JP5623318B2 - Detergent composition for precision parts - Google Patents

Description

  The present invention relates to a cleaning composition mainly used for cleaning precision parts, and in particular, adheres to the surface of parts immediately after cutting or polishing of metal parts such as aluminum and stainless steel used for electronic parts and glass substrates. The present invention relates to a cleaning composition capable of safely and efficiently removing processed oil and fine particles which are grinding pieces.

  Contaminants to be removed by cleaning in the manufacturing process of precision parts include processing oil, fine powders such as metal and glass derived from materials generated during each processing, dust, ionic substances, and fingerprints.

  For these cleanings, organic solvents such as halogenated hydrocarbons, petroleum hydrocarbons and alcohols, or aqueous cleaning agent aqueous solutions containing alkali agents and surfactants are used.

  However, in common with organic solvents, there are environmental problems and problems that ionic substances cannot be removed effectively, and petroleum hydrocarbons and alcohols have a risk of being easily flammable.

  On the other hand, an aqueous cleaning solution containing an alkali agent and a surfactant has the ability to remove virtually all pollutants, has no danger of air pollution, and is safe in handling, but exhibits sufficient cleaning power, In order to maintain, it is necessary to combine several components appropriately.

  Therefore, for example, as in Patent Documents 1 to 3, a detergent composition containing water, an alkali and / or an alkali builder, a nonionic surfactant, a chelating agent, and an anionic surfactant as required, or for precision parts A cleaning agent and a cleaning method using the same have been proposed.

  However, the composition proposed in the above-mentioned Patent Document 1 is a cleaning agent containing silicate, and when rinsing failure occurs, the silicate adheres to the material and cannot be removed. . Moreover, since the detergent composition proposed in Patent Document 2 does not contain a ligand such as carboxylic acid or phosphonic acid, the chelating performance is low and the particle removability is poor. Furthermore, since the detergent composition proposed in Patent Document 3 contains an alkali metal hydrate and exhibits alkalinity of pH 10 or higher, there is a risk of corrosion of the aluminum material.

JP-A-7-331473 JP 2004-2778 A JP 2010-109329 A

  The present invention has been made in view of the above, and is a water-based cleaning composition excellent in safety and handleability, and remains after cutting and polishing aluminum-use members such as electronic parts and glass-use members. It aims at providing the cleaning composition excellent in particle removability, such as a cutting piece, an abrasives, and an abrasive piece.

  As a result of intensive studies, the present inventors have been able to effectively remove abrasive particles adhering to the hard surface by using hydroxycarboxylic acid, organic phosphonic acid, etc. excellent in chelating performance at a predetermined ratio, and It has been found that re-adhesion can be prevented by stable dispersion, and the present invention has been completed.

That is, the cleaning composition for precision parts of the present invention is at least one selected from the group consisting of (a) glycolic acid, gluconic acid, heptonic acid, and salts thereof in order to solve the above-mentioned problems. 0.1 to 25% by weight, (b) selected from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 3-carboxy-3-phosphonohexanedioic acid, and salts thereof 0.1 to 25% by weight of at least one kind and 0.1 to 25% by weight of at least one kind selected from the group consisting of (c) ethylenediaminetetrakismethylenephosphonic acid, hexamethylenediaminetetrakismethylenephosphonic acid, and salts thereof It shall contain.

The cleaning composition for precision parts may further contain (d) 0.01 to 25% by weight of a nonionic surfactant represented by the following general formula (1).

R-O- (PO) m- (EO) n-H (1)
In the formula (1), R 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 added 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. -(PO) m- (EO) n may be either block or random, and either PO or EO may be first.

The cleaning composition for precision parts of the present invention comprises (e) methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether. , Diethylene glycol diethyl ether, triethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol Monomethyl ether, dipropylene glycol monomethyl ether, can also be assumed that further contains dipropylene glycol dimethyl ether, and N- methyl-2 0.1 to 30 wt% selected water-soluble Solvent from pyrrolidone.

The cleaning composition for precision parts of the present invention is the sum of the above components (a) to (e) (excluding components (d) and (e) that are not included) . the amount is 0.3 to 75 wt%, as the balance is water, after cutting or polishing the precision components, it can be used to remove the residual Ru fine particles to the surface of the precision parts .

