JP2013213266A - Detergent composition for iron and nonferrous metal component, and cleaning method using the same - Google Patents

Abstract

[PROBLEMS] To provide a cleaning effect that can impart rust-proofing to ferrous metal parts, without corroding non-ferrous metal parts, and is also used for cleaning electronic parts with strict appearance finishes and strict management of detergent residues. A cleaning composition that can be used, and a cleaning method using the same are provided.
A nonionic surfactant represented by general formula (1), an aliphatic carboxylic acid represented by general formula (2), and an aromatic carboxylic acid represented by general formula (3). A cleaning composition is used which is contained and adjusted to have a pH of 5 to 10 using an organic alkali.
R ¹ -O - [(PO) m · (EO) n ] -H (1)
^{R 2 - (COOH) n (} 2)
R ^3- (COOH) n (3)
In the above, R ¹ represents a linear or branched alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 30 carbon atoms, PO represents propylene oxide, EO represents ethylene oxide, and m and n are Each is an average number of added moles, m is a number in the range of 0 ≦ m ≦ 20, n is a number in the range of 0 ≦ n ≦ 20, m + n ≧ 2, and R ² has 1 to 17 represents a linear or branched alkyl group, alkenyl group or alkanol group, n represents a number of 1 to ³ , R ³ represents an aromatic hydrocarbon group, and n represents a number of 1 to 3.
[Selection figure] None

Description

  The present invention relates to a cleaning composition for ferrous and non-ferrous metal parts, and a cleaning method using the same, and more specifically, a casting or steel plate used in fields such as the automobile industry, machine industry, metal industry, and electric / electronic industry. The present invention relates to a cleaning agent composition used for cleaning ferrous metal parts typified by, and non-ferrous metal parts typified by aluminum and copper, and a cleaning method using the same.

  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. Then, after these treatments, as a preparation for the final finishing or the next step, a cleaning removal treatment of contaminants attached to the surface of the component is performed.

  Conventionally, these cleaning methods include (1) halogenated hydrocarbons such as CFC-113 and 1,1,1-trichloroethane, (2) solvents such as petroleum hydrocarbons, and (3) water-based cleaning agents. Detergents have been used.

  However, the use of halogenated hydrocarbons is restricted for environmental protection because they are substances that destroy the ozone layer. In addition, since solvents such as petroleum hydrocarbons have a flash point, they must be handled with great care. Therefore, there is an increasing demand for water-based cleaning agents.

  However, in the case of a water-based cleaning agent, when a ferrous metal is cleaned, the metal surface is easily rusted during the rinsing process or during the rinsing process or during drying, and a rust prevention measure is required. Therefore, an aqueous cleaning agent containing a rust preventive component and a cleaning method using them are disclosed (for example, Patent Documents 1 and 2).

  However, the composition proposed in Patent Document 1 is a cleaning agent in which higher alkylamines are individually blended, and nonferrous metals have a problem of corrosion. Furthermore, alkylamines having 16 or more carbon atoms have poor water rinsing properties, and are not suitable for cleaning electronic components in which the appearance finish and the cleaning agent residue are strictly controlled.

JP-A-8-319499 JP 2008-133363 A

  The present invention has been made in view of the above, has a high safety and cleaning effect, can impart rust prevention to ferrous metal parts, and does not corrode non-ferrous metal parts, so that the finish of appearance and cleaning It is an object of the present invention to provide a cleaning composition that can also be used for cleaning electronic components with strict management of the cleaning agent residue, and a cleaning method using the same.

  As a result of extensive research, the present inventors have used nonionic surfactants, aliphatic carboxylic acids, aromatic carboxylic acids, and organic alkali components as essential components of a detergent composition for ferrous and nonferrous metal parts. By adjusting and using so that pH may be in the range of 5-10, it discovered that a high washing | cleaning effect was acquired, giving the antirust effect excellent in the iron and nonferrous metal surface, and came to completion of this invention.

  That is, in order to solve the above-described problems, the cleaning composition of the present invention includes a nonionic surfactant represented by the following general formula (1) and an aliphatic carboxyl represented by the following general formula (2). An acid and an aromatic carboxylic acid represented by the following general formula (3) are contained, and the pH is adjusted to be in the range of 5 to 10 using an organic alkali.

