JP4824656B2 - Metal detergent composition and metal detergent - Google Patents

Description

  The present invention relates to a metal detergent composition used for removing processing oil, chips, fingerprints, dust, and the like adhering to ferrous metal parts and non-ferrous metal parts, and a metal detergent obtained by diluting the same.

  Ferrous metal materials typified by castings and steel plates, and non-ferrous metal materials typified by aluminum and copper are processed and used in various fields such as the automobile industry, machine industry, metal industry, and electrical industry. ing.

  These ferrous metals and non-ferrous metals are subjected to processing such as pressing, cutting and annealing in the former, and processing such as pressing and cutting are performed in the latter, in the processing step. After these treatments, as a preparation for the final finishing or the next process, a cleaning and removing treatment for contaminants adhering to the surface of the component is performed.

  Conventionally, water-based cleaning agents have been used for these cleanings in addition to halogenated hydrocarbons such as CFC-113 and 1,1,1-trichloroethane, and petroleum hydrocarbons.

  However, in the case of water-based cleaning agents, (1) a cleaning line is required for each of ferrous metals and non-ferrous metals, (2) rinsing of water is required in either case, (3) iron-based cleaning agents In metal cleaning, the process is complicated, such as removing the cleaning agent component with a rinsing liquid containing a rust-preventing component after defatting and cleaning, and requiring a rust-proofing treatment.

  A method for solving these problems has been proposed in Patent Document 1, Patent Document 2, and the like, but these inventions did not solve all of the above (1) to (3).

In addition, although the invention of Patent Document 3 has improved these problems, it has not been satisfactory in the environmental characteristics currently required. Specifically, the alkanolamine used in the present invention has concerns about harmfulness to the human body, adverse effects on the environment, etc., and falls under the scope of various laws and regulations including the PRTR Law. It has been.
JP-A-7-90657 JP 7-305186 A JP-A-9-118900

  The present invention has been made in view of the above, and can wash iron-based metals and non-ferrous metals in the same washing line, does not require rinsing of water, and is intended for rust prevention and corrosion prevention. It is intended to provide a cleaning agent that can be used without separately blending, and has good safety and environmental compatibility.

  The present inventors have found that a cleaning composition comprising a specific dicarboxylic acid, amine, amine ethylene oxide adduct, chelating agent, nonionic surfactant, glycol ether and water can solve the above-mentioned problems. The present invention has been completed based on the findings.

The metal detergent composition of the present invention contains the following components (a) to (g) in order to solve the above problems.
(A) 1-20% by weight of a dicarboxylic acid containing dodecanedioic acid,
(B) 1 to 15% by weight of one or two aminoalcohol amines selected from the group consisting of N- (β-aminoethyl) ethanolamine and N-ethylethanolamine,
(C) 1 to 20% by weight of ethylene oxide adduct of one or two alicyclic amines selected from the group consisting of cyclohexylamine EO 2 mol adduct and piperidine EO 1 mol adduct,
(D) one or two sequestering agents selected from the group consisting of L-glutamic acid diacetate, methylglycine diacetate, and gluconate 0.1 to 5% by weight,
(E) 0.1 to 10% by weight of an ether type nonionic surfactant containing polyoxyalkylene tridecyl ether,
(F) One or more glycol ethers selected from the group consisting of diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol isobutyl ether, and dipropylene glycol monomethyl ether 5-50 weight%,
(G) Water 5% by weight or more.

  The metal detergent of the present invention is prepared by diluting the metal detergent composition of the present invention to 0.5 to 20% by weight with water to a pH of 6.5 to 8.5.

  According to the present invention, an iron-based metal and a non-ferrous metal can be cleaned in the same cleaning line, and rinsing with water is unnecessary and has a rust-preventing function. It is possible to provide a metal cleaning composition and a metal cleaning agent that can be used without separately blending, and have good safety and environmental compatibility.

The component (a) used in the present invention is an aliphatic dicarboxylic acid having 10 to 12 carbon atoms (HOOC— (CH ₂ ) _8-10 —COOH), and more preferably has excellent rust resistance against iron-based components. This is dodecanedioic acid having 12 carbon atoms. Moreover, it is possible to improve defoaming property by combining sebacic acid.

  The amount of component (a) is 1 to 20% by weight, more preferably 5 to 10% by weight. If the blending amount is less than 1%, it becomes difficult to exhibit the rust prevention performance against the iron-based material, and it is uneconomical because it must be used at a high concentration in order to obtain sufficient rust prevention performance. On the other hand, if it exceeds 20% by weight, there may be an effect such that stains are likely to occur in the finished product after washing. A dicarboxylic acid having 8 or less carbon atoms, such as suberic acid, adipic acid, terephthalic acid, or monocarboxylic acid octylic acid, in any case, even when the pH of the aqueous solution is in the range of 7.0 to 8.5, Insufficient rust prevention performance for iron-based metals such as castings, etc., and to obtain rust prevention performance, it must be used at a high concentration. Is not appropriate, such as becoming uneconomical.

