JP3054309B2 - Detergent composition for metal products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cleaning composition.
The detergent using this detergent composition can be used instead of a chlorofluorocarbon-based or chlorine-based detergent, and can be suitably used as an industrial detergent for metal products and the like.

[0002]

2. Description of the Related Art Conventionally, as an industrial cleaning agent for removing dirt mainly composed of organic substances such as oils and fats, machine oil, cutting oil, and grease adhered to a member surface, a fluorocarbon-based cleaning agent such as trichlorotrifluoroethane, 1.1.1. Chlorine-based detergents such as trichloroethane have been widely used. These cleaning agents have high properties such as detergency (degreasing property), nonflammability, and drying property, and are particularly suitable for cleaning small parts and the like.

[0003] However, chlorofluorocarbon-based and chlorine-based cleaning agents have become a serious problem due to environmental pollution and toxicity, and have become difficult to use in the future. Therefore, as a substitute for CFC-based and chlorine-based cleaning agents, hydrocarbon-based cleaning agents such as kerosene, and quasi-aqueous cleaning obtained by mixing a surfactant and water containing a hydrocarbon-based solvent and a water-soluble solvent as main components. Various types of water-based detergents obtained by blending an agent or an alkali builder with a surfactant and adding a small amount of a solvent as necessary have been studied and used. However, these cleaning agents also have respective problems as described below.

[0004] That is, hydrocarbon-based cleaning agents are toxic and flammable. In addition, the quasi-aqueous solvent has a danger in handling due to the possibility of ignition due to evaporation of water, and the addition of water also has problems in metal corrosivity and wastewater treatment. On the other hand, water-based cleaning agents are extremely low in danger and toxicity, and are highly safe cleaning agents that do not affect environmental pollution. On the other hand, on the other hand, properties such as detergency (degreasing property) and drying property are inferior to solvent-based and semi-aqueous detergents, and metal corrosiveness and wastewater treatment properties become problems similarly to the semi-aqueous solvent.

JP-A-5-51599 discloses a water-based detergent containing a polyalkylene glycol monophenyl ether solvent, acetylene glycol or / and an alkylene oxide adduct thereof, a glycol ether solvent, and water. Are disclosed. This is a combination of a polyalkylene glycol monophenyl ether solvent having a relatively small solubility in water obtained by adding 1 to 2 moles of an alkylene oxide to phenol, and a glycol ether solvent completely soluble in water,
Further, the addition of water makes it a safe cleaning agent having a high detergency (degreasing power) and easy recovery of waste oil. In addition, the use of an acetylene glycol-based non-ionic surfactant makes the cleaning agent extremely low foaming.

[0006]

However, the conventional water-based cleaning agent disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 5-51599 does not consider metal corrosion. For this reason, when cleaning a metal product using this water-based cleaning agent, rust is generated on the metal product due to residual moisture or undulation, which is a problem.

In particular, in the case of a water-based cleaning agent, the pollutants in the wastewater are separated and removed, or their properties are changed to render them harmless, thereby effectively purifying the wastewater. Improvement is an important issue. Organic substances as non-preservative substances among pollutants are aerobically oxidatively decomposed by microorganisms in water with the consumption of dissolved oxygen in water. As a result, the concentration of pollutants in the wastewater decreases, and the purification of the wastewater proceeds. For this reason, if the organic matter present in the treated water has a high biological treatability, such organic matter is easily decomposed and removed, so that the wastewater can be effectively purified. Therefore, in a water-based cleaning agent, it is important to use an organic component having a high biological processing property in the cleaning composition in order to improve the wastewater treatment property.

Here, in a conventional water-based cleaning agent,
In order to improve the detergency and emulsifying power, petroleum synthetic fatty acids are generally used. Such petroleum-based synthetic fatty acids have low biotreatability. For this reason, it has been difficult for conventional water-based cleaning agents to effectively purify the wastewater. The present invention has been made in view of the above circumstances,
The problem to be solved is to provide a metal product detergent composition which can be used as a metal product water-based detergent having high rust prevention properties and waste water treatment properties (biological treatment properties) and high detergency (degreasing properties). It is a technical issue.

