JP2017031326A - Method for evaluating detergency of w/o microemulsion-type detergent, cleaning method by w/o microemulsion-type detergent, and method for forming film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for evaluating detergency of a W/O microemulsion-type detergent, a cleaning method by a W/O microemulsion-type detergent, and a method for forming a film.SOLUTION: The method for evaluating detergency of a W/O microemulsion-type detergent is an evaluation method of a W/O microemulsion-type detergent formed by mixing water and a surfactant in a solvent, where detergency is evaluated based on absorbance and a proton signal of a water molecule inH-NMR measurements.SELECTED DRAWING: None

Description

  The present invention relates to a method for evaluating the cleaning properties of a W / O microemulsion type cleaning agent, a cleaning method using a W / O microemulsion type cleaning agent, and a film forming method, and more particularly to automobiles, machines, precision equipment, electricity, electronics, The present invention relates to a cleaning method using a W / O microemulsion-type cleaning agent capable of cleaning and removing dirt composed of low-polarity dirt and high-polarity dirt adhering to parts used in various industrial fields such as optics.

  Parts (hereinafter referred to as “parts”) handled in various industrial fields such as automobiles, machines, precision equipment, electricity, electronics, optics, etc. (i) water-insoluble, mainly composed of mineral oil, during processing Various processing oils from low polarity to high polarity, such as water-soluble processing oil emulsified in water by adding surfactant to processing oil, mineral oil, etc. (ii) fine particles such as abrasives, etc. used. In particular, a lot of water-soluble processing oil is used mainly for cutting and grinding, and parts manufactured through multiple processing steps have low polarity because the processing oil used for each step varies. In many cases, various stains ranging from high polarity to high polarity are attached.

  A cleaning agent composed of water, a solvent, and a surfactant has been developed for the purpose of cleaning parts having a mixture of various types of dirt from low polarity to high polarity. 1 or 2).

  In the W / O microemulsion type cleaning agent described in Patent Documents 1 and 2, water and a surfactant form reverse micelles having an average particle diameter of about 1 to 100 nm and are dispersed in a solvent, and are transparent as a whole. It is in a liquid form and is a thermodynamically stable system (hereinafter referred to as “microemulsion”) that does not separate into layers even when left for a long period of time.

  In the W / O microemulsion-type cleaning agent described in Patent Documents 1 and 2, it is considered that dirt with low polarity is dissolved in a solvent, and dirt with high polarity is dissolved in water forming reverse micelles. When the amount of water dissolved in the W / O microemulsion-type detergent is large, the detergency against highly polar dirt increases. However, when the amount of dirt brought in increases, the reverse micelles become large in size and become cloudy (hereinafter referred to as the following). In the end, the water that had formed reverse micelles may settle down, resulting in poor cleaning. Moreover, if there is little quantity of the water melt | dissolved in a W / O microemulsion type cleaning agent, the detergency with respect to highly polar stain | pollution | contamination will become low. In managing the cleaning ability of the W / O microemulsion type detergent, it is important to control the water content of the W / O microemulsion type detergent, but it is stably incorporated into the microemulsion depending on the washing temperature. Since the amount of water changed, it was difficult to evaluate the washability only with the amount of water.

JP2013-117008A JP, 2014-214228, A

  The present invention has been made in view of the above, and provides a method for evaluating the detergency of a W / O microemulsion type cleaning agent, a cleaning method using a W / O microemulsion type cleaning agent, and a film forming method. Objective.

In order to solve the above-mentioned problems, the present inventors have conducted intensive research on the relationship between the amount of water blended in the W / O microemulsion type detergent and the detergency. Based on the absorbance and the proton signal of water in ¹ H-NMR measurement, it was found that the detergency of the W / O microemulsion detergent can be evaluated, and the present invention has been completed.

That is, the present invention is a method for evaluating the detergency of a W / O microemulsion type detergent in which water and a surfactant are blended in a solvent, and is used for the absorbance signal and the proton signal of a water molecule in ¹ H-NMR measurement. The cleaning property is evaluated based on this.

The present invention also relates to a cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are blended in a solvent, wherein the absorbance at 660 nm is less than 0.1 ABS, and water molecules in ¹ H-NMR measurement. The washed object is washed with the W / O microemulsion-type detergent whose water content and temperature are adjusted so that the proton signal of the water is 5.0 ppm or more and less than 5.2 ppm.

The present invention also relates to a cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are blended in a solvent, wherein the absorbance at 660 nm is less than 0.1 ABS, and water molecules in ¹ H-NMR measurement. Wash the object with the W / O microemulsion type cleaning agent whose water content and temperature are adjusted so that the proton signal of 4.8 ppm or more and less than 5.0 ppm and the kinematic viscosity is less than 4.0 mm ² / s. It is characterized by that.

