JPH0989638A - How to measure the amount of residual processing oil - Google Patents

Abstract

(57) Abstract: An object of the present invention is to accurately measure the amount of residual processing oil remaining on the surface of a metal product that has been subjected to metal processing and then washed with a detergent. It is to provide a measuring method of quantity. The present invention is a method for measuring the amount of residual processing oil remaining on the surface of a metal product that has been subjected to metal processing and then washed with a cleaning agent, wherein the metal product dissolves the residual processing oil. After the residual processing oil is dissolved and extracted in a washing tank containing an organic solvent that can be used, the obtained extract is filtered with an inorganic fiber filter paper, and then the oil concentration of the obtained filtrate is increased. A method for measuring the amount of residual processing oil is characterized by quantifying the amount of residual processing oil by meter or infrared absorption spectrum analysis.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for measuring the amount of residual processing oil. More specifically, the present invention relates to a measuring method capable of accurately measuring residual processing oil remaining in a metal product subjected to metal processing.

[0002]

2. Description of the Related Art Generally, when a metal material is subjected to metal working, such as roll rolling, die wire drawing, and cutting, it is carried out while applying working oil to the surface of the metal material.

When these metal workings are finished, the working oil adhering to the surface of the metal working product is industrially washed and removed with a suitable degreasing detergent.

However, a slight amount of processing oil remains on the surface of the metal processed product that has been industrially cleaned.

As such a degreasing detergent, a flame-retardant low-boiling organic solvent such as 1,1,1-trichloroethane is often used.

By the way, this 1,1,1-trichloroethane is known as a chemical substance that destroys the ozone layer of the earth, and it has been decided to abolish it after 1996.

For this reason, many industrial associations are searching for environmentally friendly degreasing detergents that do not destroy the ozone layer of the earth.
Research is ongoing.

Examples of the environment-friendly degreasing detergent that does not destroy the ozone layer include a water-based degreasing detergent and a specific hydrocarbon-based degreasing detergent. In addition, a chlorine-containing organic solvent that is not regulated may be used.

In the field of processing of such metal materials, much attention has often been paid to the amount of processing oil remaining on the surface of metal processed products after cleaning with a degreasing detergent.

However, when examining the detergency of many degreasing detergents, it was necessary to evaluate the conventional method for measuring the amount of residual processing oil.

The following two methods have been used as conventional methods for measuring the amount of residual processing oil.

(1) Infrared absorption spectrum of carbon tetrachloride extract
Toll analysis method . In this method, first, a metalworked product that has undergone metalworking is subjected to extraction treatment with carbon tetrachloride for specialized infrared absorption spectrum analysis, and the residual processing oil adhering to the surface of the metalworked product is removed from carbon tetrachloride. Dissolve in.

.. Next, the obtained carbon tetrachloride extract for specialized infrared absorption spectrum analysis is subjected to infrared absorption spectrum analysis based on the -CH bond of the processing oil by an infrared absorption spectrum analyzer.

.. Next, the amount of residual processing oil is quantified from the infrared absorption spectrum based on the obtained —CH bond and Lamber-Beer's law.

The reason why the carbon tetrachloride specialized for infrared absorption spectrum analysis is used as the extract is as follows.

That is, in general carbon tetrachloride, a specific chemical stabilizer is contained, and the specific chemical stabilizer overlaps the infrared absorption spectrum based on the --CH bond of the processing oil, which is accurate. This is because an infrared absorption spectrum based on the -CH bond of the processing oil cannot be obtained. Carbon tetrachloride for specialized use in infrared absorption spectrum analysis is a special grade that can completely prevent such overlapping of infrared absorption spectra.

Further, although there is an oil concentration meter as a simple measuring device for quantifying the amount of residual processing oil from a carbon tetrachloride extract specialized for infrared absorption spectrum analysis, accurate quantification is difficult.

As a method for quantifying the amount of residual processing oil from the carbon tetrachloride extract for specialized infrared absorption spectrum analysis, F
The T-IR method is used.

(2) Method for measuring evaporation residue of solvent extract . In this method, first, a metalworked product that has undergone metalworking is subjected to extraction treatment with a general-grade solvent such as general-grade carbon tetrachloride, and the residual processing oil adhering to the surface of the metalworked product is treated with carbon tetrachloride. Dissolve in.