R ¹ -O - [(PO) m · (EO) n ] -H (1)
In the formula (1), R ¹ represents a linear or branched alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 30 carbon atoms, PO represents propylene oxide, and EO represents ethylene oxide. , M and n are average addition mole numbers, m is a number in the range of 0 ≦ m ≦ 20, n is a number in the range of 0 ≦ n ≦ 20, and m + n ≧ 2. The addition form of [(PO) m · (EO) n] may be either block or random, and either PO or EO may be first.

^{R 2 - (COOH) n (} 2)
In the formula (2), ^{R 2} is a straight-chain or branched 1 to 17 carbon atoms, an alkyl group, an alkenyl group or represents a alkanol group, n is a number of 1-3.

R ^3- (COOH) n (3)
However, in formula (3), ^{R 3} represents an aromatic hydrocarbon group, n is a number of 1-3.

  The cleaning composition comprises 0.01 to 30% by weight of the nonionic surfactant represented by the general formula (1) and 0.01 to 30% by weight of the aliphatic carboxylic acid represented by the general formula (2). %, The aromatic carboxylic acid represented by the general formula (3) is preferably contained in an amount of 0.01 to 30% by weight.

  As said organic alkali, 1 type (s) or 2 or more types selected from the group which consists of ammonia, tetramethylammonium hydroxide, a C1-C9 alkanolamine, and a C1-C9 alkylamine can be used.

  The cleaning method of the present invention is a method in which a ferrous metal part and a non-ferrous metal part are cleaned with a cleaning solution obtained by diluting the above-described cleaning composition of the present invention 2-200 times with water, and then rinsed with water. .

  According to the cleaning composition of the present invention, particles such as processing oil, fingerprints, swarf, abrasives and polishing pieces attached after cutting / polishing and pressing ferrous metal parts and non-ferrous metal parts are effective. It is possible to remove the rust, and the iron-based metal parts can be given rust prevention. In addition, the cleaning composition of the present invention is highly safe and can be used for cleaning electronic parts where the finish of appearance and the management of cleaning agent residues are severe without corroding non-ferrous metal parts.

  As represented by the general formula (1), the nonionic surfactant used in the present invention is a linear or branched alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 30 carbon atoms, and ethylene oxide. And / or propylene oxide.

Examples of the alkyl group represented by R ¹ in the general formula (1) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl , Heptadecyl, octadecyl, nonadecyl, eicodecyl, hexosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacyl and the like. Among these, an alkyl group having 8 to 18 carbon atoms is preferable because of excellent emulsifying dispersibility in oily contaminants.

  Examples of alkenyl groups include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonacenyl, eicosenyl, eicosenyl, , Tetracocenyl, pentacocenyl, hexacocenyl, heptacocenyl, octacocenyl and nonacosenyl, triacocenyl and the like. Among them, an alkenyl group having 8 to 18 carbon atoms is preferable because of excellent emulsification dispersibility in oily contaminants.

  Examples of aromatic hydrocarbon groups include phenyl, methylphenyl, dimethylphenyl, ethylphenol, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, Dodecylphenyl, tridecylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, eicodecylphenyl, hexosylphenyl, docosylphenyl, tricosylphenyl, tetracosyl Phenyl, monostyrenated phenyl, distyrenated phenyl, tristyrenated phenyl, naphthyl, methyl naphthyl, ethyl naphthyl, propyl naphthyl, butyl naphthy , Pentylnaphthyl, hexylnaphthyl, heptylnaphthyl, octylnaphthyl, nonylnaphthyl, decylnaphthyl, undecylnaphthyl, dodecylnaphthyl, tridecylnaphthyl, tetradecylnaphthyl, pentadecylnaphthyl, hexadecylnaphthyl, heptadecylnaphthyl, octadecylnaphthyl, octadecylnaphthyl Examples include decylnaphthyl, eicodecylnaphthyl, anthracenyl, phenanthracenyl, tetracenyl, chrycenyl, pentacenyl, hexacenyl, and heptacenyl. Of these, aromatic hydrocarbon groups such as octylphenyl, nonylphenyl, decylphenyl, and styrenated phenyl are preferred because they are excellent in emulsifying dispersibility in oily contaminants.

  The average added mole number n of ethylene oxide is preferably in the range of 0 ≦ n ≦ 20, and more preferably in the range of 2 ≦ n ≦ 15. When n exceeds 20, the hydrophilicity increases and the detergency to oily contaminants decreases.