The present invention also relates to a cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent, and the absorbance at 660 nm at a measurement temperature of 40 ° C. or higher is less than 0.1 ABS, 40 The W / O microemulsion-type cleaning agent, whose water content was adjusted so that the proton signal of water molecules in a ¹ H-NMR measurement at a measurement temperature of ℃ or higher was 4.0 ppm or more and less than 4.8 ppm, The object to be cleaned is cleaned by heating to the above measurement temperature.

The present invention also relates to a cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent, and the absorbance at 660 nm at a measurement temperature of less than 40 ° C. is less than 0.1 ABS, 40 The above-mentioned W in which the water content is adjusted so that the proton signal of water molecules in ¹ H-NMR measurement at a measurement temperature of less than ° C. is 4.0 ppm or more and less than 4.8 ppm and the kinematic viscosity is less than 2.0 mm ² / s. The object to be cleaned is cleaned by heating the / O microemulsion type cleaning agent to the measurement temperature of less than 40 ° C.

  The film forming method of the present invention is characterized in that diamond-like carbon is coated on the surface of an object to be cleaned that has been cleaned by any of the above-described cleaning methods using a W / O microemulsion type cleaning agent.

The present invention can evaluate the cleaning performance based on the absorbance of the W / O microemulsion-type cleaning agent and the proton signal of water molecules in ¹ H-NMR measurement, and improves the cleaning efficiency by the W / O microemulsion-type cleaning agent. be able to.

FIG. 1 is a graph showing the relationship between the temperature of NS100M (water content 3 mass%) and the proton signal of water molecules in ¹ H-NMR measurement. FIG. 2 is a diagram showing the relationship between the temperature of NS100M (water 10 mass%) and the proton signal of water molecules in ¹ H-NMR measurement. FIG. 3 is a diagram showing the relationship between the temperature of NS220M (water content 3 mass%) and the proton signal of water molecules in ¹ H-NMR measurement. FIG. 4 is a diagram showing the relationship between the temperature of NS220M (water 10 mass%) and the proton signal of water molecules in ¹ H-NMR measurement.

  When processing parts used in various industrial fields such as automobiles, machinery, precision machinery, electrical machinery, electronics, optics, etc., water-insoluble processing oils mainly composed of mineral oils, mineral oils, etc., with water-soluble surfactants Processing oil, abrasives, etc. are used, and various stains adhere to the object to be cleaned. A W / O microemulsion-type cleaning agent in which water and a surfactant are blended in a solvent is used for cleaning a part to which various kinds of dirt are attached.

  In recent years, in order to improve the durability of articles such as automobile parts and tools, PVD (Physical Vapor Deposition) coating processing such as DLC (Diamond Like Carbon) coating has been performed, but before PVD coating processing, There are processes such as grinding, forging, electric discharge, polishing and rust prevention, and various stains adhere to the article in these processes. The W / O microemulsion type cleaning agent cleans various types of dirt, from high polarity dirt to low dirt, but sufficient detergency cannot be obtained depending on the amount of water contained in the W / O microemulsion type detergent. There was a case. In order to perform efficient cleaning with the W / O microemulsion type cleaning agent, it is necessary to evaluate the cleaning power of the W / O microemulsion type cleaning agent. Since the force is affected not only by the amount of water but also by the washing temperature and the like, it was difficult to evaluate the washability of the W / O microemulsion type detergent without washing.

As a result of intensive studies on the relationship between the amount of water and the cleaning property, and the relationship between the temperature and the cleaning property, the present inventors have determined the absorbance of the W / O microemulsion type cleaning agent, In addition, the inventors have found that the detergency of the W / O microemulsion-type detergent can be evaluated based on the proton signal of water molecules in ¹ H-NMR measurement, and have completed the present invention.

  In the present invention, the absorbance of the W / O microemulsion detergent can determine the stability of the W / O microemulsion detergent, that is, whether reverse micelles that have taken in water are stable, and the absorbance at 660 nm. Is less than 0.1 ABS, it is stable and can be washed.

Moreover, if the proton signal of water in the ¹ H-NMR measurement is present on the low magnetic field side, the degree of freedom of water added to the W / O microemulsion-type detergent is increased, and it is judged that the detergency is high. . The present inventors measured ¹ H-NMR for W / O microemulsion-type cleaning agents having different amounts of water, and the proton signal of water in the W / O microemulsion-type cleaning agent shows that the amount of water is We found that it shifts to the low magnetic field side as the number increases, and that the proton signal of water in the W / O microemulsion type cleaning agent shifts to the low magnetic field side when the temperature of the W / O microemulsion type cleaning agent decreases. It was. 1 to 4 show the relationship between the temperature of NS100M and NS220M (manufactured by JX Nippon Oil & Energy Corporation) in a W / O microemulsion type detergent and the proton signal of water molecules in ¹ H-NMR measurement. FIG. NS100M, and the amount of water blended into NS220M changed to 3 wt% and 10 wt% measured ¹ H-NMR, the chemical shift as NS100M, and got a water molecule proton signals in NS220M, temperature decreases Was confirmed to move to the low magnetic field side.