[0009]

Means for Solving the Problems The cleaning composition for metal products of the present invention, which solves the above-mentioned problems, comprises an amine soap of a vegetable fatty acid containing at least one of oleic acid and linoleic acid, and a polyoxyethylene non-ionic. An ionic surfactant, a glycol ether-based water-soluble organic solvent, a sequestering agent, and a dibasic fatty acid amine soap,
It is characterized by the fact that it consists of the remaining water.

[0010]

The detergent composition for metal products of the present invention is diluted with water at a predetermined concentration and used as an aqueous detergent. And this water-based detergent has high wastewater treatment property (biological treatment property) and rust prevention property by the action of each component shown below,
In addition, it exhibits each property such as adsorptivity, emulsifying property, solubility, permeability and dispersibility, and has high detergency.

First, when the amine soap of a vegetable fatty acid containing at least one of oleic acid and linoleic acid is dissolved in water-soluble, it is dispersed as a colloid. Colloids act strongly on oils (oils and fats) to emulsify and dissolve the oil. Further, a part of the colloid forms an electrolyte and forms a micelle as an aggregate of molecules or ions. Molecules in the micelles adhere around oils and fats and perform actions such as dispersion, adsorption, and suspension. Therefore, the amine soap of the vegetable fatty acid contributes to the improvement of detergency (defatting power).

[0012] Vegetable fatty acids which are natural fatty acids are
Compared to petroleum-based synthetic fatty acids, it has higher biotreatment properties and is easily oxidatively decomposed by microorganisms in water. Therefore, the amine soap of the vegetable fatty acid contributes to improvement of wastewater treatment property (biological treatment property). Next, the polyoxyethylene-based nonionic surfactant has a lower micelle generation concentration and a lower critical micelle concentration than other anionic and cationic surfactants. For this reason, even if the concentration of such a nonionic surfactant is low, as described above, dispersion, adsorption,
Micelles that act like suspensions are produced at high concentrations. In addition, this nonionic surfactant has extremely low surface tension as compared with other anionic surfactants. For this reason,
It has high properties such as wettability (wetability) and permeability. Therefore, the polyoxyethylene-based nonionic surfactant contributes to improvement in detergency (degreasing power).

The glycol ether-based water-soluble organic solvent is a highly hydrophilic solvent and has a high cross-linking effect with fats and oils, soap, and water, and thus has high solubilization, emulsification, and permeability properties. Therefore, the glycol ether-based water-soluble organic solvent contributes to an improvement in detergency (degreasing power). The sequestering agent can soften hard water by binding to metal ions in an aqueous solution to form a soluble chelate complex. Therefore, it is possible to prevent the detergency from decreasing due to the binding of metal ions in the aqueous solution to the soap, which contributes to the improvement in detergency (degreasing power).

The dibasic fatty acid amine soap acts as a rust preventive effect because it forms a thin film on the surface of a cleaning object or a cleaning device. For example, among the saturated fatty acids, a dibasic carboxylic acid is a raw material that reacts with hexamethylenediamine to produce a polyamide resin (nylon 6, 6, etc.), and has a property that coating film performance and water resistance are good. The dibasic fatty acid amine soap is water-soluble as a fatty acid amine soap in order to utilize such performance of the dibasic saturated fatty acid. Therefore, when the aqueous solution of the dibasic fatty acid amine soap comes into contact with the surface of the cleaning object or the cleaning device, a thin film is formed on the surface, and the thin film can prevent metal corrosion.

