention performance, direct coating performance and chemical conversion treatment performance of the composition of the present invention. Furthermore, the oil-water separation performance of the composition of the present invention was also evaluated. The results are shown in Table 2. For comparison, DK Beclear [trade name: surfactant-based water-based detergent, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.] (Comparative Example 1), Elise K [[trade name: surfactant-based water-based detergent The same test as above was performed using the agent, manufactured by Asahi Kasei Kogyo Co., Ltd. (Comparative Example 2), water (Comparative Example 3) and trichloroethane (Comparative Example 4). The results are also shown in Table 2.

[Evaluation Method] (a) Cleaning Performance The amount of oil adhering to the test piece was examined, and the oil removal rate was calculated based on the following formula.

[0034]

[Equation 1]

The criteria for judgment are as follows. ⊚: Oil removal rate 96 to 100%, ◯: Oil removal rate 81 to 95%, Δ: Oil removal rate 51 to 80%, ×: Oil removal rate 0 to 50%.

(B) Anticorrosion Performance A test piece is subjected to an indoor exposure test (method A, left indoors for 14 days), and a method of dipping and storing in each cleaning composition of Examples 1 to 5 and Comparative Examples 1 to 4 (B Method for 1 day at 50 ° C.) to evaluate rust prevention performance. In addition to iron, as test pieces, zinc pieces, aluminum pieces, and copper pieces (having the same size) that were washed and dried in the same manner as above were used. The judgment criteria are as follows.
⊚: rust rate 0%, ◯: rust rate 1 to 5%, △: rust rate 6 to
25%, x: Rust generation rate is 26% or more.

(C) Direct Coating Performance A test piece was baked and coated with an acrylic resin or an epoxy resin so as to have a film thickness of 15 μm, and subjected to a goose eye test (method A) and an Erichsen test (method B). The criteria for the goose eye test are as follows. ∘: 1% cellophane tape peeling area 0 mm, ○: 1 mm cellophane tape peeling area 1 to 5%, Δ: 1 mm cellophane tape peeling area 6
-25%, x: Cellotape peeling area of 1 mm square 26
%that's all. The criteria for the Erichsen test are as follows. ⊚: No peeling after extrusion of 7 mm, ◯: No peeling after extrusion of up to 5 mm, Δ: No peeling after extrusion of up to 2 mm, ×: Peeling after extrusion of up to 2 mm.

(D) Chemical conversion treatment performance The test piece was washed with water, surface-conditioned, subjected to chemical conversion treatment (zinc phosphate treatment), washed with water and dried, and the surface condition was observed by an electron microscope. The judgment criteria are as follows. ◯: There is no scale (a portion where zinc phosphate crystal particles do not adhere). The size of crystal grains is constant and fine. X: Large scale. The size of crystal grains is not uniform.

(E) Oil-Water Separation Performance Detergent compositions of Examples 1 to 5 / various oils = 1/1 (V /
V) was placed in a Nessler tube and shaken 100 times while maintaining the temperature at 70 ° C. After allowing this to stand for 10 minutes, the liquid separation state of the cleaning composition and various oils was observed. Comparative Examples 1 to 4
The same cleaning agent was used for the same test. The judgment criteria are as follows. ⊚: better than water, ∘: equivalent to water,
Δ: worse than water, ×: marked emulsification, almost no liquid separation.

[0040]

[Table 2]

From Table 2, the detergent composition of the present invention is superior to the conventional detergents in terms of cleaning performance, rust prevention performance, direct coating performance, chemical conversion treatment performance and oil-water separability. I understand.

Test Example 2 A piece of metal (SPCC-D material, 60 × 80 × 0.8 mm) was subjected to acetone degreasing, alkaline degreasing, warm water washing, room temperature water washing and drying according to a conventional method, and then uniformly coated on one surface thereof. A rosin-based flux was applied, dried, and soldered at 20 points. Then, it was immersed in the detergent composition of the present invention of Example 1 and washed, and rinsed with water to prepare a test piece.

The cleaning conditions are as follows. Cleaning solution: the cleaning composition of the present invention of Example 1, cleaning solution concentration: 50% and 1
00%, washing temperature: 70 ° C., washing time: 1 minute, 2 minutes and 5 minutes, washing machine: ultrasonic washing machine [trade name: UT-204,
Sharp Corporation], 39 KHz maximum.

The conditions of the rinse cleaning are as follows. Rinse temperature: 70 ° C., Rinse time: 30 seconds, Cleaning device: Ultrasonic cleaning device [trade name: UT-204, manufactured by Sharp Corporation],
Maximum 39 KHz.

The following rosin-based flux was used. Preflux: SS-20 and HS-10
0, post flux: SF-270, SF-310,
SF-1230, SRM-800G [Both are trade names,
Also manufactured by Sanwa Chemical Industry Co., Ltd.] The flux cleaning performance of the composition of the present invention was evaluated as follows. That is, the test piece (288 cm ² ) after the above-mentioned washing was placed at a temperature of 50 ° C. for 7 days.
After immersion in 200 ml of 5% isopropyl alcohol aqueous solution and ultrasonic cleaning for 1 minute, the electrical conductivity (μS / cm, 25 ° C.) of the isopropyl alcohol was examined, and the initial resistance value before cleaning (0.26 μS / cm, 25 The increase value from (° C) was determined. The results are shown in Table 3.

[0046]

[Table 3]

From Table 3, it can be seen that the composition of the present invention showed almost no increase in electric conductivity and was almost completely cleaned.

Claims (1)

[Claims] 1. A general formula: [In the formula, X represents a hydrogen atom, an alkyl group, an amino group or a hydroxy group. ] The tetrazole compound and its salt represented by these, and general formula [Where X is the same as above. ] A detergent composition containing as an active ingredient at least one compound selected from the tetrazole compound represented by the formula and a salt thereof and a surfactant.