JP2018177982A - Detergent composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition excellent in removal property of a fine particle or the like after polishing treatment using a polishing agent.SOLUTION: The detergent composition contains aliphatic hydrocarbon (A) of 60.0 to 85.0 mass%, an anionic surfactant (B) of 10.0 to 15.0 mass%, water (C) of 1.0 to 15.0 mass%, and a prescribed pH adjustment agent (D), has pH of 1.5 or more and less than 4.0, and constitutes W/O microemulsion or solubilization type W/O emulsion.SELECTED DRAWING: None

Description

  The present invention relates to cleaning compositions, in particular, parts used in various industrial fields such as automobiles, machinery, precision instruments, electricity, electronics, optics, etc., pipes and devices of various factories such as petroleum refining plants and chemical plants, automobiles and The present invention relates to a cleaning agent composition used for cleaning a part from which an industrial machine or the like is disassembled, and a metal product used in daily life.

  Parts handled in various industrial fields such as automobiles, machinery, precision instruments, electricity, electronics and optics (hereinafter referred to as "parts") are water insoluble mainly in (i) mineral oil etc. Water-soluble processing oil obtained by adding a surfactant to processing oil, (ii) mineral oil, etc. and emulsifying in water, (iii) fine particles such as abrasive, etc. are used. In particular, water-soluble processing oils are often used mainly for cutting, grinding, etc. For parts manufactured through a plurality of processing steps, the processing oil used is different for each process, so the polarity is low. There are many cases in which various stains from multiple to highly polar ones are combined and attached.

  A cleaning agent consisting of water, a solvent, and a surfactant has been developed for use in cleaning parts in which various stains such as low polarity to high polarity are combined and attached. 1 to 3). The W / O microemulsion-type detergents described in Patent Documents 1 to 3 enable extensive cleaning of stains such as stains with low polarity and stains with high polarity.

  However, even with the W / O microemulsion-type cleaners described in Patent Documents 1 to 3, buffing using a polishing agent performed for the purpose of deburring, smooth finishing, rounding, and polishing of parts after forming and processing In addition, the smut, which is a complex of fine particles and organic matter adhering to parts after barrel polishing, can not be sufficiently cleaned. In addition, cleaning of the smut, in which the decomposition product or modification product of the additive that adheres to the part after press working, the carbide, the wear metal powder, and the like, can not be sufficiently performed.

  On the other hand, for the purpose of cleaning and the like of parts after polishing processing, a surface treatment method of magnesium alloy members (see, for example, Patent Document 4) and a metal surface treatment agent (see, for example, Patent Document 5) have been proposed. Also in these inventions, the cleaning property of the processing oil that can be attached in other steps is insufficient, and the removability of the smut attached in the polishing step is not sufficient.

Japanese Patent Application Laid-Open No. 09-157698 JP, 2013-117008, A JP, 2014-214228, A JP, 2005-256064, A Japanese Patent Application Laid-Open No. 09-67600

  The present invention is made in view of the above, and an object of the present invention is to provide a cleaning agent composition excellent in the removability of a smut containing fine particles and the like after polishing processing using an abrasive.

  In order to solve the problems described above and achieve the object, the detergent composition of the present invention comprises an aliphatic hydrocarbon (A), an anionic surfactant (B), water (C) and oxalic acid. At least one pH adjuster (D) selected from dimethyl oxalate and malonic acid, and 60.0 to 85.0% by mass of the aliphatic hydrocarbon (A), the anionic interface The active agent (B) is contained at a ratio of 10.0 to 15.0% by mass and the water (C) at a ratio of 1.0 to 15.0% by mass, and the pH is 1.5 or more and less than 4.0 , W / O microemulsion or solubilized W / O emulsion.

  The detergent composition of the present invention is also selected from aliphatic hydrocarbon (A), anionic surfactant (B), water (C), oxalic acid, dimethyl oxalate, and malonic acid 60.0 to 85.0% by mass of the aliphatic hydrocarbon (A), containing at least one pH adjuster (D) and a nonionic surfactant (E), the anionic surfactant 8.0-15.0 mass% of agent (B), 1.0-20.0 mass% of said water (C), 2.0-5.0 mass of said nonionic surfactant (E) % And having a pH of 1.5 or more and less than 4.0, and a W / O microemulsion or a solubilized W / O emulsion.

  Further, the detergent composition of the present invention, in the above-mentioned invention, contains 10.0 to 20.0% by mass in total of the anionic surfactant (B) and the nonionic surfactant (E). The invention is characterized in that the anionic surfactant (B) and the nonionic surfactant (E) are blended in a ratio (mass ratio) of 2.0 to 5.0: 1.