Water is added to uniformly disperse and mix the above components. The cleaning agent obtained by diluting the cleaning composition of the present invention with water is effective for ultrasonic cleaning of small parts such as automobiles and machines, electric and electronic devices, parts having a solid surface of a predetermined shape, jigs and the like. Can be used for In particular,
Since this cleaning agent has high wettability and high permeability, it exhibits performance suitable for ultrasonic cleaning of small parts. According to this cleaning agent, the contaminants are dirt in which organic powder such as oils and fats, machine oil, quenching oil, grease, and flux are mixed, and metal powder, carbon, and inorganic powder are mixed therein. Can also be effectively removed.

Further, when the cleaning agent according to the present invention is applied to ultrasonic cleaning, a vegetable fatty acid containing at least one of oleic acid and linoleic acid dissolves in an aqueous solution to form a colloid, which causes Brownian motion. (Chemical effect)
And a cavitation effect of the ultrasonic cleaning apparatus (a physical effect in which a pressure of several thousand atmospheres is generated in the vicinity when bubbles are generated and disappear), so that higher cleaning power can be expected.

[0017]

【Example】

(Preferred Embodiment) The mixing ratio of the cleaning composition for metal products of the present invention is preferably as follows. (A) Amine soap of vegetable fatty acid containing at least one of oleic acid and linoleic acid: 5 to 20 parts by weight (b) Polyoxyethylene nonionic surfactant: 5 to 15 parts by weight (c) Glycol ether Water-soluble organic solvent: 5 to 15 parts by weight (d) Sequestering agent: 5 to 15 parts by weight (e) Dibasic fatty acid amine soap: 5 to 15 parts by weight (f) Water: balance At this time, the above components The proportion of (f) water added to (a), (b), (c), (d) and (e) is not particularly limited, but from the viewpoint of minimizing the volume of the entire detergent composition, What is necessary is just to add the minimum amount of water in which the components can be uniformly dispersed and mixed.

(A) When the blending ratio of the amine soap of the vegetable fatty acid containing at least one of oleic acid and linoleic acid is less than 5 parts by weight, the detergency (emulsification, adsorption, etc.) is reduced, and the amount is less than 20 parts by weight. If the amount is too large, a problem occurs in solubility at the time of use dilution due to uneven mixing of components and an increase in viscosity. (B) If the compounding ratio of the polyoxyethylene-based nonionic surfactant is less than 5 parts by weight, the detergency (wetting property,
If the amount exceeds 15 parts by weight, the load on the wastewater treatment is increased.

(C) If the blending ratio of the glycol ether-based water-soluble organic solvent is less than 5 parts by weight, there is a problem in solubility at the time of use dilution due to heterogeneous mixing of amine soap and increase in viscosity, and 15 parts by weight. If it is larger than this, the load on the wastewater treatment will be increased. (D) If the compounding ratio of the sequestering agent is less than 5 parts by weight, the hardness component (Mg, Ca content) of the diluent reacts with the amine soap to become insoluble and the performance of the conventional amine soap can be sufficiently exhibited. If the amount is more than 15 parts by weight, more chemicals than necessary as ion-sequestering and builder will be added, and the load of wastewater treatment and the load of price will be increased.

(E) If the compounding ratio of the dibasic fatty acid amine soap is less than 5 parts by weight, the temporary rust preventive power (no rusting for 24 hours) as a rust preventive agent cannot be maintained,
If the amount is more than 15 parts by weight, the quality becomes excessive and the wastewater treatment is burdened. When the detergent composition of the present invention is diluted with water and used as a detergent, it is preferable to dilute the detergent composition with water so that the concentration of the concentrate becomes 1 to 8 wt% when the detergent composition is used as a stock solution. More preferably, the content is 2 to 5% by weight. If the concentration of this stock solution is lower than 1 wt%, there is a problem in rust prevention. On the other hand, if the concentration is higher than 8 wt%, the detergency (degreasing power) does not increase, which is disadvantageous in cost.