  The average added mole number m of propylene oxide is preferably in the range of 0 ≦ m ≦ 20, and more preferably in the range of 0 ≦ m ≦ 5. When m exceeds 20, the hydrophobicity increases and the rinsing property of the cleaning agent decreases.

Furthermore, the addition form of ethylene oxide and propylene oxide may be either block or random, and either may be bonded to R ¹ —O— first. The sum (m + n) of the average addition mole number n of ethylene oxide and the average addition mole number m of propylene oxide is 2 or more, preferably in the range of 2 ≦ m + n ≦ 40, and more preferably in the range of 2 ≦ m + n ≦ 20.

  The said nonionic surfactant can also be used individually by 1 type, and can also use 2 or more types together.

Next, examples of the aliphatic carboxylic acid used in the present invention include acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, and tridecanoic acid. , Tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, propanedioic acid, butanedioic acid, pentanedioic acid, hexanedioic acid, heptanedioic acid, octanedioic acid, nonanedioic acid, decanedioic acid, undecane diacid Acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, citric acid, glycolic acid, lactic acid, acrylic acid, methacrylic acid, crotonic acid Oleic acid, fumaric acid, maleic acid and the like. Among these, aliphatic carboxylic acids having 8 to 10 carbon atoms in R ¹ are preferable because the film formed on the surface of the material tends to be dense and has an excellent rust prevention effect. Specific examples thereof include octanoic acid and nonanoic acid. , Decanoic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid. These aliphatic carboxylic acids can be used alone or in combination of two or more.

Examples of the aromatic carboxylic acid used in the present invention include benzoic acid, p-toluic acid, p-ethylbenzoic acid, p-isopropylbenzoic acid, p-tert-butylbenzoic acid, xylic acid, isophthalic acid, Examples include terephthalic acid, salicylic acid, cinnamic acid, toluic acid, hemimellitic acid, trimellitic acid, trimesic acid, hydroxybenzoic acid, dihydroxybenzoic acid, and trihydroxybenzoic acid. Among them, an aromatic carboxylic acid having 8 to 10 carbon atoms of R ² is preferable because the film formed on the surface of the material tends to be dense and has an excellent antirust effect. Specific examples thereof include p-ethylbenzoic acid, Examples thereof include p-isopropylbenzoic acid and p-tert-butylbenzoic acid. These aromatic carboxylic acids can also be used individually by 1 type, and can also use 2 or more types together.

  Furthermore, examples of the organic alkali for pH adjustment used in the present invention include ammonia, tetramethylammonium hydroxide, alkanolamine, and alkylamine alkylamine.

  As the alkanolamine and alkylamine, those having 1 to 9 carbon atoms are preferable. Examples include monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, methylethanolamine, Examples include dimethylethanolamine, methyldiethanolamine, ethylethanolamine, diethylethanolamine, ethyldiethanolamine, cyclohexylamine, and triisopanolamine.

  As the organic alkali, monoethanolamine, diethanolamine, and triethanolamine are preferable because they are excellent in rust prevention among the above. These organic alkalis can also be used individually by 1 type, and can also use 2 or more types together.

  As a blending ratio of each of the above components in the cleaning composition of the present invention, the content of the nonionic surfactant is preferably 0.01 to 30% by weight, and more preferably 0.1 to 10% by weight. If it is less than 0.01% by weight, the osmotic force of the cleaning agent is not exhibited, and if it exceeds 30% by weight, the cleaning agent removability (rinsing property) tends to be inferior.

  The content of the aliphatic carboxylic acid is preferably 0.01 to 30% by weight, and more preferably 0.1 to 15% by weight. If it is less than 0.01% by weight, sufficient rust preventive properties are not exhibited, and if it exceeds 30% by weight, it is difficult to dissolve in the cleaning agent.

  The content of the aromatic carboxylic acid is preferably 0.01 to 30% by weight, more preferably 0.1 to 15% by weight. If it is less than 0.01% by weight, sufficient rust preventive properties are not exhibited, and if it exceeds 30% by weight, it is difficult to dissolve in the cleaning agent.