  In the detergent composition of the present invention, in the above invention, the anionic surfactant (B) is a dialkyl sulfosuccinic acid ester salt, and the nonionic surfactant (E) is a sorbitan fatty acid ester. It is characterized by

  In the detergent composition of the present invention according to the above-mentioned invention, the aliphatic hydrocarbon (A) is a paraffinic hydrocarbon or an olefinic hydrocarbon having 9 to 13 carbon atoms.

  The detergent composition of the present invention is characterized in that, in the above-mentioned invention, the saturated water content measured by the turbidity is 10% by mass or more.

  Moreover, the cleaning agent composition of the present invention is characterized in that it does not contain a polar solvent in the above-mentioned invention.

  Further, the cleaning agent composition of the present invention is characterized in that it is used for cleaning the fine particles after the polishing treatment in the above-mentioned invention.

  The detergent composition of the present invention is characterized in that it is used to wash fine particles after press processing in the above-mentioned invention.

  Further, the cleaning composition of the present invention is characterized in that it is used in the above-mentioned invention for the pretreatment cleaning of the coating step of diamond like carbon.

  The detergent composition according to the present invention contains an aliphatic hydrocarbon (A), an anionic surfactant (B) and water (C) in a predetermined ratio, and the inorganic oxide fine particles derived from the abrasive are suitable. The pH is adjusted by the pH adjuster (D) so as to stably disperse, and a W / O microemulsion or a solubilizing W / O emulsion that rapidly dissolves the organic substance is formed, and the pH adjuster (D ) Functions also as a chelating agent and promotes the peeling of the inorganic oxide fine particles derived from the abrasive from the parts, so that it is possible to wash the smut after the polishing process which is difficult to wash.

  In the processing of parts used in various industrial fields such as automobiles, machinery, precision machinery, electricity, electronics, optics, etc., water-soluble materials containing a water-insoluble processing oil mainly composed of mineral oil etc., a mineral oil etc. Fine particles of processing oil, abrasives and the like are used, and various stains adhere to the object to be cleaned.

  In recent years, PVD (Physical Vapor Deposition) coating processing including DLC (diamond like carbon) coating has been applied to improve the durability of articles such as automobile parts and tools, but before PVD coating processing, There are processes such as grinding, forging, electric discharge, polishing, and rust prevention, and various dirt adheres to the articles in these processes. A W / O microemulsion or a solubilized W / O emulsion, in which a solvent is mixed with water and a surfactant (hereinafter referred to as “W / O microemulsion type cleaner”), is polar A variety of stains can be cleaned from high stains to low stains, but the cleanability of stains attached to parts after buffing and barreling, and stains attached by pressing using a water-insoluble processing oil should be sufficient. I could not say that.

  The polishing agent used in the polishing process such as buffing is obtained by solidifying with a wax an inorganic oxide such as silica, alumina, cerium oxide or the like, an abrasive fine powder such as diamond, an auxiliary agent and a lubricating oil component. The polishing agent adheres to parts in a state in which each component is oxidized or carbonized and dried by heat generated in the polishing process, so cleaning is difficult, and the cleaning becomes more difficult with time.

  On the other hand, water-insoluble processing oil used for press processing is obtained by dissolving additives such as oil agent and extreme pressure agent in mineral oil, and decomposition products of the additive due to heat generation and pressure in the press processing process. If the dirt is a composite dirt of modified products, carbides, wear metal powder, etc. and it adheres to parts, the cleaning could not be performed sufficiently.

  The dirt (hereinafter referred to as "smut") attached to parts in the polishing step or pressing step is a composite of inorganic oxide particles and an organic substance, and in order to remove this, an organic substance is used as a cleaning agent. It is required to have the function of dissolving and dispersing inorganic oxide particles.

  Conventional W / O microemulsion cleaners can dissolve organic substances derived from abrasives in the oil layer, but may be because the dispersibility of the inorganic oxide particles is not sufficient, so the smut cleanability after the polishing treatment It was low. Moreover, although the conventional W / O microemulsion-type detergent can dissolve the organic matter derived from the water-insoluble press oil in the oil layer, it may be because the dispersibility of the carbide and the wear metal powder is not sufficient, after pressing The washability of the smut was sometimes low.

  The present inventors focused on the electrokinetic potential of inorganic oxide particles (hereinafter referred to as zeta potential) in order to improve the detergency of smut. In general, it is known that the zeta potential of inorganic oxide particles largely changes depending on pH, for example, in alumina sols, it is positively charged at low pH and negatively charged at high pH. Therefore, by adjusting the pH of the detergent composition, the zeta potential of the inorganic oxide particles contained in the smut is positively or negatively charged to suppress the aggregation of the inorganic oxide particles, which is stable in the detergent. Based on the presumption that it may be dispersed, the present invention has been completed.