  The moisture content and temperature of NS100M and the chemical shift of water molecules are summarized in Table 1.

From the approximate curve created using the data in Table 1, the chemical shift of water molecules at 40 ° C. when the water content in NS100M is 0.1% by mass is 3.8 ppm, and 10% when the water content is 50% by mass. The chemical shift of water molecules at ° C was estimated to be 5.5 ppm. When the water content is 0.1% by mass and 40 ° C., the water present in NS100M is mostly water bound to the hydrophilic group of the surfactant that forms reverse micelles (hereinafter referred to as “bound water”). Yes, at a water content of 50% by mass and 10 ° C., most of the water present in NS100M exists as free water (hereinafter referred to as “free water”) that is not constrained by the surfactant in the reverse micelles. Conceivable. Therefore, the chemical shift of bound water can be defined in a pseudo manner as 3.8 ppm, and the chemical shift of free water can be defined as 5.5 ppm. The single proton signal of the water molecule shown in FIGS. 1 to 4 means that the exchange rate of the above-mentioned combined water and free water is fast. Therefore, the ratio of free water or bound water can be calculated from the following formula from each chemical shift.
Chemical shift under specified conditions = chemical shift of free water (5.5) x x + chemical shift of bound water (3.8) x (1-x)

  In the above formula, x is the ratio of free water in NS100M, and (1-x) is the ratio of bound water. For example, the chemical shift of NS100M at a moisture of 0.3% by mass and 10 ° C is 4.3 ppm, but by adding 4.3 to the left side of the above formula, the NS100M at a moisture of 0.3% by mass and 10 ° C in NS100M The ratio of free water and combined water is required. The percentage of free water of NS100M at a moisture of 0.3% by mass and 10 ° C. is 29%, and the percentage of bound water is 71%.

In the present invention, if the W / O microemulsion-type cleaning agent has an absorbance at 660 nm of less than 0.1 ABS and a proton signal of a water molecule in ¹ H-NMR measurement of 5.0 ppm or more and less than 5.2 ppm, it is judged that washing is possible. To do.

In addition, when the proton signal of the water molecule in ¹ H-NMR measurement is less than 5.0 ppm, the detergency is judged by the kinematic viscosity in addition to the absorbance and the proton signal of water in the ¹ H-NMR measurement.

In the present invention, the absorbance at 660 nm of the W / O microemulsion type detergent is less than 0.1 ABS, the proton signal of water molecules in ¹ H-NMR measurement is 4.8 ppm or more and less than 5.0 ppm, and the kinematic viscosity is 4.0 mm. If it is less than ² / s, it is determined that cleaning is possible.

Furthermore, when the proton signal of the water molecule in ¹ H-NMR measurement is 4.0 ppm or more and less than 4.8 ppm, the washing performance is also improved by the washing temperature in addition to the absorbance and the proton signal of water in ¹ H-NMR measurement. to decide.

In the present invention, the W / O microemulsion-type detergent has an absorbance at 660 nm at a measurement temperature of 40 ° C. or higher, less than 0.1 ABS, and a proton signal of water molecules in ¹ H-NMR measurement at a measurement temperature of 40 ° C. or higher. Is 4.0 ppm or more and less than 4.8 ppm, and it is determined that cleaning is possible when the cleaning temperature is a measured temperature of 40 ° C. or higher.

In the present invention, W / O micro-660nm absorbance at the measurement temperature below 40 ° C. the emulsion type cleaning agent is less than 0.1ABS, the water molecules in the ¹ H-NMR measurement at 40 ° C. or more measured temperatures When the proton signal is 4.0 ppm or more and less than 4.8 ppm, the kinematic viscosity is less than 2.0 mm ² / s, and the washing temperature is a measurement temperature of less than 40 ° C., it is determined that washing is possible.

  Next, the W / O microemulsion type cleaning agent used in the present invention will be described. The W / O microemulsion type cleaning agent according to the present invention is a cleaning agent in which water and a surfactant are blended in a solvent.

  As long as the W / O microemulsion-type cleaning agent forms a W / O microemulsion, the amount of water in the cleaning agent is not limited, but the amount of water in the W / O microemulsion-type cleaning agent is 0.00. It is preferable that it is 1 mass% or more and less than 50 mass%. As long as the water content in the W / O microemulsion type cleaning agent is 0.1% by mass to 50% by mass, cleaning can be performed by the method of the present invention described below. The water content of the W / O microemulsion-type cleaning agent is preferably in the range of 0.1% by mass to 50% by mass even after various dirt components are brought in by use. The water content of the W / O microemulsion-type cleaning agent to which the cleaning method of the present invention is applied is preferably 0.3% by mass to 20% by mass, more preferably 1% by mass to 15% by mass, and more preferably 1% by mass. % To 10% by mass is particularly preferable.