  Since the content of the organic alkali is adjusted so that the pH of the composition is 5 to 10, it varies depending on the blending amount of the aliphatic carboxylic acid and the aromatic carboxylic acid. When the pH is higher than 10, an influence on non-ferrous metals such as aluminum and copper occurs. When the pH is lower than 5, problems such as a decrease in rust prevention and precipitation of carboxylic acid in the cleaning liquid occur.

  In addition, a known antifoaming agent, preservative, antioxidant, pH adjuster and the like can be added to the cleaning composition of the present invention within a range not departing from the object of the present invention.

  As the antifoaming agent, various known ones such as silicon-based, higher alcohol-based, polyglycol-based, and mineral oil-based can be used.

  In addition, known anionic surfactants, cationic surfactants, amphoteric surfactants, and fluorosurfactants can be used in combination as long as they are within the scope of the present invention.

  Furthermore, if necessary, inorganic alkalis such as KOH and NaOH may be added singly or in combination, and used as a strong alkali detergent.

  The cleaning method using the cleaning composition of the present invention includes cleaning the ferrous metal parts and non-ferrous metal parts with a cleaning solution obtained by diluting the cleaning composition of the present invention with water, and then rinsing with water. Method is used. The dilution ratio of the cleaning composition is usually 2 to 200 times, preferably 5 to 50 times. If it is less than 2 times, a great amount of labor is required for rinsing the cleaning agent, and if it exceeds 200 times, the detergency is inferior.

  The object to be cleaned is not particularly limited, but it is effective for both ferrous metal parts typified by castings and steel sheets and non-ferrous metal parts typified by aluminum and copper. It can be suitably used for cleaning in a processing step such as electronic industry. Specifically, fine particles such as processing oil, fingerprints, swarf, abrasives remaining after polishing and polishing pieces adhering to the component in the processing step can be effectively removed.

  As the cleaning method, various cleaning methods such as immersion cleaning, ultrasonic cleaning, brush cleaning, scrub cleaning, jet cleaning, spray cleaning, and hand cleaning are not particularly limited, and can be used alone or in combination.

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to these Examples. Unless otherwise specified, the blending ratio and the like are based on mass (parts by mass, mass%).

  A cleaning composition was prepared according to the formulation shown in Table 1 below, and the following evaluation was performed. The results are shown in Table 2.

1. Detergency for oil-based processing oil A steel plate (SPCC) uniformly coated with oil-based processing oil (manufactured by Nippon Tool Oil Co., Ltd., product name: NO.630) was heat-treated at 100 ° C. for 3 minutes and cooled to obtain a test piece. .

  A 10-fold diluted product of each cleaning composition in Table 1 was prepared and used as a cleaning solution. The obtained cleaning liquid was heated to 50 ° C., washed the steel plate using a 38 kHz, 300 W ultrasonic cleaner, rinsed with warm water heated to 40 ° C., air blown, and then 80 ° C. Was dried with hot air for 5 minutes.

  The oil content of the steel plate before cleaning, and the oil residue and cleaning agent residue remaining on the steel plate after cleaning are extracted using a solvent, the extraction amount is measured by spectrophotometry, and the cleaning rate is obtained from the following equation, The cleaning performance was evaluated from the cleaning rate according to the following criteria.

Cleaning rate (%) = (Uncleaned steel plate extraction amount−Cleaning steel plate extraction amount) / Uncleaned steel plate extraction amount × 100
◎: Cleaning rate of 95% or more ○: Cleaning rate of 75% or more to less than 95% △: Cleaning rate of 50% or more to less than 75% ×: Cleaning rate of less than 50%

2. Detergency to water-soluble processing oil Steel plate (SPCC) uniformly coated with water-soluble processing oil (product name: UC-178AE, manufactured by Nippon Tool Oil Co., Ltd.) is heat-treated at 100 ° C. for 3 minutes, cooled, and then tested. It was.

  A 20-fold diluted product of each cleaning agent in Table 1 was prepared and used as a cleaning solution. The obtained cleaning liquid was heated to 50 ° C., washed the steel plate using a 38 kHz, 300 W ultrasonic cleaner, rinsed with warm water heated to 40 ° C., air blown, and then 80 ° C. Was dried with hot air for 5 minutes.

  The oil content of the steel plate before cleaning and the oil residue remaining on the steel plate after cleaning were extracted using a solvent, the extraction amount was measured by spectrophotometry, and the cleaning performance was compared according to the following criteria.