[0020] Next, the obtained carbon tetrachloride extract is transferred to an evaporation dish, and carbon tetrachloride as a solvent is heated to a boiling point or higher to evaporate and volatilize.

[0021]. Next, the obtained evaporation residue is weighed with an analytical balance to determine the amount of residual processing oil.

In this method, as the solvent, 1,1,1-trichloroethane, dichloromethane and the like can be used in addition to general grade carbon tetrachloride.

However, these two methods have the following drawbacks.

Difficulties of the above method (1) In this method, a metalworked product subjected to metalworking is subjected to extraction treatment with carbon tetrachloride specializing for infrared absorption spectrum analysis, and the measured values greatly differ depending on the extraction conditions. .

For example, if the extraction conditions are not rigorously determined among the three manufacturers, the cleaning equipment manufacturer, the cleaning agent manufacturer, and the metalworking manufacturer, the obtained measurement values will differ greatly. Also, even if the same measurer decides the extraction conditions quite rigorously, the obtained measurement values will differ greatly.

Difficulties of the above method (2) In this method, a metalworked product subjected to metalworking is subjected to extraction treatment with carbon tetrachloride in the same manner as in the method (1), but the measured value greatly differs depending on the extraction conditions. . In addition, in the method (2), the measurement value is likely to fluctuate due to the influence of fluctuations in the weight of the extraction container, evaporation of the solvent, volatilization conditions, evaporation of the residual processing oil, alteration, and moisture condensation due to heat of evaporation There is.

[0027]

SUMMARY OF THE INVENTION The present invention has been made in view of the above point, and its purpose is to eliminate the above-mentioned drawbacks of the prior art and to perform metal working before cleaning with a cleaning agent. Another object of the present invention is to provide a method for measuring the amount of residual processing oil that can accurately measure the amount of residual processing oil remaining on the surface of a metal product that has received the heat treatment.

[0028]

SUMMARY OF THE INVENTION The gist of the present invention is that a metal product that has been subjected to metal processing and then a cleaning treatment with a detergent is subjected to an extraction treatment with an organic solvent, and then the extracted liquid is treated with an inorganic fiber. In this method, fine metal powder is removed by filtering with filter paper, and the amount of residual processed oil is measured by an oil concentration meter or infrared absorption spectrum analysis of the filtrate.

That is, as a result of diligent study by the inventor of the cause of the variation in the analysis value of the measured value of the residual processing oil, in addition to the largest cause of the variation, the fine metal powder mixed in the residual processing oil is The inventors of the present invention have found out that there is one and have reached the present invention.

Such fine metal powder is generated during metal working, and the fine metal powder is mixed into the residual working oil as it is, or the residual working oil is left on the surface of the metal product subjected to the metal working. It is fixed with a mechanically embedded form.

The fine metal powder adhered to the surface of the metal product together with the residual processing oil in a mechanically embedded form is
It is difficult to remove even if washed with a normal degreasing detergent. The ultrasonic cleaning treatment is effective for removing the fine metal powder fixed to the surface of the metal product together with the residual processing oil in a mechanically embedded form.

In this ultrasonic cleaning treatment, first, a metal product subjected to metal working was immersed in a carbon tetrachloride solution, and then ultrasonic waves were applied to the carbon tetrachloride solution to mechanically embed it on the surface of the metal product. The fine metal powder adhered in a shape peels off and falls into the carbon tetrachloride solution. That is, the residual processing oil remaining on the surface of the metal product is dissolved by the dissolving power of carbon tetrachloride and mechanically separated by ultrasonic waves, and is completely extracted by its synergistic action.

The quality of this ultrasonic cleaning treatment depends on the size of the ultrasonic cleaning treatment tank used, the amount of carbon tetrachloride put in the treatment tank,
It is important to properly size and quantity the metal products to be cleaned.