  Next, as the amino alcohol amine as the component (b), N, N-dimethylethanolamine, N- (β-aminoethyl) ethanolamine, N-methylethanolamine, N-ethylethanolamine, N-butylethanol Examples include amines and N-butyldiethanolamine. These amino alcohol amines may be used alone or in combination.

  Further, as the (c) component cycloaliphatic amine ethylene oxide adduct, cyclohexylamine ethylene oxide 1 mol adduct, cyclohexylamine ethylene oxide 2 mol adduct, cyclohexylamine ethylene oxide 3 mol adduct, piperidine ethylene oxide 1 Mole adducts and the like can be mentioned. These alicyclic amine ethylene oxide adducts may be used alone or in combination.

  The blending amounts of the component (b) and the component (c) are 1 to 15% by weight and 1 to 20% by weight, respectively. The blending amount of the component (b) and the component (c) is (a The range of 50% by weight or more of the amount of dodecanedioic acid used as the component is not more than 200% by weight. That is, when diluted with water to 0.5 to 20.0% by weight, the pH of the detergent (diluted detergent composition) is in the range of 6.5 to 8.5. As a pH adjuster, it is added in conjunction with the amount of dodecanedioic acid. The pH of the stock solution (cleaning composition before dilution) does not matter. If the pH of the cleaning agent is less than 6.5, dodecanedioic acid will precipitate in the aqueous solution, or sufficient rust prevention performance and cleaning performance will not be obtained for ferrous metals, and if the pH exceeds 8.5 When washing non-ferrous metals, particularly aluminum, etc., it is not preferable because it may cause an adverse effect such as discoloration, or may become irritating to the human body, particularly the skin. On the other hand, when an inorganic alkali such as NaOH is used, it becomes a white residue after washing and adversely affects the appearance of the component, so that its use is not preferable.

  In addition, as the sequestering agent (chelating agent) of component (d), L-glutamic acid diacetate, methylglycine diacetate, gluconate, ethylenediaminetetraacetate, nitrilotriacetic acid, iminodiacetic acid, hydroxyethyl Ethylenediamine triacetate, diethylenetriaminepentaacetate, glycol etherdiaminetetraacetate, hydroxyethylenediaminetetraamine hexaacetate, hydroxyethyliminodiacetate, triethylenetetramine hexaacetate, diencorate, hydroxyethane diphosphonate, Examples thereof include citrate and malate. These include alkali metal salts, ammonium salts, alkanolamine salts and the like. L-glutamic acid diacetate, methylglycine diacetate, and gluconate are preferable from the viewpoint of improving the cleaning property when blended with little influence on the human body and the environment. These sequestering agents may be used alone or in combination.

  The amount of component (d) is 0.1 to 5% by weight. If the blending amount is less than 0.1% by weight, water is used when the cleaning composition is diluted with hard water such as industrial water or well water, or when contaminants containing inorganic components such as calcium are mixed. An insoluble precipitate is generated, which may cause troubles in the facility and may cause poor cleaning, which is not preferable. On the other hand, if it exceeds 5% by weight, the finish after washing deteriorates, which is not preferable.

  Specific examples of the (e) component ether type nonionic surfactant include polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, polyoxyethylene allyl ether, polyoxyalkylene allyl ether, polyoxyethylene styrene. Phenyloxy ether, polyoxyalkylene styrenated phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene glyceryl ether, and the like.

  The blending amount of the component (e) is 0.1 to 5% by weight, and if it is less than 0.1% by weight, sufficient cleaning performance cannot be obtained, and if it exceeds 5% by weight, it is emulsified with contaminants. The oil / water separation performance is deteriorated, the life of the cleaning agent is shortened, and it becomes easy to appear as a stain after cleaning.

  Furthermore, examples of the glycol ether of component (f) include diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol isobutyl ether, and dipropylene glycol monomethyl ether.

  The blending amount of the component (f) is 5 to 50% by weight, and if it is less than 5% by weight, the separability of contaminants removed when washing contaminants such as processing oil is deteriorated, and the cleaning agent Is not economical because the lifespan is shortened. On the other hand, if it exceeds 50% by weight, the finish after washing deteriorates, which is not preferable. In addition, the lower alcohol ethylene oxide 1 mol adduct having 2 to 4 carbon atoms is feared to have an adverse effect on the human body, and the adduct of 3 mol or more is poor in detergency and solubilization effect and easily appears as a stain after washing, It is not preferable in terms of appearance.