  The cleaning composition of the present invention is a cleaning agent and cleaning agent that removes particles such as cutting pieces remaining after cutting / polishing such as aluminum parts used in electronic parts, stainless steel parts, glass parts, etc. Removability (rinsability) is extremely excellent.

  Examples of (a) hydroxycarboxylic acid used in the present invention include glycolic acid, lactic acid, tartronic acid, glyceric acid, malic acid, tartaric acid, citric acid, gluconic acid, heptonic acid and the like.

  Examples of the salt of the above-mentioned (c) hydroxycarboxylic acid include salts of metal ions such as sodium, potassium and lithium, ammonia, monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine, Examples thereof include salts of onium ions such as diethylamine, triethylamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, diethylethanolamine, and ethyldiethanolamine, and acid forms (such as hydrogen atoms). Sodium, potassium, ammonia, monoethanolamine, and diethanolamine salts are preferable.

  These hydroxycarboxylic acids and salts thereof can be used alone or in combination of two or more.

  Next, (b) the organic phosphonic acid having 10 or less ligands used in the present invention includes ethane-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, 1-hydroxy Ethane-1,1-diphosphonic acid (HEDP), ethanehydroxy-1,1,2-triphosphonic acid, ethane-1,2-dicarboxy-1,2-diphosphonic acid, methanehydroxyphosphonic acid, nitrilotrimethylenephosphonic acid ( NTMP), 3-carboxy-3-phosphonohexanedioic acid (PBTC) and the like. In addition, (b) the organic phosphonic acid having 10 or less ligands is cheaper than the organic phosphonic acid having 11 or more ligands (c) described later, and the solubility in water is low. It has the advantage of being expensive.

  (B) Organic phosphonic acid salts include metal ion salts such as sodium, potassium and lithium, ammonia, monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine and diethylamine. , Salts of onium ions such as triethylamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, diethylethanolamine, and ethyldiethanolamine, and acid forms (hydrogen atoms and the like). Sodium, potassium, ammonia, monoethanolamine, and diethanolamine salts are preferable.

  These (b) organic phosphonic acids and salts thereof can be used singly or in combination of two or more.

  Examples of the organic phosphonic acid (c) having 11 or more ligands used in the present invention include ethylenediaminetetrakismethylenephosphonic acid, hexamethylenediaminetetrakismethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid, and salts thereof. Is mentioned.

  In addition, (c) types of organic phosphonates include metal ion salts such as sodium, potassium and lithium, ammonia, monoethanolamine, diethanolamine, triethanolamine, methylamine, dimethylamine, trimethylamine, ethylamine and diethylamine. , Salts of onium ions such as triethylamine, methylethanolamine, dimethylethanolamine, methyldiethanolamine, ethylethanolamine, diethylethanolamine, and ethyldiethanolamine, and acid forms (hydrogen atoms and the like). Sodium, potassium, ammonia, monoethanolamine, and diethanolamine salts are preferable.

  These (c) organic phosphonic acids having 11 or more ligands and salts thereof may be used alone or in combination of two or more.

  Further, (d) the nonionic surfactant that can be used in the present invention is an alkylene such as ethylene oxide or propylene oxide in a linear or branched alkyl group, alkenyl group or aromatic hydrocarbon group having 1 to 30 carbon atoms. Oxide is added.

  Examples of the alkyl group represented by the general formula (1) include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl Eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl and the like.

  Examples of the alkenyl group include ethenyl, propenyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, triecenyl, triecenyl, Hexacocenyl, heptacocenyl, octacocenyl and nonacosenyl, triaconenyl and the like.