For example, when the size of the ultrasonic cleaning treatment tank is small, the amount of carbon tetrachloride is small, and the amount of metal products to be cleaned is large, the ultrasonic waves having straightness do not act on all the metal products. As a result, the residual processing oil remaining on the surface of the metal product is incompletely dissolved in carbon tetrachloride, and the fine metal powder that is mechanically embedded in the surface of the metal product is also incompletely removed. Becomes

On the other hand, when the size of the ultrasonic cleaning treatment tank is large and the amount of carbon tetrachloride is large and the amount of metal products to be cleaned is small, the ultrasonic waves having a straight line action act on all metal products, As a result, the residual processing oil remaining on the surface of the metal product is completely dissolved in carbon tetrachloride, and the fine metal powder that is mechanically embedded in the surface of the metal product is completely removed. .

Here, as a matter of course, the longer the ultrasonic wave is applied, the more complete the dissolution of the residual processing oil remaining on the surface of the metal product in carbon tetrachloride, and the more mechanically embedded the surface of the metal product. The removal of the fine metal powder stuck in shape is also more complete.

The fine metal powders vary from large ones to extremely fine ones.

The extremely fine metal powder floats for a long time without settling at the bottom of the carbon tetrachloride extract. It is difficult to obtain an accurate absorption spectrum as a result of such a fine metal powder that floats and blocks the infrared rays in the infrared absorption spectrum analysis without blocking the infrared rays. As a result, it is difficult to accurately measure the amount of residual processing oil using a carbon tetrachloride extract containing fine metal powder that floats.

[0039] In addition, when a fine metal powder that floats in the infrared absorption spectrum analysis blocks infrared rays without transmitting them, the apparent absorbance increases, and as a result, the amount of residual processing oil becomes larger than the true value. I will make a mistake.

In the above method (2), there is a problem with a heavy metal powder which settles to the bottom of the carbon tetrachloride extract in a short time. That is, the density of metal powder that is heavy enough to settle at the bottom of the carbon tetrachloride extract in a short time is several times greater than that of residual processing oil, and as a result, the larger the amount of metal powder mixed in, the more apparent residual processing The mistake that the amount of oil becomes large occurs.

Therefore, if the fine metal powder present in the carbon tetrachloride extract can be effectively removed, the residual processing oil can be accurately measured.

The present inventor has found that the inorganic fiber filter paper is the most suitable for effectively removing the fine metal powder present in the carbon tetrachloride extract, and has arrived at the present invention.

That is, since the inorganic fiber filter paper effectively removes the fine metal powder and is neither dissolved nor extracted in the extraction solvent of the residual processing oil, there is no measurement error, and as a result, the residual processing oil can be accurately measured. It is possible.

On the other hand, general cellulose type filter paper is dissolved and extracted in the extraction solvent of residual processing oil, and the extracted cellulose etc. are overlapped with the peak absorption of the infrared absorption spectrum of the residual processing oil and the residual processing oil is extracted. Is difficult to measure accurately.

As the inorganic fiber filter paper, there are glass fiber filter paper, ceramic fiber filter paper, rock wool fiber filter paper and the like.

The particle retaining ability of these inorganic fiber filter papers is not particularly limited, but is preferably about 3 μm or less.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION Next, examples of the method for measuring the amount of residual processing oil according to the present invention will be described.

First, a copper strip rolled by the following rolling conditions was industrially manufactured.

The production lots used in Examples 1 to 4 and Comparative Examples 1 to 4 below are A lots, and Examples 5 to 7 below.
The lot used in Comparative Examples 5 to 7 is B lot.

(Rolling conditions) Copper strip thickness after processing 0.04 mm Processing degree 5% Processing oil used Synthetic oil (viscosity: 3 cSt, specific gravity;
0.8) Next, the copper strip obtained above was industrially washed under the following conditions.

(Industrial cleaning conditions) Cleaning solvent name: 1,1,1-trichloroethane Cleaning time: 2 seconds Cleaning method: 1,1,1-Trichloroethane Transporting and moving in cleaning tank Next, the copper industrially cleaned as described above. The residual processed oil was measured by the measuring method of the residual processed oil of Examples and Comparative Examples.

Example 1 First, a plurality of industrially cleaned copper strips of A lot were cut into a plurality of copper strips of about 0.8 cm ² and collected.

Next, these finely cut copper strips were placed in a washing tank containing 20 ml of carbon tetrachloride, and ultrasonic waves were applied for 1 minute to remove residual processing oil from the copper strips into carbon tetrachloride. Dissolved and extracted.