  The cleaning composition according to the first embodiment of the present invention comprises an aliphatic hydrocarbon (A), an anionic surfactant (B), water (C), oxalic acid, dimethyl oxalate, and At least one pH adjuster (D) selected from malonic acid; 60.0 to 85.0% by mass of the aliphatic hydrocarbon (A); and the anionic surfactant (B) 10.0-15.0 mass%, the said water (C) is contained in the ratio of 1.0-15.0 mass%, While pH is 1.5 or more and less than 4.0, W / O microemulsion Alternatively, it is characterized in that it forms a solubilizing W / O emulsion.

  The detergent composition according to the first embodiment of the present invention comprises aliphatic hydrocarbon (A), anionic surfactant (B) and water (C) in a predetermined ratio, Dissolve the organic matter in the smut quickly. In addition, the washing ability of the smut is improved by setting the pH to 1.5 or more and less than 4.0 with at least one pH adjuster (D) selected from oxalic acid, dimethyl oxalate, and malonic acid. . This is because the zeta potential of the inorganic oxide particles in the smut is positively charged by contact with the detergent composition, and the aggregation of the inorganic oxide particles is suppressed, that is, the dispersibility of the inorganic oxide particles is improved. It is considered that the pH adjuster (D) also functions as a chelating agent to promote the exfoliation of the inorganic oxide fine particles from the parts. The stability of the W / O microemulsion or the solubilized W / O emulsion varies with pH, but the detergent composition of the present invention is stable even at pH 1.5 or more and less than 4.0. Alternatively, it is a solubilizing type W / O emulsion, and it is possible to wash a smut which is difficult to wash in which organic matter and inorganic oxide particles are complexed.

The components of the cleaning composition according to the first embodiment of the present invention will be described below.
The aliphatic hydrocarbon (A) used in the detergent composition according to the first embodiment of the present invention preferably has 9 to 13 carbon atoms. When the carbon number of the aliphatic hydrocarbon (A) is less than 9, the flash point of the detergent composition is lowered, and the possibility of ignition is increased. In addition, when the number of carbon atoms is larger than 14, the viscosity of the cleaning composition may be increased, and the cleaning efficiency may be reduced. The aliphatic hydrocarbon (A) preferably has 10 to 13 carbon atoms, and more preferably 10 to 12 carbon atoms.

  The aliphatic hydrocarbon (A) is preferably a paraffinic hydrocarbon or an olefinic hydrocarbon. When the aliphatic hydrocarbon (A) is a paraffinic hydrocarbon or an olefinic hydrocarbon, it is preferable because a stable W / O microemulsion or a solubilized W / O emulsion can be formed.

  Examples of the aliphatic hydrocarbon (A) according to the first embodiment of the present invention include normal heptane, normal octane, normal nonane, normal decane, normal undecane, normal dodecane, normal tridecane, normal tetradecane, and normal pentadecane. Etc., normal paraffin hydrocarbons, isoheptane, isooctane, isononane, isodecane, isoundecane, isododecane, isotridecane, isotridecane, isoparadecane, isoparaffin hydrocarbons such as isopentadecane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, tetramethylcyclohexane, Ethylcyclohexane, propylcyclohexane, butylcyclohexane, pentylcyclohexane, bicyclohexyl, decal , Cycloparaffinic hydrocarbons such as methyl decalin, dimethyl decalin and ethyl decalin, normal heptene, normal octene, normal nonene, normal decene, normal undecene, normal dedecene, normal tridecene, normal tetradecene, normal pentadecene, isoheptene, iso octene , Isononene, isodecene, isoundecene, isododecene, isotridecene, isotetradecene, isopentadecene, isopentadecene, cyclohexene, methylcyclohexene, dimethylcyclohexene, trimethylcyclohexene, tetramethylcyclohexene, ethylcyclohexene, propylcyclohexene, butylcyclohexene, pentylcyclohexene, etc. Hydrogen can be used. These may be used alone or in combination of two or more. Among these, normal decane, normal undecane, normal decane, isodecane, isoundecane and isododecane are preferable in that safety and washing efficiency can be compatible.

  In the cleaning composition according to the first embodiment of the present invention, the compounding amount of the aliphatic hydrocarbon (A) is 60.0 to 85.0% by mass. If the content of the aliphatic hydrocarbon (A) is less than 60.0% by mass, the detergency with respect to less polar stains may be reduced, and if it is more than 85.0% by mass, the highly polar stains may be reduced. There is a risk that the washability may decrease. It is preferable that the compounding quantity of aliphatic hydrocarbon (A) is 75.0-80.0 mass%.