Further, as one preferred embodiment of the detergent composition for metal products of the present invention, (a) tall oil fatty acid amine soap: 5 to 20 parts by weight (b) polyethylene glycol paraisooctyl phenyl ether: 5 to 15 parts by weight (C) dipropylene glycol monomethyl ether: 5 to 15 parts by weight (d) ethylenediaminetetraacetylic acid: 5 to 15 parts by weight (e) dibasic fatty acid amine soap: 5 to 15 parts by weight (f) water: balance Detergent compositions can be mentioned.

(A) As the amine soap of vegetable fatty acid, an amine soap of only one of oleic acid and linoleic acid may be used, but an amine soap of vegetable fatty acid containing both oleic acid and linoleic acid is used. Is preferred. When using an amine soap of a single vegetable fatty acid of oleic acid or linoleic acid, it is necessary to extract and purify oleic acid or linoleic acid from a certain natural vegetable fatty acid, which is disadvantageous in terms of cost, and This is because if the amine soaps of both oleic acid and linoleic acid are included, it is possible to expect improvement in the cleaning properties according to the respective properties. As the amine soap of vegetable fatty acid containing both oleic acid and linoleic acid, the above-mentioned tall oil fatty acid amine soap can be mentioned. Tall oil fatty acid is obtained by separating fatty acid from tall oil as a product obtained when pulp is manufactured from pine wood by the kraft method, and its component is oleic acid: 4
0 to 50%, linoleic acid: 40 to 45%, saturated acid: 10
%.

The amine soap of oleic acid constituting the above-mentioned tall oil fatty acid amine soap is obtained, for example, by the following formula 1, and the amine soap of linoleic acid forming the tall oil fatty acid amine soap is obtained, for example, by the following formula 2. Can be

[0024]

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[0025]

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(B) Examples of the polyoxyethylene-based nonionic surfactant include pn-octylphenol and on-octylphenol in addition to the above-mentioned polyethylene glycol paraisooctylphenyl ether. In addition, polyethylene glycol paraisooctyl phenyl ether is represented by the following formula (3).

[0027]

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(C) Examples of the glycol ether-based water-soluble organic solvent include propylene glycol monomethyl ether, propylene glycol dimethyl ether and the like in addition to the above-mentioned dipropylene glycol monomethyl ether. In addition, dipropylene glycol monomethyl ether is represented by the following formula (4).

[0029]

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(D) As the sequestering agent, the above ethylenediaminetetraacetylic acid can be used. In addition, ethylenediaminetetraacetic acid is represented by the following formula (5).

[0031]

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Example 1 The following components were mixed to prepare a cleaning composition of Example 1. (A) Tall oil fatty acid amine soap: 13% by weight (b) Polyethylene glycol paraisooctyl phenyl ether: 7% by weight (c) Dipropylene glycol monomethyl ether: 6% by weight (d) Ethylene diamine tetraacetic acid: 6% by weight (e) Dibasic Fatty acid amine soap: 9 wt% (f) Water: balance The detergent composition was used as a stock solution, and diluted with ion-exchanged water so that the stock solution concentration became 2 wt%, to obtain an aqueous detergent according to Example 1.

(Comparative Example 1) 1.1.1.
Trichloroethane was prepared as the cleaning agent of Comparative Example 1. Comparative Example 2 A cleaning composition of Comparative Example 2 was prepared by mixing the following components.

Fatty acid amine soap (caprylic acid): 10 to 20% by weight Surfactant (cationic amine oxide type): 20 to 30% by weight Water: balance The concentration of the undiluted solution is 2% by weight using this detergent composition as a undiluted solution. To obtain a water-based detergent as a chlorine-based alternative detergent according to Comparative Example 2.