Next, the obtained carbon tetrachloride extract was applied to a glass fiber filter paper (GF-75 manufactured by Advantech Toyo Co., Ltd.).
By filtering with a filter paper), fine copper powder mixed in carbon tetrachloride was removed.

Next, the filtrate was divided into two parts, and the residual processed oil was measured by an oil concentration meter and the residual processed oil was measured by infrared absorption spectrum analysis (FT-IR).

(Example 2) Extraction of residual processing oil, removal of fine copper powder, and measurement of residual processing oil were carried out in the same manner as in Example 1 except that ultrasonic waves were applied for 20 minutes.

Example 3 First, two industrially washed copper strips of A lot were cut into two pieces of 7 cm square and collected.

Next, these two cut copper strips were placed in a washing tank containing 100 ml of carbon tetrachloride, and then ultrasonic treatment was applied for 3 minutes to each copper strip for residual processing. The oil was dissolved in carbon tetrachloride and extracted.

Thereafter, the fine copper powder is removed in the same manner as in Example 1,
The residual processing oil was measured.

(Example 4) Extraction of residual processing oil and extraction of fine copper were carried out in the same manner as in Example 3 except that 13 strips of industrially cleaned copper strips of A lot were cut into 7 cm square and collected. The powder was removed and the residual processing oil was measured.

(Example 5) First, six industrially washed copper strips of lot B were cut and sampled into 6 strips of 7 cm square.

Next, these cut copper strips were placed in a washing tank containing 30 ml of carbon tetrachloride, and ultrasonic waves were applied to each strip for 3 minutes to remove residual processing oil from the copper strips to carbon tetrachloride. Dissolved in and extracted.

Thereafter, as in Example 1, removal of fine copper powder,
The residual processing oil was measured.

(Embodiment 6) Extraction of residual processing oil and extraction of fine copper powder were carried out in the same manner as in Embodiment 5 except that 12 pieces of industrially washed B lot copper strips of 7 cm square were used. The removal and residual processing oil were measured.

(Example 7) Example 5 except that 11 industrially washed copper lots of B lot having a size of 10 cm square were used.
In the same manner as above, extraction of residual processing oil, removal of fine copper powder, and measurement of residual processing oil were performed.

Infrared absorption spectrum analysis is 2000 cm -1
The reproducibility was secured by connecting the two absorbances at 3400 cm −1 with a straight line and performing background processing.

Therefore, even if fine copper powder is suspended in the carbon tetrachloride extract and the transmitted light of infrared rays is reduced over the entire wavelength, the peak of oil can be measured correctly.

(Comparative Example 1) First, a plurality of industrially cleaned copper strips of A lot were cut into a plurality of 0.8 cm ² copper strips and collected.

Next, these finely cut copper strips were placed in a washing tank containing 20 ml of carbon tetrachloride, and ultrasonic waves were applied for 20 minutes to remove residual processing oil from the copper strips into carbon tetrachloride. Dissolved and extracted.

Next, the carbon tetrachloride extract was divided into two, and the residual processed oil was measured with an oil concentration meter and the residual processed oil was measured with infrared absorption spectrum analysis.

Comparative Example 2 The residual processed oil was dissolved and extracted in carbon tetrachloride in the same manner as in Comparative Example 1 except that ultrasonic waves were applied for 20 minutes.

Next, the obtained carbon tetrachloride extract was applied to a glass fiber filter paper (GF-75 manufactured by Advantech Toyo Co., Ltd.).
By filtering with a filter paper), fine copper powder mixed in carbon tetrachloride was removed.

Next, the filtrate was divided into two, and the residual processed oil was measured with an oil concentration meter and the residual processed oil was measured with infrared absorption spectrum analysis.

(Comparative Example 3) Two pieces of industrially washed copper strips of A lot were cut into 7 cm square copper strips.
It was collected.

Next, these cut copper strips are placed in a washing tank containing 30 ml of carbon tetrachloride, and ultrasonic waves are applied to each strip for 3 minutes to remove residual processing oil from the copper strips to carbon tetrachloride. Dissolved in and extracted.