  Aromatic hydrocarbon groups include phenyl, methylphenyl, dimethylphenyl, ethylphenol, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, undecylphenyl, dodecylphenyl, triphenyl Decylphenyl, tetradecylphenyl, pentadecylphenyl, hexadecylphenyl, heptadecylphenyl, octadecylphenyl, nonadecylphenyl, eicosylphenyl, heneicosylphenyl, docosylphenyl, tricosylphenyl, tetracosylphenyl, monostyrene Phenyl, distyrenated phenyl, tristyrenated phenyl, naphthyl, methyl naphthyl, ethyl naphthyl, propyl naphthyl, butyl naphthyl, pen Lunaphtyl, hexylnaphthyl, heptylnaphthyl, octylnaphthyl, nonylnaphthyl, decylnaphthyl, undecylnaphthyl, dodecylnaphthyl, tridecylnaphthyl, tetradecylnaphthyl, pentadecylnaphthyl, hexadecylnaphthyl, heptadecylnaphthyl, octadecylnaphthyl, , Eicosyl naphthyl, anthracenyl, phenanthracenyl, tetracenyl, chrycenyl, pentacenyl, hexacenyl, heptacenyl and the like.

  In the present invention, those having an average added mole number n of ethylene oxide in the range of 0 ≦ n ≦ 20 are used. Preferably, the range is 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 in the range of 0 ≦ m ≦ 20, and preferably in the range of 0 ≦ m ≦ 5. When m exceeds 20, the hydrophobicity increases and the rinsing property of the cleaning agent decreases.

  These (d) nonionic surfactants can be used alone or in combination of two or more.

  Furthermore, examples of the water-soluble high-boiling solvent (e) that can be used in the present invention include alcohol solvents, glycol solvents, pyrrolidone solvents, and the like. Examples of the water-soluble alcohol solvent include methanol, ethanol, isopropyl alcohol, and the like. Water-soluble glycol ethers include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, triethylene glycol monoethyl ether, ethylene glycol Monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl Ether, dipropylene glycol dimethyl ether. Examples of the water-soluble pyrrolidone solvent include N-methyl-2-pyrrolidone.

  These water-soluble high-boiling solvents can be used alone or in combination of two or more.

  The blending ratio of each constituent component in the cleaning composition of the present invention is preferably (a) at least one content selected from the group consisting of hydroxycarboxylic acids and salts thereof is 0.1 to 25% by weight. More preferably, it is 0.5 to 10% by weight. If it is less than 0.1% by weight, the particle removability is hardly exhibited, and if it exceeds 25% by weight, it becomes difficult to completely dissolve in a predetermined amount of water, and thus it becomes difficult to obtain a stable cleaning composition.

  The content of at least one selected from the group consisting of (b) the organic phosphonic acid having 10 or less ligands and salts thereof is preferably 0.1 to 25% by weight, more preferably 0.8. 5 to 10% by weight. If it is less than 0.1% by weight, the particle removability is hardly exhibited, and if it exceeds 25% by weight, it becomes difficult to completely dissolve in a predetermined amount of water, and thus it becomes difficult to obtain a stable cleaning composition.

  The content of at least one selected from the group consisting of (c) the organic phosphonic acid having 11 or more ligands and salts thereof is preferably 0.1 to 25% by weight, more preferably 0.8. 5 to 10% by weight. If it is less than 0.1% by weight, the particle removability is hardly exhibited, and if it exceeds 25% by weight, it becomes difficult to completely dissolve in a predetermined amount of water, and thus it becomes difficult to obtain a stable cleaning composition.

  By blending the above (d) nonionic surfactant, the detergent composition of the present invention improves the penetrating power to fine parts and exhibits excellent cleaning power. Furthermore, the ability to remove cutting oil is improved by the emulsifying power of the nonionic surfactant to oily contamination.

  When considering the removal of the cutting oil, (d) the nonionic surfactant is preferably 0.01 to 25% by weight, more preferably 0.1 to 10% by weight. If it is less than 0.01% by weight, the emulsifying power of the oil-based cutting oil is not exhibited, and if it exceeds 25% by weight, the detergent removability (rinsing property) tends to be inferior.

  In the cleaning composition of the present invention, by blending (e) a water-soluble high-boiling solvent, the penetrating power to fine portions is improved, and an excellent cleaning power is exhibited. Further, the cleaning power of the cutting oil is improved by the penetration of the water-soluble high-boiling solvent into the oily contamination.