  The anionic surfactant (B) used in the detergent composition according to the first embodiment of the present invention can be appropriately selected according to the purpose. For example, petroleum sulfonate, funnel oil, etc. Sulfonates, sulfates, carboxylates and the like can be exemplified.

  Among them, as the sulfonate, a sulfonate of a hydrocarbon having 8 to 22 carbon atoms is preferable. As a sulfate ester salt, a C8-C18 sulfated oil and a C8-C18 alkyl sulfate ester salt are preferable. As carboxylic acid salts, dialkyl sulfosuccinic acid ester salts having 6 to 13 carbon atoms in the alkyl group, alkyl di salts of sulfosuccinic acid having 6 to 13 carbon atoms, and polyoxyethylene alkyl sulfosacs having 6 to 13 carbon atoms in the alkyl group Acid disalts are preferred. The above anionic surfactant (B) is preferable because it can form a stable W / O microemulsion or a solubilized W / O emulsion. In particular, dialkyl sulfosuccinic acid ester salts having an alkyl group having 6 to 13 carbon atoms such as sodium di (2-ethylhexyl) sulfosuccinate form a more stable W / O microemulsion or a solubilized W / O emulsion. It is preferably used to

  As the sulfonate used as the anionic surfactant (B), it is preferable to use a substance other than the alkylbenzene sulfonate because the influence on the environment is reduced and management becomes easy.

  Examples of salts of surfactants used as the anionic surfactant (B) include alkali metal salts, alkaline earth metal salts, ammonium salts, and alkanolamine salts having 1 to 5 carbon atoms, but sulfonic acids An acid form such as sulfuric acid ester, carboxylic acid and the like can also be used. The surfactants exemplified above may be used alone or in combination of two or more.

  In the cleaning composition according to the first embodiment of the present invention, the compounding amount of the anionic surfactant (B) is 10.0 to 15.0% by mass. If the blending amount of the anionic surfactant (B) is less than 10.0% by mass, the cleaning property for highly polar stains may decrease, and if it is more than 15.0% by mass, less polar stains There is a risk that the cleaning ability for It is preferable that the compounding quantity of anionic surfactant (B) is 11.0-15.0 mass%.

  Distilled water, ion exchange water, etc. can be used as water (C) used by the cleaning agent composition concerning a 1st embodiment of the present invention. The compounding quantity of water (C) is 1.0-15.0 mass%. When the content of water (C) is less than 1.0% by mass, the cleaning property for highly polar stains may be reduced, and when it is more than 15.0% by mass, the cleaning property for poorly polar soiled is It may decrease. It is preferable that it is 3.0-15.0 mass%, and, as for the compounding quantity of water (C), it is especially preferable that it is 3.0-10.0 mass%.

  The detergent composition according to the first embodiment of the present invention comprises at least one pH adjuster (D) selected from oxalic acid, dimethyl oxalate and malonic acid. The pH adjuster (D) may be used as a mixture of one or more of oxalic acid, dimethyl oxalate and malonic acid.

  The compounding amount of the pH adjuster (D) is an amount such that the pH of the detergent composition is 1.5 or more and less than 4.0. By setting the pH of the detergent composition to 1.5 or more and less than 4.0 with the pH adjuster (D), the zeta potential of the inorganic oxide particles in the smut is positively charged, and the dispersibility of the inorganic oxide particles Improves the cleanability of the smut. Moreover, since the pH adjuster (D) used in the present invention also functions as a chelating agent, it can promote peeling of the inorganic oxide fine particles from parts. Furthermore, corrosiveness to metal parts can also be reduced by setting the pH to 1.5 or more and less than 4.0.

  Moreover, since the cleaning agent composition of this invention is an aliphatic hydrocarbon (A) as a main component, although pH measurement by a general pH meter can not be performed, pH can be measured by pH test paper. . For example, using pH measurement areas 0.0 to 1.8, 1.8 to 3.8, and 3.8 to 5.5 of stripe pH test paper (PEHANON), the pH is 1.5 or more and 4.0 or more. It can be measured if it is less than.

  In addition, the cleaning agent composition according to the second embodiment of the present invention comprises an aliphatic hydrocarbon (A), an anionic surfactant (B), water (C), oxalic acid and dimethyl oxalate. And at least one pH adjuster (D) selected from malonic acid, and a nonionic surfactant (E), wherein the aliphatic hydrocarbon (A) is 60.0 to 85.0. % By mass, 8.0 to 15.0% by mass of the anionic surfactant (B), 1.0 to 20.0% by mass of the water (C), the non-ionic surfactant (E) It is characterized in that it contains 2.0 to 5.0% by mass, has a pH of 1.5 to less than 4.0, and forms a W / O microemulsion or a solubilized W / O emulsion. I assume.