  As a solvent used for the W / O microemulsion type cleaning agent, for example, an organic solvent used as a base material for industrial cleaning agents such as aliphatic hydrocarbons, aromatic hydrocarbons, and terpenes is appropriately selected according to the purpose. For example, normal octane, normal nonane, normal decane, normal undecane, normal dodecane, normal tridecane, isooctane, isononane, isodecane, isoundecane, isododecane, methylcyclohexane, indene, indane, decalin, tetralin, carbon Olefin having 8 to 18 carbon atoms, alkylcyclopentane, alkylcyclohexane, alkylbenzene, alkylindene having 10 to 18 carbon atoms, alkylindane, alkyldecalin having 11 to 18 carbon atoms, alkyltetralin, alkylnaphtha , Myrcene, selenium, osymene, pinene, limonene, camphene, terpinolene, tricyclene, terpinene, fenchen, ferrandlene, sylvestrene, sapien, p-menthen-1, p-menthen-3, p-cymene, p-menthane , Naphtha, kerosene and the like. These may be used alone or in combination of two or more. Moreover, as long as a W / O microemulsion can be formed stably, you may mix | blend and use another solvent. Of the above solvents, normal decane, normal undecane, normal dodecane, and normal tridecane are particularly preferable from the viewpoints of safety and detergency.

  The surfactant used in the W / O microemulsion type detergent is selected from anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants depending on the purpose. For example, fatty acid monocarboxylate, N-acyloyl glutamate, alkylbenzene sulfonate, α-olefin sulfonate, naphthalene sulfonate-formaldehyde condensate, sulfosuccinic acid dialkyl ester, sulfuric acid Alkyl salt, alkyl polyoxyethylene sulfate, alkyl phosphate, alkylamine salt, alkyltrimethylammonium salt, dialkyldimethylammonium salt, alkyldimethylbenzylammonium salt, N, N-dimethyl-N-alkylaminoacetic acid betaine, 2- Alkyl-1-hydro Cyethyl-1-carboxymethylimidazolinium betaine, glycerin fatty acid ester, sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block copolymer, polyethylene glycol fatty acid ester And surfactants such as polyoxyethylene sorbitan fatty acid ester and fatty acid alkanolamide. These may be used alone or in combination of two or more. Of the above surfactants, it is preferable to use an anionic surfactant and a nonionic surfactant in combination.

  The blending amount of the surfactant in the W / O microemulsion type detergent is not limited as long as it forms a W / O microemulsion, but it may be 10% by mass or more and 20% by mass or less. preferable. In addition, when an anionic surfactant and a nonionic surfactant are used in combination, the proportion of the anionic surfactant and the nonionic surfactant is the same as that of the anionic surfactant. It is preferably 2 to 5 times the surfactant.

  Examples of commercially available W / O microemulsion type detergents in which water and a surfactant are mixed in the solvent used in the present invention include “NS Clean” (registered trademark) 100M and 220M (JX Nippon Mining & Energy Corporation) )) Is exemplified.

  In addition, the W / O microemulsion type cleaning agent may contain various additives as long as it is mainly composed of the above-described components. In the present specification, “mainly” means that the ratio of the exemplified components (solvent, surfactant, water) in the W / O microemulsion type cleaning agent is 90.0% by mass or more. means.

  Examples of the additive include a rust inhibitor, an antioxidant, an antiseptic, a chelating agent, an alkali agent, a bleaching agent, and an odorant. Examples of the rust preventive include fatty acid ester rust preventives such as pentaerythritol monoester and sorbitan monooleate, amine rust preventives such as amines and amine salts, aromatic carboxylic acids, alkenyl succinic acids, and naphthenates. Examples include carboxylic acid rust preventives, organic sulfonic acid rust preventives such as petroleum sulfonate, organic phosphate ester rust preventives, and oxidized paraffin rust preventives.

  Next, a cleaning method using the W / O microemulsion type cleaning agent of the present invention will be described for each embodiment.

In the first embodiment of the present invention, the amount of water and the amount of water so that the absorbance at 660 nm is less than 0.1 ABS, and the proton signal of water molecules in ¹ H-NMR measurement is 5.0 ppm or more and less than 5.2 ppm. The object to be cleaned is cleaned with a W / O microemulsion type cleaning agent whose temperature is adjusted.

  In the first embodiment of the present invention, the absorbance at 660 nm of the W / O microemulsion-type cleaning agent used for cleaning is less than 0.1 ABS. The absorbance of the W / O microemulsion-type detergent can be measured with a colorimeter or an ultraviolet-visible spectrophotometer. The W / O microemulsion type detergent forms reverse micelles in which a surfactant is a molecular assembly in a solvent, and water is taken into the reverse micelles to form a stable microemulsion. By forming a stable microemulsion, it is possible to clean from low polarity dirt to high dirt. In the first embodiment of the present invention, whether or not it is a stable microemulsion is determined by absorbance. In the first embodiment, a W / O microemulsion detergent with an absorbance at 660 nm of less than 0.1 ABS is considered a stable microemulsion.