Comparative Example 3 The following components were mixed to prepare a detergent composition of Comparative Example 3. Fatty acid amine soap (caprylic acid): 10 to 20 wt% Dibasic fatty acid amine soap: 10 to 20 wt% Surfactant (nonionic special ether type): 1 to 5 wt% (nonionic polyethylene type): 1 to 5 wt% (cation System): 1 to 5 wt% Water: Balance Water-based cleaning as a chlorine-based alternative cleaning agent according to Comparative Example 3 by diluting this cleaning composition as a stock solution with ion-exchanged water so that the stock solution concentration becomes 2 wt%. Agent was obtained.

(Evaluation of Detergency) Using the cleaning agents of Example 1 and Comparative Examples 1 and 3, two kinds of parts P were used as follows.
(80 mm x 150 mm), small parts Q (12 mm x 5
mm washer) was subjected to ultrasonic cleaning, and the cleaning property was evaluated. After weighing the parts (the weighing result at this time is referred to as weighing A), machine oil as a contaminated oil was applied and the parts were weighed again (the weighing result at this time was referred to as weighing B). The part to which the machine oil was applied was immersed in the aqueous cleaning agent heated to 60 ° C., and ultrasonic cleaning was performed with a total cleaning time of 3 minutes. This was performed by applying ultrasonic waves of 28 kHz, 45 kHz, and 100 kHz to the liquid three times for 20 seconds each. After the ultrasonic cleaning, the parts removed from the cleaning agent were rinsed (the parts were moved up and down three times in ion-exchanged water), and then dried with hot air at 105 ° C. for 15 minutes. Then, after cooling the part to room temperature, the part was weighed (the weighing result at this time is C).

From the weighing results A, B, and C, the cleaning rate (oil removal rate) was determined according to the following formula. Table 1 shows the results. [Washing rate calculation formula] Washing rate (%) = ｛1-[(Weight C−Weight A) / (Weight B)
-Weighing A)] x 100

[0038]

[Table 1] From the results in Table 1, the cleaning agent of Example 1 has improved detergency (oil removal rate) as compared with the cleaning agent according to Comparative Example 3 as a conventional water-based cleaning agent, and the chlorine-based cleaning agent It is understood that the cleaning agent according to Comparative Example 1 is equivalent to the cleaning agent according to Comparative Example 1.

As described above, the cleaning agent of the first embodiment exhibits the same detergency as a conventional chlorine-based cleaning agent, and thus can be replaced with a conventional chlorine-based cleaning agent. It is not necessary to change the ultrasonic cleaning equipment for the cleaning agent. Further, according to the cleaning agent of the first embodiment, as compared with the case of using the chlorine-based cleaning agent, the toxicity is extremely low, the safety for the human body can be secured high, and a favorable working environment free from evaporation and air diffusion. Can be secured.

(Evaluation of Wastewater Treatment Properties) The cleaning agents of Example 1 and Comparative Examples 2 and 3 were subjected to coagulation treatment and activated sludge treatment as described below to evaluate wastewater treatment properties. In order to perform coagulation treatment with chemicals, sulfuric acid (acid decomposition), caustic soda (pH adjuster), slaked lime (neutralization), sulfuric acid band (coagulant) and polymer coagulant (coagulation aid) are shown below in proportions, respectively. Prepared with 1 l of pure water as an additive chemical.

Sulfuric acid: 100 g / l Caustic soda: 100 g / l Slaked lime: 100 g / l Sulfuric acid band: 100 g / l High molecular coagulant: 1 g / l
(2000 to 3000 ppm for the flocculant and 50 to 100 ppm for the high-molecular flocculant) to form the components in the liquid as flocs, and remove the components to remove the COD in the liquid.
(Chemical oxygen demand) and BOD (Biological oxygen demand)
Coagulation treatment to reduce the Table 2 shows the results of the water quality measurement after the treatment.

Subsequently, the COD was adjusted to 50 mg / L by diluting the cleaning agent after the coagulation treatment with pure water, and this was placed in a glass container of about 20 L. Then, activated sludge was introduced into the glass container at a rate of 2000 mL / L. Next, while controlling the air amount with an air flow meter, an appropriate amount of air (200 ± 20 mL / mi
In (n), activated sludge treatment was performed by aeration for 24 hours. Table 2 also shows the results of the water quality measurement after the treatment.