  The aliphatic hydrocarbon (A), the anionic surfactant (B), the water (C) and the pH adjuster (D) used in the detergent composition according to the second embodiment of the present invention The same ones as used in the embodiments of can be used.

  The cleaning composition according to the second embodiment of the present invention comprises a nonionic surfactant (E). By blending the non-ionic surfactant (E), the detergency against stains such as processing oil and wax can be improved. In addition, by combining the anionic surfactant (B) and the nonionic surfactant (E), it becomes possible to increase the blending amount of water in the detergent composition, and it is possible to use a highly polar stain. It is possible to improve the washability.

  Although the nonionic surfactant (E) used in the second embodiment of the present invention can be appropriately selected according to the purpose, for example, polyalkylene glycols and fatty acid esters are exemplified. be able to. In particular, fatty acid esters are preferred because they can form a stable W / O microemulsion or a solubilized W / O emulsion.

  Examples of polyalkylene glycols used as the nonionic surfactant (E) include polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, and the like. When using polyalkylene glycols as the nonionic surfactant (D), the thermal stability can be improved.

The polyoxyethylene polyoxypropylene block copolymer is a compound represented by the following formula (1) or formula (2).
_{HO- (C 2 H 4 O)} a - (C 3 H 6 O) b - (C 2 H 4 O) c -H (1)
_{HO- (C 3 H 6 O)} a - (C 2 H 4 O) b - (C 3 H 6 O) c -H (2)
In said Formula (1) and Formula (2), a is 2-160, b is 10-60, c is 2-160 are preferable.

The polyoxyethylene polyoxypropylene block copolymer used as the nonionic surfactant (E) preferably has a polyoxypropylene moiety having a molecular weight of 3,500 or less and a polyethylene oxide moiety of 50 mass% or less.
The polyoxyethylene polyoxypropylene alkyl ether is a compound represented by the following formula (3).
R ¹ -O- (C ₃ H ₆ O) _m- (C ₂ H ₄ O) _n -H (3)
In said Formula (3), R < ¹ > is a C6-C16 alkyl group, and 2-16 of n and m are preferable.

  As polyalkylene glycols used as the nonionic surfactant (E), using substances other than polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether reduces the influence on the environment, and It is preferable because management becomes easy.

  Examples of fatty acid esters used as the nonionic surfactant (E) include sorbitan fatty acid esters, ethylene glycol fatty acid esters, glycerin fatty acid esters, propylene glycol fatty acid esters, polyoxy fatty acid esters and the like. Fatty acid esters are preferable because they can improve the detergency. Among them, sorbitan fatty acid ester is preferable because it can form a more stable W / O microemulsion or a solubilized W / O emulsion.

  The blend ratio of each component in the detergent composition according to the second embodiment of the present invention is 60.0 to 85.0 mass% of aliphatic hydrocarbon (A), and anionic surfactant (B) It is preferable to make 8.0-15.0 mass%, 1.0-20.0 mass% of water (C), and 2.0-5.0 mass% of nonionic surfactant (E). .

  In the detergent composition according to the second embodiment of the present invention, when the blending amount of the anionic surfactant (B) is less than 8.0% by mass, the cleaning property for highly polar dirt is lowered. In some cases, when it is more than 15.0% by mass, the cleaning property for low polarity stains may be reduced. It is preferable that the compounding quantity of anionic surfactant (B) is 10.0-15.0 mass%.

  In the detergent composition according to the second embodiment of the present invention, if the compounding amount of water (C) is less than 1.0% by mass, the cleaning property for highly polar stains may be reduced. If the amount is more than 20.0% by mass, the cleaning property to the less polar stain may be reduced. It is preferable that it is 3.0-15.0 mass%, and, as for the compounding quantity of water (C), it is especially preferable that it is 3.0-10.0 mass%.

  In the detergent composition according to the second embodiment of the present invention, when the blending amount of the nonionic surfactant (E) is less than 2.0% by mass, the cleaning property for highly polar dirt is lowered. If the amount is more than 5.0% by mass, the cleaning property to the less polar stain may be reduced. It is preferable that the compounding quantity of nonionic surfactant (E) is 3.0-5.0 mass%.

  In addition, in the detergent composition according to the second embodiment of the present invention, the total amount of anionic surfactant (B) and nonionic surfactant (E) is 10.0 to 20.0% by mass. It is preferable to mix | blend anionic surfactant (B) and nonionic surfactant (E) by the ratio (mass ratio) of 2.0-5.0: 1 while including.