Moreover, in the 1st Embodiment of this invention, the proton signal of the water molecule in ¹ H-NMR measurement of the W / O microemulsion type cleaning agent used for washing | cleaning is 5.0 ppm or more and less than 5.2 ppm. When the proton signal of the water molecule in the ¹ H-NMR measurement of the W / O microemulsion type cleaning agent is 5.0 ppm or more, the ratio of free water in the water blended in the W / O microemulsion type cleaning agent is 71. % Or more, improving the cleaning power. If the proton signal is less than 5.2 ppm, a stable microemulsion is formed.

In the first embodiment of the present invention, ¹ H-NMR was measured under the following conditions. The ¹ H-NMR spectrum may be acquired under the following conditions, and the ¹ H-NMR apparatus is not limited.
Apparatus: Varian NMR System 500
Measurement nuclide: ¹ H (resonance frequency 499 MHz)
The measurement was performed with a double tube using a 5 mmΦ sample tube and a 3 mmΦ sample tube, and the sample was placed in the 3 mmΦ sample tube and the solvent deuterated chloroform was placed in the 5 mmΦ sample tube.

  In the first embodiment of the present invention, the washing temperature is preferably 10 ° C to 50 ° C. When the temperature is low, the ratio of the bound water in the reverse micelles in the water blended in the W / O microemulsion type cleaning agent decreases, and the ratio of free water that contributes to cleaning increases. However, if the temperature is too low, the kinematic viscosity of the W / O emulsion-type cleaning agent increases, and the cleaning agent is less likely to penetrate into the soil component. On the other hand, when the temperature is high, the kinematic viscosity of the W / O microemulsion-type cleaning agent becomes small and easily penetrates into the dirt component, so that the cleaning property is improved. However, if the temperature is too high, there is a possibility of ignition.

  In the first embodiment of the present invention, the water content and temperature of the W / O microemulsion-type cleaning agent are not limited as long as the above-described absorbance and proton signal chemical shift are satisfied. If the chemical shift of the proton signal is less than 5.0 ppm and it is desired to shift the signal to the low magnetic field side (5.0 ppm or more), the chemical can be added by adding water to the W / O microemulsion type detergent. The shift can be moved to the low magnetic field side. In addition, since a light absorbency may rise with the compounding quantity of water, it is preferable to determine the water content to mix | blend after confirming that a light absorbency is in the said range. In addition, when the absorbance at 660 nm is 0.1 ABS or more due to excessive moisture and less than 0.1 ABS, the water is evaporated by performing ultrasonic irradiation, bubbling operation, etc. on the W / O microemulsion type cleaning agent. As a result, the absorbance can be lowered.

In the second embodiment of the present invention, the absorbance at 660 nm is less than 0.1 ABS, the proton signal of water molecules in ¹ H-NMR measurement is 4.8 ppm or more and less than 5.0 ppm, and the kinematic viscosity is 4.0 mm. ^The object to be cleaned is cleaned with a W / O microemulsion type cleaning agent whose water content and temperature are adjusted to be less than ² / s.

  In the second embodiment of the present invention, as in the first embodiment, a W / O microemulsion type cleaning agent having an absorbance at 660 nm of less than 0.1 ABS is used.

Further, in the second embodiment of the present invention, the W / O micro of a proton signal of a water molecule in ¹ H-NMR measurement is 4.8 ppm or more and less than 5.0 ppm, and the kinematic viscosity is less than 4.0 mm ² / s. Wash with an emulsion cleaner. When the proton signal of the water molecule in the ¹ H-NMR measurement of the W / O microemulsion-type detergent is 4.8 ppm or more and less than 5.0 ppm and the kinematic viscosity is less than 4.0 mm ² / s, W / O micro The proportion of free water in the emulsion-type cleaning agent is 59% or more and less than 71%, but since the kinematic viscosity is low, the cleaning property can be improved by the penetration of the cleaning agent into the soil component.

In the second embodiment of the present invention, the ¹ H-NMR may be measured under the same conditions as in the first embodiment. The kinematic viscosity may be measured with a viscometer.

In the second embodiment of the present invention, the cleaning temperature is appropriately selected from 10 ° C to 50 ° C. The washing temperature is adjusted so that the absorbance at 660 nm is less than 0.1 ABS, the proton signal of the water molecule in ¹ H-NMR measurement is 4.8 ppm or more and less than 5.0 ppm, and the kinematic viscosity is less than 4.0 mm ² / s. By selecting, it is possible to wash even a dry water-soluble processing oil that is very difficult to wash.

  In the second embodiment of the present invention, the water content of the W / O microemulsion-type cleaning agent is not limited as long as the absorbance, the chemical shift of the proton signal, and the viscosity are satisfied. For example, when the chemical shift of the proton signal is less than 4.8 ppm and it is desired to shift to the low magnetic field side (4.8 ppm or more), the chemical shift can be reduced by adding water to the W / O microemulsion type detergent. It can move to the low magnetic field side. In addition, since the light absorbency and kinematic viscosity rise with the compounding quantity of water, it is preferable to determine the water content to mix | blend, after confirming that a light absorbency and kinematic viscosity are in the said range.