  When considering the removal of the cutting oil, the amount of (e) the water-soluble high-boiling solvent is preferably 0.1 to 30% by weight, more preferably 1 to 20% by weight. However, the total amount of (a)-(e) shall be 100 weight% or less. When the blending amount is less than 0.1% by weight, the oil-based cutting oil is not solubilized, and when it exceeds 30% by weight, it becomes difficult to produce a uniform aqueous solution, and a stable cleaning composition cannot be obtained.

  The cleaning composition of the present invention can be obtained by mixing the components (a) to (c), or the component (d) and / or the component (e) and water as necessary. Usually, the total amount of these components (a) to (e) (provided that the components not included in the components (d) and (e) are excluded) is 0.3 to 75% by weight. And the balance is preferably water.

  In addition, the detergent composition of the present invention may be used by adding known antifoaming agents, antiseptics, rust inhibitors, antioxidants, pH adjusters, etc. within a range not departing from the object of the present invention. May be.

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

  A known anionic surfactant, cationic surfactant, amphoteric surfactant, or fluorosurfactant can be used in combination as long as it is within the scope of the present invention.

  Although the cleaning object of the cleaning composition of the present invention is not limited, it is particularly suitable for cleaning electronic parts-related materials using metals such as aluminum and stainless steel and inorganic materials such as glass. Examples include aluminum, stainless steel, and glass parts used in hard disk drives.

  In addition, the contaminants to be removed by the cleaning composition of the present invention are cutting oil remaining after cutting and polishing, cutting pieces such as aluminum, stainless steel and glass, and abrasives, and there are no restrictions on the abrasive grains used. And alumina, silica, cerium oxide, silicon carbide, zirconium oxide, silicon, diamond and the like.

  The detergent composition of the present invention is used as it is or diluted with water to 200 times or less (however, based on volume, the same applies hereinafter). When it exceeds 200 times, the detergency becomes poor. It is usually preferable to dilute 5 to 100 times from the balance of detergency and rinsing properties. After washing, it is usually preferable to rinse with water.

  Specific cleaning methods include various cleaning methods such as immersion cleaning, ultrasonic cleaning, brush cleaning, scrub cleaning, jet cleaning, spray cleaning, and hand cleaning, and can be used alone or in combination. According to the cleaning method, it is preferable to dilute to an appropriate concentration within a range of 200 times or less as described above.

  Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited to these Examples.

  The detergent components (a) to (e) and water were mixed in the proportions (% by weight) shown in Table 1 and Table 2 below to obtain detergent compositions (Examples 1 to 24, Comparative Examples 1 to 9). Prepared.

  About the cleaning composition obtained by the above, each evaluation of the following 1-4 was performed. The results are shown in Table 3.

1. Particle dispersibility 1 (Dispersibility of cleaning liquid mixed with abrasive)
A 50-fold diluted product of each cleaning composition of each Example and Comparative Example was prepared, and 0.1 g of alumina powder (manufactured by Nippon Light Metal Co., Ltd., average particle size 0.67 μm) was added to 100 g of the solution. The mixture was stirred in a 100 ml closed graduated cylinder and allowed to stand at 25 ° C. for 24 hours to confirm the dispersion state of the abrasive grains.

  After being allowed to stand for 24 hours, when the volume of the transparent aqueous layer formed in the upper layer was xml, the numerical value represented by “100-x” was defined as “dispersion volume (volume%)”. When the volume of the transparent aqueous layer is 0 ml and the dispersion volume is 100%, it is shown that a good dispersion state is obtained, and the reattachment of particles can be prevented. When the volume of the transparent water layer is 30 ml or more and the dispersion volume is 70% or less, some sedimentation of abrasive grains occurs, which indicates that there is a problem in detergency due to aggregation of particles.

2. Particle dispersibility 2 (Zeta potential of cleaning liquid mixed with abrasive)
A 50-fold diluted product of each cleaning composition of each Example and Comparative Example was prepared, and 0.1 g of alumina powder (manufactured by Nippon Light Metal Co., Ltd., average particle size 0.67 μm) was added to 100 g of the solution. After blending and stirring, the zeta potential was measured with a zeta potential measurement system (ELSZ-1 manufactured by Otsuka Electronics Co., Ltd.).