  In the detergent composition according to the second embodiment of the present invention, the total blending amount of the anionic surfactant (B) and the nonionic surfactant (E) is less than 10.0% by mass. In this case, the cleaning efficiency for highly polar stains may be low. In addition, if the total blending amount is larger than 20.0% by mass, there is a possibility that the cleaning efficiency for low polarity stains may be lowered. The total blending amount of the anionic surfactant (B) and the nonionic surfactant (E) is preferably 12.0 to 20.0 mass%.

  In the detergent composition according to the second embodiment of the present invention, the blending ratio (mass ratio) of the anionic surfactant (B) to the nonionic surfactant (E) is the nonionic surfactant When agent (E) is 1, it is preferable that anionic surfactant (B) is 2.0 to 5.0 times. If the blending ratio of the anionic surfactant (B) is less than 2.0 times or more than 5.0 times that of the nonionic surfactant (E), the cleaning efficiency for highly polar stains may be lowered. There is.

  The detergent composition according to the first and second embodiments of the present invention forms a W / O microemulsion or a solubilizing W / O emulsion. By forming the W / O microemulsion or the solubilizing W / O emulsion, it is possible to dissolve the organic matter and to prevent uneven washing. In addition, since the detergent composition of the present invention forms a stable W / O microemulsion or solubilized W / O emulsion even at low temperature, it can exhibit high cleanability without heating, It is possible to wash weak materials.

  Conventionally, in order to form a stable W / O microemulsion or a solubilized W / O emulsion, in addition to water, a non-aqueous cleaning agent to be an oil layer, and a surfactant, glycol ethers, alcohols Polar solvents such as glycols and polyoxyalkylene alkyl ethers have been used. Since the cleaning agent of the present invention does not contain a polar solvent, it may be a specific resin or rubber material that may be corroded by the polar solvent, such as ABS resin, acrylic resin, vinyl chloride, nitrile rubber, urethane rubber, fluororubber, etc. It can be used for washing the to-be-cleaned material which uses the material of (1). In addition, it is possible to use a resin cleaning jig.

  In the present specification, the W / O microemulsion means water (C) and an anionic surfactant (B), or water (C), an anionic surfactant (B) and a nonionic surfactant. (E) forms micelles with an average particle diameter of about 10 to 100 nm and is in the state of being dispersed in an oil layer, in the present invention, aliphatic hydrocarbon (A), and is in the form of a semitransparent or transparent liquid . In addition, the solubilizing type W / O emulsion refers to water (C) and anionic surfactant (B), or water (C), anionic surfactant (B) and nonionic surfactant (E) Is in the form of micelles having an average particle diameter of about 1 to 10 nm, and is dispersed in the oil layer, in the present invention, in the aliphatic hydrocarbon (A), and is in the form of a transparent liquid. The W / O microemulsion or the solubilizing W / O emulsion does not cause phase separation even when it is left for a long time because the particle size of the dispersed water (C) is small. The average particle size of the micelles can be measured by a zeta potential, particle size, and molecular weight measuring device.

  The saturated water content of the detergent composition according to the first and second embodiments of the present invention is preferably 10.0% by mass or more. When the saturated water content is 10.0% by mass or more, the water (C) is dispersed at a high rate in the aliphatic hydrocarbon (A), and therefore the polarity is maintained while maintaining the cleaning property of the low polarity dirt. It is possible to improve the cleanability of the high dirt. The saturated water content of the detergent composition of the present invention is preferably 10.0% by mass or more, and more preferably 10.0 to 35.0% by mass.

  The saturated water content of the detergent composition can be determined by using a composition comprising an aliphatic hydrocarbon (A) and an anionic surfactant (B), or an aliphatic hydrocarbon (A), an anionic surfactant (B) and Water (C) is blended in a composition comprising a nonionic surfactant (E), and water when the turbidity (JIS K 0101) of the detergent composition after addition of water (C) reaches 100 NTU It says the ratio (mass%) in the detergent composition of (C). Although the turbidity of the detergent composition used a portable turbidity meter 2100P (manufactured by Central Science Co., Ltd.), it is not limited thereto.

  Further, in the cleaning composition according to the first and second embodiments of the present invention, aliphatic hydrocarbon (A), anionic surfactant (B), water (C), pH adjuster (D) In addition to the nonionic surfactant (E), other detergent components, various additives, and the like may be added as long as the effects of the present invention are not impaired.

  Here, as other cleaning agent components, hydrocarbons other than aliphatic hydrocarbons (A), for example, alkylbenzenes such as trimethylbenzene, ethyltoluene, tetramethylbenzene etc., and alkylnaphthalenes such as methylnaphthalene, ethylnaphthalene, dimethylnaphthalene etc. Is illustrated.