Cleaning rate (%) = (Uncleaned steel plate extraction amount−Cleaning steel plate extraction amount) / Uncleaned steel plate extraction amount × 100
◎: Cleaning rate of 95% or more ○: Cleaning rate of 75% or more to less than 95% △: Cleaning rate of 50% or more to less than 75% ×: Cleaning rate of less than 50%

3. Rust prevention against iron A 50-fold diluted product of each cleaning agent in Table 1 was prepared and used as a cleaning solution. Cast iron powder (FC200) is spread on a petri dish, and 2 ml of the resulting cleaning solution is dropped into 2 g of this cast iron powder, and the rusting situation at room temperature for 6 hours is confirmed. did.

◎: No rust ○: Less than 5% rust △: More than 5% to less than 25% R: More than 25% rust

4). Corrosiveness to copper A 50-fold diluted product of each cleaning agent in Table 1 was prepared and used as a cleaning solution. After immersing the copper plate (C1020P) in 100 ml of the obtained cleaning solution and leaving it in an airtight container at 40 ° C. for 24 hours, check the weight change of the copper plate and the presence or absence of the corrosion change of the copper plate surface. Compared.

◎: No change in weight (less than 0.01%) and no corrosion ○: Change in weight 0.01% to less than 0.10% and no corrosion △: Change in weight 0.10% or more, but no corrosion ×: Weight change 0.10% or more and corrosion

5. Corrosiveness to aluminum A 50-fold diluted product of each cleaning agent in Table 1 was prepared and used as a cleaning solution. After immersing the aluminum plate (A1050P) in 100 ml of the obtained cleaning solution and leaving it in an airtight container at 40 ° C. for 24 hours, check the weight change of the aluminum plate and the presence or absence of corrosion change on the surface of the aluminum plate. Comparison was made according to the following criteria.

◎: No change in weight (less than 0.01%) and no corrosion ○: Change in weight 0.01% to less than 0.10% and no corrosion △: Change in weight 0.10% or more, but no corrosion ×: Weight change 0.10% or more and corrosion

  The cleaning composition of the present invention adheres after cutting / polishing and pressing ferrous metal parts and non-ferrous metal parts in, for example, processing processes in the automobile industry, machine industry, metal industry, electrical / electronic industry, etc. It can be used to clean particles such as processing oil, fingerprints, chips, abrasives and abrasive pieces.

Claims (4)

Contains a nonionic surfactant represented by the following general formula (1), an aliphatic carboxylic acid represented by the following general formula (2), and an aromatic carboxylic acid represented by the following general formula (3) And a detergent composition prepared by adjusting the pH to be in the range of 5 to 10 using an organic alkali.
R ¹ -O - [(PO) m · (EO) n ] -H (1)
In the formula (1), R ¹ represents a linear or branched alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 30 carbon atoms, PO represents propylene oxide, and EO represents ethylene oxide. , M and n are average addition mole numbers, m is a number in the range of 0 ≦ m ≦ 20, n is a number in the range of 0 ≦ n ≦ 20, and m + n ≧ 2. The addition form of [(PO) m · (EO) n] may be either block or random, and either PO or EO may be first.
^{R 2 - (COOH) n (} 2)
In the formula (2), ^{R 2} is a straight-chain or branched 1 to 17 carbon atoms, an alkyl group, an alkenyl group or represents a alkanol group, n is a number of 1-3.
R ^3- (COOH) n (3)
However, in formula (3), ^{R 3} represents an aromatic hydrocarbon group, n is a number of 1-3.   The nonionic surfactant represented by the general formula (1) is 0.01 to 30% by weight, the aliphatic carboxylic acid represented by the general formula (2) is 0.01 to 30% by weight, and the general formula The cleaning composition according to claim 1, comprising 0.01 to 30% by weight of the aromatic carboxylic acid represented by (3).   The organic alkali is one or more selected from the group consisting of ammonia, tetramethylammonium hydroxide, an alkanolamine having 1 to 9 carbon atoms, and an alkylamine having 1 to 9 carbon atoms, The cleaning composition according to claim 1 or 2.   Washing ferrous metal parts or non-ferrous metal parts with a cleaning solution obtained by diluting the detergent composition according to any one of claims 1 to 2 with water 2-200 times, and then rinsing with water. A cleaning method characterized by.