In the third embodiment of the present invention, the absorbance at 660 nm at a measurement temperature of 40 ° C. or higher is less than 0.1 ABS, and the proton signal of a water molecule is 4 in ¹ H-NMR measurement at a measurement temperature of 40 ° C. or higher. The object to be cleaned is cleaned by heating a W / O microemulsion type cleaning agent whose water content is adjusted to 0.0 ppm or more and less than 4.8 ppm to a measurement temperature of 40 ° C. or more.

  In the third embodiment of the present invention, a W / O microemulsion type cleaning agent having an absorbance at 660 nm of less than 0.1 ABS at a measurement temperature of 40 ° C. or higher is used.

Further, in the third embodiment of the present invention, the W / O microemulsion type cleaning in which the proton signal of the water molecule in the ¹ H-NMR measurement at the measurement temperature of 40 ° C. or more is 4.0 ppm or more and less than 4.8 ppm. Wash with chemicals. When the proton signal of the water molecule in the ¹ H-NMR measurement at a measurement temperature of 40 ° C. or higher of the W / O microemulsion type cleaning agent is 4.0 ppm or more and less than 4.8 ppm, the contamination component into the cleaning agent Detergency can be improved by dissolution and diffusion.

In the third embodiment of the present invention, the ¹ H-NMR may be measured under the same conditions as in the first embodiment.

In the third embodiment of the present invention, the cleaning temperature is a measurement temperature of 40 ° C. or higher. Select the washing temperature so that the absorbance at 660 nm is less than 0.1 ABS at a measurement temperature of 40 ° C. or higher, and the proton signal of the water molecule in the ¹ H-NMR measurement is 4.0 ppm or more and less than 4.8 ppm. Thus, it is possible to wash a dry water-soluble processing oil that is very difficult to wash.

  In the third embodiment of the present invention, the water content of the W / O microemulsion-type detergent is not limited as long as the above absorbance and proton signal chemical shift are satisfied at a measurement temperature of 40 ° C. or higher. Absent.

In the fourth embodiment of the present invention, the absorbance at 660 nm at a measurement temperature of less than 40 ° C. is less than 0.1 ABS, and the proton signal of a water molecule is 4 in ¹ H-NMR measurement at a measurement temperature of less than 40 ° C. The W / O microemulsion-type cleaning agent, whose water content is adjusted so that the kinematic viscosity is 0.0 ppm or more and less than 4.8 ppm and less than 2.0 mm ² / s, is heated to the measurement temperature of less than 40 ° C. Wash the wash.

  In the fourth embodiment of the present invention, a W / O microemulsion type cleaning agent having an absorbance at 660 nm of less than 0.1 ABS at a measurement temperature of less than 40 ° C. is used.

In the third embodiment of the present invention, the proton signal of the water molecule in the ¹ H-NMR measurement at a measurement temperature of less than 40 ° C. is 4.0 ppm or more and less than 4.8 ppm, and the kinematic viscosity is 2.0 mm ^2. Cleaning is performed with a W / O microemulsion type cleaning agent of less than / s. The proton signal of the water molecule in the ¹ H-NMR measurement of the W / O microemulsion type cleaning agent at a measurement temperature of less than 40 ° C. is 4.0 ppm or more and less than 4.8 ppm, and the kinematic viscosity is less than 2.0 mm ² / s. In this case, the proportion of free water is less than 59% in the physical properties of water blended in the W / O microemulsion type detergent, but the kinematic viscosity is sufficiently low, so that the detergent penetrates into the dirt component. Detergency can be improved.

In the fourth embodiment of the present invention, the ¹ H-NMR may be measured under the same conditions as in the first embodiment. Moreover, what is necessary is just to measure dynamic viscosity with a viscometer similarly to 2nd Embodiment.

In the fourth embodiment of the present invention, the cleaning temperature is appropriately selected from 10 ° C. or higher and lower than 40 ° C. The washing temperature is adjusted so that the absorbance at 660 nm is less than 0.1 ABS, the proton signal of water molecules in ¹ H-NMR measurement is 4.0 ppm or more and less than 4.8 ppm, and the kinematic viscosity is less than 2.0 mm ² / s. By selecting, it is possible to wash even a dry water-soluble processing oil that is very difficult to wash.

  In the fourth embodiment of the present invention, the water content of the W / O microemulsion-type cleaning agent is not limited as long as the above-described absorbance and chemical signal shift of the proton signal are satisfied.