  Finally, (g) component water is added in an amount of 5% by weight or more as the balance in order to make the composition into a uniform liquid product. If it is less than 5% by weight, flammability is exhibited, and the liquid falls under the Fire Service Act Type 4 and Type 3 petroleum, and there is a problem in handling safety, which is not appropriate. Examples of water used in the present invention include city water, well water, pure water (water that has been desalted with an ion exchange resin, etc.), ultrapure water (not only inorganic ions, organic matter, viable bacteria, fine particles, Water from which dissolved gas, etc. has been removed), various functional waters that have been proposed in recent years, and pure water and ultrapure water, etc., from the point of low metal ion content that adversely affects the electronic control unit preferable.

  The metal detergent composition of the present invention combines (b) an amino alcohol amine and (c) an ethylene oxide adduct of an alicyclic amine with (a) a dicarboxylic acid such as dodecanedioic acid as described above. Thus, rust prevention and corrosion prevention for ferrous and non-ferrous metals are synergistically improved.

  It also contains (e) an ether type nonionic surfactant for the purpose of washing assistance and defoaming function, and (f) the nonionic surfactant is solubilized by using an ethylene oxide adduct of a lower alcohol. Can create a uniform transparent product. Further, by blending an ethylene oxide adduct of a lower alcohol, it is possible to improve the separability of contaminants removed when the contaminants are washed.

  The metal detergent composition of the present invention may further contain a known antifoaming agent, preservative, antioxidant and the like, if necessary. Moreover, you may add a well-known anionic surfactant, an amphoteric surfactant, and a fluorine-type surfactant as needed.

  As a cleaning method using the cleaning agent of the present invention, those conventionally used are appropriately used and are not particularly limited. For example, an immersion method, an ultrasonic cleaning method, an immersion rocking method, and a spray method are used. It is possible to carry out various cleaning methods such as a hand wiping method alone or in combination.

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

[Examples and Comparative Examples]
Each component was mix | blended and mixed in the ratio shown in the following Table 1 and Table 2, and the metal cleaning composition was prepared.

  Regarding the obtained cleaning composition, (1) Influence on non-ferrous materials (Test-1), (2) Influence on ferrous materials (Test-2), (3) Finishability (Test-3), ( 4) Product stability (Test-4), (5) Detergency (Test-5), (6) Foaming property (Test-6), (7) Oil / water separation property (Test-7), (8) Resistance Hard water (Test-8), (9) Safety (Test-9), (10) Environmental compatibility (Test-10) were examined. The results are shown in “Table 3” and “Table 4”.

[Test-1]
The effects on non-ferrous materials were compared by the following methods. That is, the detergent composition obtained above was diluted to a concentration of 10% by weight with water to obtain a detergent.

  The obtained cleaning agent was heated to 50 ° C., and a standard aluminum plate (JIS H4000 A2024P) subjected to constant treatment was immersed in this solution for 1 hour.

After a predetermined time, this plate was taken out and its surface was wiped clean with gauze, and then the aluminum surface condition was compared according to the following criteria. The pH of the solution (cleaning agent) is also shown.
[Standard]
○: No change in color tone Δ: A slight change in color tone ×: Significant change in color tone

[Test-2]
The antirust property to iron materials was compared by the following methods. That is, the cleaning composition obtained above was diluted to 1% by weight with water to obtain a cleaning composition.

  Cast iron powder (FC20) was spread on a petri dish, and 2 ml of the obtained cleaning agent was dropped on the cast iron powder, and the rusting situation in 2 hours at room temperature was confirmed, and compared according to the following criteria.

[Standard]
A: No rusting O: Rusting less than 5% Δ: Rusting 5% or more to less than 25% ×: Rusting 25% or more.

[Test-3]
The finish was compared by the following method. That is, the cleaning composition obtained above was diluted to 1% by weight with water to obtain a cleaning composition.

  The obtained cleaning agent was heated to 50 ° C., and a standard steel plate (SPCC-SB) subjected to a constant treatment was immersed in this solution for 1 minute.

  After 1 minute, this plate was taken out, dried with hot air at 80 ° C., and then the surface finish was compared according to the following criteria.

[Standard]
○: The finished state is good. △: The finished state is slightly bad. X: The finished property is bad.

[Test-4]
Product stability was compared by the following method. That is, two 100 ml samples of the cleaning composition were prepared as described above, one was left at 50 ° C. for one week, the other was left at -50 ° C. for one week, and the liquid state thereafter was observed. The product stability of the cleaning agent was evaluated according to the following criteria.

[Standard]
○: A transparent liquid is maintained at 50 ° C and -50 ° C after 1 week. ×: Turbidity and precipitation at 50 ° C and -50 ° C or both after 1 week.・ Separation, etc. occurs and the clear liquid is not maintained.

[Test-5]
The detergency was compared by the following method. In addition, the steel plate (SPCC) which apply | coated A heavy oil uniformly was heat-processed for 3 minutes at 100 degreeC, and it used for the test, after cooling.