Next, the carbon tetrachloride extract was divided into two parts, and the residual processed oil was measured with an oil rich clock and the residual processed oil was measured with infrared absorption spectrum analysis.

(Comparative Example 4) Residual processing oil was tetrachlorinated from copper strips in the same manner as in Comparative Example 3 except that there were 13 industrially cleaned copper strips of A lot having a size of 7 cm square. It was dissolved in carbon and extracted.

Thereafter, in the same manner as in Comparative Example 2, fine copper powder was removed and residual processing oil was measured. (Comparative Example 5) Residual processing oil was extracted, fine copper powder was removed, and remaining was carried out in the same manner as in Comparative Example 4 except that 6 industrially washed B lot copper strips of 7 cm square were used. The processing oil was measured.

(Comparative Example 6) * Extraction of residual processing oil, removal of fine copper powder, measurement of residual processing oil in the same manner as in Comparative Example 4 except that 12 copper strips 7 cm square were used. I went.

(Comparative Example 7) Extraction of residual processing oil, removal of fine copper powder and measurement of residual processing oil were carried out in the same manner as in Comparative Example 4 except that one piece of copper strip 10 cm square was used. went.

Table 1 shows the measurement results in each of the above examples.

[0082]

[Table 1]

As can be seen from Table 1, the measured values of the residual processing oils of Comparative Examples 1 to 7 are several times depending on the copper strip lot, the measuring method, the size of the copper strips, the number of copper strips, the ultrasonic treatment time, etc. -10 times different.

On the other hand, the measured values of the residual processing oils of Examples 1 to 7 of the present invention are slightly different between copper strip lots and between the oil concentration meter measuring method and the infrared absorption spectrum measuring method. , The size of the copper strip, the number of copper strips, the ultrasonic treatment time, etc. did not differ greatly, and reproducible data were obtained.

Table 2 shows the results of measuring the residual processed oil with an oil concentration clock for the filtrate obtained by filtering the carbon tetrachloride extract with different kinds of filter paper.

[0086]

[Table 2]

As can be seen from Table 2, C1 is the oil content value (mg
/ L) is 0. This is 0 even if it filters with a glass filter.

However, in C2, the oil content value after filtration was 1.3, although the measurement solution was a blank sample of carbon tetrachloride for oil content measurement. This is due to the fact that the paper filter used an oil content carbon tetrachloride to dissolve impurities in the paper filter and cause an error.

On the other hand, there is no great change in the oil content measurement value of the filtrate filtered with the glass fiber filter paper, and it can be understood that the influence of the particle retention ability can be neglected to some extent.

A centrifugal separation method or the like can be applied to remove the fine metal powder of the extract. This is because carbon tetrachloride has a large difference of 1.63, residual processing oil is 0.83, and copper powder is 8.96.

[0091]

Industrial Applicability According to the method of measuring the amount of residual processing oil of the present invention, the residual processing oil remaining on the metal surface in metalworking can be accurately and reproducibly measured, and is industrially useful.

Claims (5)

[Claims] 1. A method of measuring the amount of residual processing oil remaining on the surface of a metal product that has been subjected to metal processing and then washed with a cleaning agent, the method being capable of dissolving the residual processing oil in the metal product. After the residual processing oil was dissolved and extracted in a washing tank containing an organic solvent, the obtained extract was filtered through a filter paper made of inorganic fiber, and then the residual processing oil amount in the obtained filtrate was measured. A method for measuring the amount of residual processing oil, which comprises quantifying. 2. The method for measuring the amount of residual processing oil according to claim 1, wherein the inorganic fiber filter paper is one selected from glass fiber filter paper, ceramic fiber filter paper, and rookeool fiber filter paper. 3. The method for measuring the amount of residual processing oil according to claim 1, wherein the inorganic fiber filter paper has a particle retention capacity of 3 μm or less. 4. The residual processing oil is dissolved in a washing tank containing an organic solvent capable of dissolving the residual processing oil,
The method for measuring the amount of residual processing oil according to claim 1, wherein ultrasonic waves are added during extraction. 5. The method for measuring the amount of residual processing oil according to claim 1, wherein the measuring method for quantifying the amount of residual processing oil is an oil concentration meter measuring method or an infrared absorption spectrum analysis measuring method.