  In the cleaning method of the present invention, after the object to be cleaned is cleaned according to the first embodiment, the second embodiment, the third embodiment, and the fourth embodiment, the object to be cleaned is surface-activated. It is preferable to perform a rinsing step of immersing in a rinsing liquid composed of a solvent substantially free of an agent. The solvent is preferably the same as the solvent used in the W / O microemulsion type cleaning agent of the present invention or rinsed with a solvent having a lower boiling point than the solvent used. Rinsing is preferably performed twice or may be performed three times or more. By performing the rinsing step, it is possible to remove the W / O microemulsion type cleaning agent remaining on the surface of the object to be cleaned and the surfactant blended in the W / O microemulsion type cleaning agent.

  The cleaning method of the present invention is performed by immersing an object to be cleaned in the above-described W / O microemulsion type cleaning agent or rinsing liquid, or spraying a W / O microemulsion type cleaning agent or rinsing liquid onto the object to be cleaned. Is preferred. In the case of cleaning by dipping in a W / O microemulsion type cleaning agent and a rinsing liquid, the cleaning effect can be improved by performing ultrasonic waves, stirring, air bubbling, rocking of an object to be cleaned, and the like.

  Embodiments of the present invention are illustrated below by examples, but the present invention is not limited to these examples.

“NS Clean” (registered trademark) 100M (manufactured by JX Nippon Mining & Energy Co., Ltd.), which is a W / O microemulsion type detergent containing a surfactant and water (3 mass%) in an aliphatic hydrocarbon 1) The amount of surfactant is the same as “NS Clean” (registered trademark) 100M, and the amount of surfactant is the same as that of sample 2, “NS Clean” (registered trademark) 100M, with a moisture content of 10% by mass. For the sample 3 having a water content of 0.3% by mass, the absorbance at 660 nm, the kinematic viscosity, and the chemical shift of the proton signal of the water molecule in ¹ H-NMR measurement, It changed to 10 degreeC, 25 degreeC, and 40 degreeC, and measured, respectively. The results are shown in Table 2.

  Moreover, the washing | cleaning test was done on the following washing | cleaning conditions using the samples 1-3. A simulated soil is prepared by diluting a water-soluble cutting / grinding fluid “Unisolve” (registered trademark) CS (manufactured by JX Nippon Mining & Energy Corporation) 10 times or 2 times with distilled water. Immerse the degreased simulated parts (wave type cage with claws, made of SUS) in water-soluble cutting oil diluted 10-fold or 2-fold, pull up, and air dry (40 ° C, 3 hours, circulating) Weigh the simulated parts. Simulated parts were immersed in samples 1 to 3 at a predetermined temperature, and washed with an ultrasonic cleaner (W-113, manufactured by Honda Electronics Co., Ltd.) at 28 kHz for 3 minutes. After cleaning, the simulated part is immersed in “NS Clean” (registered trademark) 100 (manufactured by JX Nippon Mining & Energy Co., Ltd., the same main component of the aliphatic hydrocarbon as in samples 1 to 3) at 25 ° C. While rinsing was performed for 1 minute. The rinsing process was performed twice in two tanks each charged with “NS Clean” (registered trademark) 100. After rinsing, the simulated part was dried at 80 ° C. for 20 minutes, allowed to cool, the simulated part was weighed, and the amount of residue of simulated dirt was calculated. When the amount of the residue was less than 1 mg, it was marked with ◯ and when the amount of residue was 1 mg or more. The results are shown in Table 2.

“NS Clean” (registered trademark) 220M (manufactured by JX Nippon Mining & Energy Co., Ltd.), which is a W / O microemulsion type detergent containing a surfactant and water (3 mass%) in an aliphatic hydrocarbon 4) “Sample 5”, “NS Clean” (registered trademark) 220M, the same amount of surfactant and 10% by mass of the moisture content of sample 5 were measured for absorbance at 660 nm, kinematic viscosity, and ¹ H-NMR measurement. The chemical shift of the proton signal of water molecules was measured by changing the temperature of samples 4 and 5 to 10 ° C, 25 ° C, and 40 ° C, respectively. The results are shown in Table 3.

  Further, using the samples 4 and 5, a cleaning test was performed under the following cleaning conditions. A simulated soil is prepared by diluting a water-soluble cutting / grinding fluid “Unisolve” (registered trademark) CS (manufactured by JX Nippon Mining & Energy Corporation) 10 times or 2 times with distilled water. Immerse the degreased simulated parts (wave type cage with claws, made of SUS) in water-soluble cutting oil diluted 10-fold or 2-fold, pull up, and air dry (40 ° C, 3 hours, circulating) Weigh the simulated parts. Simulated parts were immersed in samples 4 and 5 at a predetermined temperature, and washed with an ultrasonic cleaner (H-113, manufactured by Honda Electronics Co., Ltd.) for 3 minutes at 28 kHz. After cleaning, the simulated part is immersed in “NS Clean” (registered trademark) 200 (manufactured by JX Nippon Mining & Energy Co., Ltd., mainly composed of aliphatic hydrocarbons having a boiling point lower than those of Samples 4 and 5) at 25 ° C., Rinse was performed for 1 minute while rocking. The rinsing process was performed twice in two tanks each charged with “NS Clean” (registered trademark) 200. After rinsing, the simulated part was dried at 80 ° C. for 20 minutes, allowed to cool, the simulated part was weighed, and the amount of residue of simulated dirt was calculated. When the amount of the residue was less than 1 mg, it was marked with ◯ and when the amount of residue was 1 mg or more. The results are shown in Table 3.