  The additives include rust inhibitors, antioxidants, preservatives, chelating agents, alkali agents, bleaching agents, odorants and the like. Antirust agents include, for example, fatty acid ester anticorrosion agents such as pentaerythritol monoester and sorbitan monooleate, amine anticorrosion agents such as amines and amine salts, aromatic carboxylic acids, alkenylsuccinic acids and naphthenates Examples thereof include carboxylic acid-based rust inhibitors, organic sulfonic acid-based rust inhibitors such as petroleum sulfonate, organic phosphate ester-based rust inhibitors, oxidized paraffin-based rust inhibitors, and the like.

  The blending amount of the above-mentioned other components to the detergent composition is not limited as long as the effects of the present invention are not impaired, but 10.0 mass% or less in the detergent composition is preferable, 5.0 It is more preferable that it is mass% or less, and it is further more preferable that it is 1.0 mass% or less. If the content of other components exceeds 10.0% by mass, the cleaning effect on highly polar soils may be reduced, and a stable W / O microemulsion or solubilized W / O emulsion may be used. May inhibit formation.

  The cleaning composition according to the first and second embodiments of the present invention can be manufactured by measuring, mixing, and stirring predetermined amounts of the above-described respective components. There is no limitation on the order of mixing and the stirring method, and a detergent composition that forms a stable W / O microemulsion or a solubilizing W / O emulsion by mixing and stirring predetermined proportions of each component. Can be manufactured.

  The cleaning method using the cleaning agent composition of the first and second embodiments of the present invention comprises immersing the object to be cleaned in the cleaning agent composition of the present invention and the cleaning agent composition for the object to be cleaned It can be carried out by spray spraying, wiping the surface of the object to be cleaned with a sponge or the like impregnated with the detergent composition, or the like. In the case of cleaning by immersion in the cleaning composition, the cleaning effect can be improved by performing ultrasonic wave, stirring, air bubbling, rocking of the object to be cleaned, and the like. In particular, ultrasonic waves are preferably used to improve the removability of the abrasive-derived inorganic oxide particles. Further, the cleaning effect can be improved by heating and cleaning the cleaning composition.

  Removal of the surfactant contained in the detergent composition and the detergent composition remaining on the surface of the article to be cleaned after the cleaning of the article to be cleaned by the detergent composition according to the first and second embodiments of the present invention For the purpose, it is preferable to rinse with an aliphatic hydrocarbon (A) used as the cleaning agent composition of the present invention or a hydrocarbon having a boiling point lower than that of the aliphatic hydrocarbon (A), such as normal decane. The rinse may be performed once or twice or more.

  As described above, the cleaning composition according to the first and second embodiments of the present invention is excellent in the removability of the smut in which the inorganic oxide particles and the organic matter are attached to the component after the polishing step and the pressing step. In addition, the cleaning composition according to the first and second embodiments of the present invention is a stable W / O microemulsion or a solubilizing W / O emulsion, so that other soils, for example, water insoluble It is also excellent in the washability of processing oil and water-soluble processing oil. Among them, the smut that adheres to parts in the pressing process using a water-insoluble press oil can be cleaned with the cleaning composition of the present invention, and has excellent adhesion in PVD coating processes such as DLC coating after cleaning. And coatings without pinholes and the like can be obtained.

  Hereinafter, the present invention will be specifically described by way of examples and comparative examples, but the present invention is not limited to the following examples.

(Stability of W / O microemulsion or solubilized W / O emulsion)
Whether the detergent composition is prepared with the components and proportions shown in the Examples and Comparative Examples shown in Tables 1 to 5 and the prepared detergent composition forms a W / O microemulsion or a solubilized W / O emulsion It was judged by measuring the turbidity of the detergent composition whether or not. The turbidity of the detergent composition was measured using a portable turbidity meter 2100P (manufactured by Central Science Co., Ltd.). It was determined that a detergent composition having a turbidity of 100 NTU or less stably formed a W / O microemulsion or a solubilized W / O emulsion. The case where the turbidity was 100 NTU or less was ○, and the case where the turbidity was more than 100 NTU was x. The surfactant (B) in Tables 1 to 5 is sodium di (2-ethylhexyl) sulfosuccinate, and the surfactant (E) is sorbitan trioleate.

(PH)
The cleaning composition was prepared according to the components and proportions shown in the Examples and Comparative Examples shown in Table 1 to Table 5, and the pH of the prepared cleaning composition was adjusted to the pH measurement area 0.0 of stripe pH test paper (PEHANON). It measured using -1.8, 1.8-3.8, and 3.8-5.5. The prepared detergent composition is dropped onto a pH test paper, and the hue of the central portion without a measurement scale is compared with the hue sample with the measurement scale above and below to determine the pH of the most similar hue. The What can not be measured with the above-mentioned pH test paper was measured with stripe pH test paper of other pH measurement areas (5.2 to 6.8 etc.).
(Copper plate corrosion)
30 g of the detergent composition prepared and prepared with the components and proportions shown in the examples and comparative examples shown in Tables 1 to 5 is collected in a 50 mL sample bottle and polished by a P400 No. buff copper plate (2.0 × 12) Soak 5 × 75 mm) and take out the copper plate after 24 hours. The evaluation of corrosion was visually judged that there was no discoloration on the surface of the copper plate (o) and there was discoloration on the surface of the copper plate (x).