[0043]

[Table 2]

From the results shown in Table 2, the cleaning agent of Example 1 has a higher BOD and COD removal rate than the cleaning agents of Comparative Examples 2 and 3 as conventional water-based cleaning agents, It turns out that processability is high. Therefore, according to the cleaning agent of the first embodiment, the burden on the wastewater treatment plant can be reduced when the waste liquid after the cleaning is subjected to the activated sludge treatment as compared with the conventional water-based cleaning agent. Further, compared with the waste liquid of the chlorine-based cleaning agent, the waste liquid of the cleaning agent according to the first embodiment, which is a water-based cleaning agent, has high safety (low toxicity and harmfulness) and is easy to handle. In addition, the chlorine system requires a waste treatment company to treat it, but the cleaning agent can be decomposed by biological treatment, so that the treatment property is easy, and the number of waste liquid treatment steps and cost can be reduced.

(Evaluation of Rust Prevention Property 1) Each of the sample solutions shown in Table 3 (each sample diluted with ion-exchanged water at various concentrations) was applied to a polished and cleaned steel test piece with a dropper.
20 drops of water droplets of 20 mm
After a lapse of time, the occurrence of rust on the water drop portion was observed. Table 3 shows the results.

[0046]

[Table 3] From the results shown in Table 3, it can be seen that the dibasic fatty acid amine soap exhibits a rust-preventive effect even at an extremely low concentration, and has a higher rust-preventive effect than amine oleate soap or tall oil fatty acid amine soap.

(Evaluation of rust prevention 2) Washed cast iron (FC-2)
25 g of the cutting powder of 0) was placed in a petri dish with a lid, and each of the sample solutions shown in Table 4 (each component diluted with ion-exchanged water at a concentration of 1%) was put therein until the cutting powder was completely immersed. Was. The sample liquid was poured out, the liquid was drained to the extent that a small amount of the sample liquid remained, and the rusting state of the cutting powder was observed from the upper and lower surfaces of the petri dish at room temperature for an elapsed time. Table 4 shows the results. In Table 4, ◎ indicates no rust, は indicates one or two points of rust, Δ indicates ten or more points of rust, and x indicates several tens to one-third of the cutting powder. And xx indicates that rust was generated in 1/3 or more of the cutting powder.

[0048]

[Table 4] From the results in Table 4, it can be seen that the dibasic fatty acid amine soap has a higher rustproofing power than amine oleate soap and tall oil fatty acid amine soap.

[0049]

As described above in detail, according to the cleaning composition for metal products of the present invention, the cleaning composition (degreasing property) can be obtained even though it is a water-based cleaning agent, by the constitution described in the claims.
Further, it is possible to provide a water-based cleaning agent having high rust prevention and high wastewater treatment (biological treatment).

Therefore, the cleaning agent according to the present invention can be used as an industrial cleaning agent which can be replaced with a chlorofluorocarbon-based or chlorine-based cleaning agent which is a major problem due to environmental pollution and can clean metal parts. Can be used.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C11D 3:20 3:33) (72) Inventor Miki Soma 6-1, Meiwa-cho, Toyota-shi, Aichi Prefecture Inside Toyota Chemical Industry Co., Ltd. (56) References JP-A-2-16200 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C23G 5/032 C11D 10/04 C11D 9:02 C11D 1:72 C11D 3:20 C11D 3:33

Claims (1)

(57) [Claims] 1. An amine soap of a vegetable fatty acid containing at least one of oleic acid and linoleic acid, a polyoxyethylene-based nonionic surfactant, a glycol ether-based water-soluble organic solvent, and a sequestering agent And a dibasic fatty acid amine soap, and water.