Sample 1 (“NS Clean” (registered trademark) 100M, moisture content 3% by mass), Sample 3 (“NS Clean” (registered trademark) 100M, moisture content 0.3% by mass) and Sample 4 (“NS clean”) "(Registered trademark) 220M, water content 3% by mass), the absorbance at 660 nm, the kinematic viscosity, and the chemical shift of the proton signal of the water molecule in ¹ H-NMR measurement were measured at a temperature of 30 ° C. The results are shown in Table 4. In addition, a cleaning test was performed using Sample 1, Sample 3, and Sample 4 under the following cleaning conditions. A simulated soil is prepared by diluting a water-soluble cutting / grinding fluid “Unisolve” (registered trademark) CS (manufactured by JX Nippon Mining & Energy Corporation) twice with distilled water. A degreased simulated part (cold rolled steel sheet, 1.2 × 30 × 30 mm) is dipped in a 2-fold diluted water-soluble cutting oil, pulled up, heated (80 ° C., 30 minutes, circulation type), and then a sample at 30 ° C. 1, each sample was immersed in Sample 3 or Sample 4, and was cleaned at 45 kHz for 1 minute with an ultrasonic cleaner (W-113, manufactured by Honda Electronics Co., Ltd.). The cleaned simulated part was immersed in “NS Clean” (registered trademark) 100 (manufactured by JX Nippon Mining & Energy Corporation) at 25 ° C. and rinsed for 30 seconds while rocking. The rinsing process was performed twice in two tanks each charged with “NS Clean” (registered trademark) 100. After rinsing, the simulated part was dried at 80 ° C. for 30 minutes, allowed to cool, and then visually observed for external appearance. The results are shown in Table 4. Further, a simulated part without a stain was DLC coated, and the appearance was visually observed. No abnormalities such as pinholes and film peeling were marked with ◯, and abnormalities such as pinholes and film peeling were marked with X. The results are shown in Table 4.

  As described above, the W / O microemulsion type cleaning agent evaluation method, the cleaning method using the W / O microemulsion type cleaning agent, and the film forming method according to the present invention are the same as those before PVD coating processing, particularly DLC coating. Suitable for processing.

Claims (6)

A method for evaluating the detergency of a W / O microemulsion type detergent in which water and a surfactant are mixed in a solvent,
A method for evaluating detergency of a W / O microemulsion-type detergent, comprising evaluating detergency based on absorbance and proton signals of water molecules in ¹ H-NMR measurement. A cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent,
The W / O microemulsion-type detergent whose water content and temperature are adjusted so that the absorbance at 660 nm is less than 0.1 ABS and the proton signal of water molecules in ¹ H-NMR measurement is 5.0 ppm or more and less than 5.2 ppm. A method for cleaning with a W / O microemulsion type cleaning agent, wherein the object to be cleaned is cleaned with A cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent,
The water content and temperature are adjusted so that the absorbance at 660 nm is less than 0.1 ABS, the proton signal of the water molecule in ¹ H-NMR measurement is 4.8 ppm or more and less than 5.0 ppm, and the kinematic viscosity is less than 4.0 mm ² / s. A cleaning method using a W / O microemulsion-type cleaning agent, wherein an object to be cleaned is cleaned with the adjusted W / O micromicroemulsion-type cleaning agent. A cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent,
The absorbance at 660 nm at a measurement temperature of 40 ° C. or higher is less than 0.1 ABS, and the proton signal of water molecules in ¹ H-NMR measurement at a measurement temperature of 40 ° C. or higher is 4.0 ppm or more and less than 4.8 ppm. A cleaning method using a W / O microemulsion type cleaning agent, wherein the object to be cleaned is cleaned by heating the W / O microemulsion type cleaning agent with adjusted water content to the measurement temperature of 40 ° C. or higher. A cleaning method using a W / O microemulsion-type cleaning agent in which water and a surfactant are mixed in a solvent,
Absorbance at 660 nm at a measurement temperature of less than 40 ° C. is less than 0.1 ABS, proton signal of water molecule in ¹ H-NMR measurement at a measurement temperature of less than 40 ° C. is 4.0 ppm or more and less than 4.8 ppm, and kinematic viscosity is The W / O microemulsion type cleaning agent, whose water content is adjusted to be less than 2.0 mm ² / s, is heated to the measurement temperature of less than 40 ° C. to wash the object to be cleaned. Cleaning method with / O microemulsion type cleaning agent.   6. A film forming method comprising coating the surface of an object to be cleaned, which has been cleaned by the cleaning method using the W / O microemulsion type cleaning agent according to any one of claims 2 to 5, with diamond-like carbon.

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