  When the zeta potential is about 20 mV or more with the same sign, the potential between the particles is 15 kT (k: Poltzmann constant, T: absolute temperature), and the particles are easily dispersed. Furthermore, if the same sign exceeds about 40 mV, electrostatic repulsion between particles increases, and a stable dispersion state is obtained, and reattachment of particles does not occur during cleaning. On the other hand, when the zeta potential is about 20 mV or less with the same sign, the particles are likely to aggregate with each other, affecting the cleaning properties. That is, the larger the absolute value of the zeta potential, the better the dispersibility and the better the cleaning property.

3. Particle dispersibility 2 (Zeta potential of cleaning liquid mixed with abrasive)
A 50-fold diluted product of each cleaning composition of each Example and Comparative Example was prepared, and 0.1 g of cerium oxide powder (manufactured by ACG Seimi Chemical Co., Ltd., average particle size 1 μm) was added to 100 g of the solution. After blending and stirring, the zeta potential was measured with a zeta potential measurement system (ELSZ-1 manufactured by Otsuka Electronics Co., Ltd.).

4). Cleaning test A 2.5-inch hard disk chassis part for aluminum immediately after cutting of the screw hole was used as a test piece.

  A 50-fold diluted product of each cleaning composition of each Example and Comparative Example was prepared, the temperature was adjusted to 40 ° C., the test piece was immersed, and ultrasonic cleaning was performed at 40 KHz and 300 W for 3 minutes. Then, using ion-exchange water, it was immersed at 25 ° C. for 3 minutes and ultrasonically cleaned. After the above treatment, the amount of residual particles of hard disk chassis components and the amount of organic contaminants were determined, and the detergency was compared.

  As for the amount of particles, one cleaning component was extracted with 100 ml of ultrapure water, and the number of particles of 0.2 μm or more was confirmed with a particle counter (manufactured by Lion Co., Ltd., in-liquid particle counter KL-30A). The smaller the number of remaining particles, the higher the cleaning performance.

  Further, one cleaning component was extracted with 100 ml of ultrapure water, and the amount of residual organic contaminants was confirmed with a total organic carbon meter (TOC-V, manufactured by Shimadzu Corporation). The lower the TOC concentration, the smaller the residue amount of the cutting oil and the cleaning agent, and the higher the cleaning property and the rinsing property.

  As can be seen from the results shown in Table 3, the cleaning compositions of the examples had significantly better particle dispersibility than the comparative examples, and therefore excellent cleaning properties and were extremely easy to rinse. It was.

Claims (4)

(A) 0.1 to 25% by weight of at least one selected from the group consisting of glycolic acid, gluconic acid, heptonic acid, and salts thereof,
(B) 1-hydroxyethane-1,1-diphosphonic acid, nitrilotrimethylenephosphonic acid, 3-carboxy-3-phosphonohexanedioic acid, and at least one selected from the group thereof 0.1 to 0.1 25% by weight, and (c) at least one selected from the group consisting of ethylenediaminetetrakismethylenephosphonic acid, hexamethylenediaminetetrakismethylenephosphonic acid, and salts thereof 0.1 to 25% by weight
A cleaning composition for precision parts, comprising: (D) The cleaning composition for precision parts according to claim 1, further comprising 0.01 to 25% by weight of a nonionic surfactant represented by the following general formula (1).
R-O- (PO) m- (EO) n-H (1)
In the formula (1), R 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 added 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. -(PO) m- (EO) n may be either block or random, and either PO or EO may be first. (E) methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, triethylene glycol monoethyl ether, Ethylene glycol monopropyl ether, diethylene glycol monopropyl ether, triethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, triethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene Glycol monomethyl ether, and that dipropylene glycol dimethyl ether, and additionally containing 0.1 to 30% by weight of a water-soluble solvent agent selected from N- methyl-2-pyrrolidone (provided that the total amount becomes 100% or less by weight The cleaning composition for precision parts according to claim 1 or 2, wherein The total amount of the components (a) to (e) (provided that the components other than the components (d) and (e) are not included) is 0.3 to 75% by weight, The balance is water,
After cutting or polishing the precision parts, characterized in that it is used to remove the residual Ru fine particles to the surface of the precision parts for precision component according to any one of claims 1 to 3 Cleaning composition.