(Abrasive cleaning test)
A detergent composition was prepared with the components and proportions shown in the Examples and Comparative Examples shown in Tables 1 to 5, and the prepared cleaning composition was used to conduct a smut cleaning test. The to-be-cleaned object is obtained by barrel-polishing a work of SUS430 series, and a black smut adheres to the surface. The cleaning is performed by immersing the object to be cleaned in the cleaning composition of the examples and comparative examples shown in Tables 1 to 5, ultrasonic cleaning for 3 minutes (28 khz, 25 ° C.), and then ultrasonic cleaning for 3 minutes with normal decane. (28 khz, 25 ° C.) was carried out twice and dried for 30 minutes in warm air (80 ° C.). The evaluation of the washability was visually judged that there was no residue on the work (o) and the presence of residue (x).

  As shown in Tables 1 to 5, the pH is adjusted to 1.5 or more and less than 4.0 by a predetermined pH adjuster (D), and the W / O microemulsion or the solubilized W / O emulsion is stably made. In the cleaning composition of the embodiment to be formed, it was confirmed that the smut to be attached by the polishing process can be removed by the cleaning.

  The cleaning agent composition of the present invention is a part treated in various industrial fields such as automobiles, machinery, precision instruments, electricity, electronics, optics, etc., pipes and devices of various factories such as petroleum refining plants and chemical plants, automobiles and industrial machines It is useful for the cleaning of various articles such as dismantled parts, metal products and resin products used in daily life, and it is suitably used for smut cleaning after polishing process and press process, PVD coating processing, especially It is suitable as a cleaning agent for the pretreatment of DLC coatings where surface cleanliness is required.

Claims (10)

Aliphatic hydrocarbon (A),
Anionic surfactant (B),
Water (C),
At least one pH adjuster (D) selected from oxalic acid, dimethyl oxalate, and malonic acid;
60.0 to 85.0 mass% of the aliphatic hydrocarbon (A), 10.0 to 15.0 mass% of the anionic surfactant (B), 1.0 to 15 of the water (C) Contained at a rate of 0. 0% by mass,
A detergent composition characterized by having a pH of 1.5 or more and less than 4.0 and forming a W / O microemulsion or a solubilized W / O emulsion. Aliphatic hydrocarbon (A),
Anionic surfactant (B),
Water (C),
At least one pH adjuster (D) selected from oxalic acid, dimethyl oxalate, and malonic acid;
Containing a nonionic surfactant (E),
60.0 to 85.0 mass% of the aliphatic hydrocarbon (A), 8.0 to 15.0 mass% of the anionic surfactant (B), 1.0 to 20 of the water (C) .0 mass%, containing 2.0 to 5.0 mass% of the nonionic surfactant (E),
A detergent composition characterized by having a pH of 1.5 or more and less than 4.0 and forming a W / O microemulsion or a solubilized W / O emulsion.   While containing the said anionic surfactant (B) and the said nonionic surfactant (E) in a total of 10.0-20.0 mass%, the said anionic surfactant (B) and the said nonionic The detergent composition according to claim 2, wherein the surfactant (E) is blended in a ratio (weight ratio) of 2.0 to 5.0: 1. The anionic surfactant (B) is a dialkyl sulfosuccinic acid ester salt,
The detergent composition according to claim 2 or 3, wherein the non-ionic surfactant (E) is sorbitan fatty acid ester.   The detergent composition according to any one of claims 1 to 4, wherein the aliphatic hydrocarbon (A) is a paraffinic hydrocarbon having 9 to 13 carbon atoms or an olefinic hydrocarbon. .   The detergent composition according to any one of claims 1 to 5, wherein the saturated water content measured by the turbidity is 10% by mass or more.   The detergent composition according to any one of claims 1 to 6, which does not contain a polar solvent.   The detergent composition according to any one of claims 1 to 7, which is used for washing fine particles after the polishing treatment.   It is used for washing | cleaning of the microparticles | fine-particles after press processing, The cleaning agent composition as described in any one of Claims 1-7 characterized by the above-mentioned.   The detergent composition according to any one of claims 1 to 7, which is used for pre-treatment cleaning of a coating step of diamond-like carbon.