  The cleaning composition obtained above was diluted with water to a concentration of 10% by weight to obtain a cleaning composition.

  The obtained cleaning agent is heated to 50 ° C., washed with a 28 kHz, 150 W ultrasonic cleaner, diluted to 1% by weight, and then washed with a product heated to 50 ° C. After air blowing, hot air drying at 80 ° C. was performed for 5 minutes.

  Next, the oil remaining on the steel sheet and the cleaning agent residue were extracted using a solvent, measured by spectrophotometry, and the cleaning performance was compared according to the following criteria.

[Standard]
A: Removal rate of 95% or more B: Removal rate of 75% or more and less than 95% Δ: Removal rate of 50% or more and less than 75% ×: Removal rate of less than 50%

[Test-6]
The foamability was compared by the following method. The cleaning composition obtained above was diluted with water to a concentration of 10% by weight to obtain a cleaning composition.

  50 ml of the resulting cleaning agent was placed in a 100 ml graduated Nessler tube and heated to 50 ° C.

  Next, the Nessler tube was vigorously shaken 100 times in 30 seconds, the amount of foam after 30 seconds was confirmed, and the foaming performance was compared according to the following criteria.

[Standard]
○: Foam volume of 10 ml or less Δ: Foam volume of over 10 ml and 20 ml or less ×: Foam volume of over 20 ml

[Test-7]
Oil water separation was compared by the following method. The cleaning composition obtained above was diluted with water to a concentration of 10% by weight to obtain a cleaning composition.

  50 ml of the obtained cleaning agent was placed in a 100 ml graduated Nessler tube, and 5 ml of oily processing oil (mineral oil, manufactured by Nippon Kogyo Oil Co., Ltd., product name: 3050) was further added and heated to 50 ° C.

  Next, the Nessler tube was vigorously shaken 100 times in 30 seconds, and then allowed to stand at 50 ° C., and the oil separation state after 30 minutes was confirmed, and the oil-water separation performance was compared according to the following criteria.

[Standard]
○: Separation rate of 80% or more Δ: Separation rate of 50% or more and less than 80% ×: Separation rate of less than 50%

[Test-8]
Hard water resistance was compared by the following method. The cleaning composition obtained above was diluted to a concentration of 10% by weight using tap water from Kyoto City, thereby obtaining a cleaning composition.

  100 ml of the resulting cleaning agent was allowed to stand at 50 ° C. for 30 minutes, the subsequent liquid state was observed, and the hard water resistance of the cleaning agent was evaluated according to the following criteria.

[Standard]
○: A colorless transparent liquid remains after 30 minutes. ×: A white precipitate is formed after 30 minutes.

[Test-9]
The safety of the cleaning compositions obtained above was compared according to the following criteria.

[Standard]
○: Standard handling is possible (not restricted by laws and regulations of the Fire Services Act and the Poisonous and Deleterious Substances Control Law)
×: Sufficient consideration is required for handling (restricted by laws and regulations of the Fire Service Act and the Poisonous and Deleterious Substances Control Law).

[Test-10]
The environmental compatibility of the cleaning compositions obtained above was compared according to the following criteria.

[Standard]
○: Not restricted by laws and regulations such as PRTR Law and Occupational Safety and Health Law ×: Restricted by laws and regulations such as PRTR Law and Occupational Safety and Health Law

  From the results shown in Table 3, the metal detergent compositions of the present invention shown in the examples all have excellent performance and characteristics in a well-balanced manner in each of [Test-1] to [Test-10]. It turns out that it has. On the other hand, from the results shown in Table 4, it can be seen that one of the items is greatly inferior even though the comparative example has an excellent point.

Claims (2)

A metal detergent composition comprising the following components (a) to (g):
(A) 1 to 20% by weight of a dicarboxylic acid containing dodecanedioic acid
(B) 1 to 15% by weight of one or two amino alcohol amines selected from the group consisting of N- (β-aminoethyl) ethanolamine and N-ethylethanolamine
(C) 1 to 20% by weight of ethylene oxide adduct of one or two alicyclic amines selected from the group consisting of cyclohexylamine EO 2 mol adduct and piperidine EO 1 mol adduct
(D) One or two sequestering agents selected from the group consisting of L-glutamic acid diacetate, methylglycine diacetate, and gluconate 0.1 to 5% by weight
(E) Ether type nonionic surfactant containing polyoxyalkylene tridecyl ether 0.1 to 10% by weight
(F) One or more glycol ethers selected from the group consisting of diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol isopropyl ether, diethylene glycol monobutyl ether, diethylene glycol isobutyl ether, and dipropylene glycol monomethyl ether 5-50 weight%
(G) Water 5% by weight or more   A metal detergent comprising the metal detergent composition according to claim 1 diluted to 0.5 to 20% by weight with water to a pH of 6.5 to 8.5.