JPH08271448A - High sensitivity penetrating liquid employed in penetration flaw detection method - Google Patents

Abstract

PURPOSE: To provide a high sensitivity penetration liquid being employed in the penetration flaw detection method in order to detect even an extremely fine defect on the surface. CONSTITUTION: The high sensitivity penetration liquid is composed of 5-10wt.% of visible dye or fluorescent dye, 10-40wt.% of base solvent comprising an organic solvent for dissolving the dye having boiling point of 190 deg. or above, and 30-85wt.% of dilute solvent comprising a volatile organic solvent compatible with the base solvent having boiling point of 110 deg. or below. The penetration liquid is employed in the penetration flaw detection method where 50-80wt.% of dilute solvent evaporates and self-condenses at the time of penetration processing. With such a method, a flaw of only 3μm deep can be detected when a fluorescent dye is mixed and a flaw of 20μm deep can be detected when a visible dye is mixed.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a penetrant liquid used in a penetrant flaw detection test method, which has an extremely fine flaw depth of 20 μm when a visible dye is blended and a flaw depth of 3 μm when a fluorescent dye is blended. Provided is a high-sensitivity penetrant capable of reliably detecting even a surface opening defect portion.

[0002]

2. Description of the Related Art Penetration testing methods are used to detect surface cracks such as fine cracks and pinholes present on the surfaces of various components (eg automobile components) and various components (eg nuclear reactor components). ) Is commonly used to detect
It is standardized in "JIS Z 2343-1992" (hereinafter referred to as "JIS standard").

As seen in the JIS standard, a dye penetrant and a fluorescent penetrant are used in the penetrant testing method, both of which are commercially available.

As is well known, the dyeing penetrant is a highly penetrative liquid obtained by dissolving a visible dye (usually a red dye such as Oil Red 5BN: Shirad Chemical Co., Ltd. or Sudan Red 462: BASF Co.) in an organic solvent. , The fluorescent penetrant is a fluorescent dye (usually a dye that emits yellow-green fluorescence under an ultraviolet light, such as Florescent Bright varnish agent 6
8: Nippon Kayaku Co., Ltd. or Fluorol 7GA: GAF Co., Ltd.) is a highly permeable liquid obtained by dissolving it in an organic solvent.

And in the case of any of the penetrants, "Non-destructive inspection handbook [new edition] edited by Japan Association for Non-destructive Inspection"
・ Page 720, Nikkan Kogyo Shimbun, published on April 28, 1978, "The solvent of the penetrant needs not only the dissolving power for the dye but also the penetrating property for the defective part. Therefore, in many cases By combining several types of solvents, the formulation is assembled on the basis of the balance of the characteristics of each component.
Solvents are roughly divided into basic ones and those which have a diluting function. It is essential that the basic solvent (Applicant's note: referred to by those skilled in the art as "base solvent") dissolves the dye well and makes the hue of the fluorescent dye or coloring dye clear. In addition, it is required to have a high boiling point and be hard to volatilize, not corrosive to metals, and having no or little odor. Generally, high boiling point esters, high boiling point alcohols, polyhydric alcohol derivatives and the like are used from the above viewpoint. In addition to the purpose of adjusting viscosity and fluidity appropriately, the diluting solvent also serves to reduce material costs. The requirements for this are that it is well compatible with the basic solvent, is not corrosive to metals, has no unpleasant odor, and has low toxicity. The penetrant may be used in an open tank or may be taken out of a closed container after each use, and the volatility of the diluent solvent may be changed accordingly. In any case, a chain or cyclic hydrocarbon is generally used. The quality of the balance between the basic solvent and the diluting solvent is an important factor that determines the quality of the performance, which affects the properties of the penetrant (viscosity, surface tension, wettability, etc.). As described in "...", two kinds of organic solvents, that is, a base solvent and a diluting solvent, are combined and blended.

Further, "Japanese Patent Laid-Open No. 3-175345"
In the example, a combination example of a base solvent and a diluting solvent is used, "... the solvent-removable dyeing penetrant uses a red oil-soluble dye (for example, Oil Red 5BN: manufactured by Shirado Chemical Co., Ltd.) as a dye, 1 to 5 parts by weight of the dye is used in an amount of 20 to 50 parts by weight of a base solvent composed of a plasticizer (for example, DOP: dioctyl phthalate) or a vegetable oil (for example, soybean oil), xylene, alkylbenzene, trichloroethane, trifluorotrichloroethane, carbitol, and It is a highly penetrating liquid dissolved in 50 to 80 parts by weight of a diluting solvent consisting of a volatile low / medium-boiling point organic solvent selected from butyl carbitol and the like. A typical commercially available product is Super Check UP-NU. (Product name: Mark Tech Co., Ltd.) In addition, the solvent-removable fluorescent penetrant is a firefly that develops a yellow-green color under UV light as a dye. Dye (for example, C.I Solvent Yellow 43:. Made by the United States Morton Co., Ltd.), C.I.
Fluorescent bright varnish agent 68: manufactured by Nippon Kayaku Co., Ltd., which is dissolved in a base solvent and a diluting solvent in the same manner as in the solvent-removable dye-penetrating liquid, and has a high penetrability. A typical commercially available product is Super Glow OD-6000 (trade name: manufactured by Mark Tech Co., Ltd.). … ”Is specifically shown.

Incidentally, "Japanese Patent Publication No. 34-3948" discloses a solid organic fluorescent material containing "... dinaphthylene oxide, tetracene, dihydrotetracene, pyrene, or a mixture thereof as a main component. Boiling point solvent such as benzene,
Although a fluorescent penetrating solution prepared by dissolving it in toluene or the like at a concentration of about 0.1% or more is disclosed, to the present inventors' knowledge,
This fluorescent penetrant is not in practical use, and the dyeing penetrant and the fluorescent penetrant currently in practical use are both prepared by combining two kinds of organic solvents, the base solvent and the diluent solvent described above. .

[0008]

Regarding the flaw detection limit when the penetrant flaw detection test method is carried out using the dye penetrant and the fluorescent penetrant currently in practical use (commercially available), see "Magazine / Nondestructive Inspection No. 1". Vol. 44, No. 2, pp. 71-73, Japan Non-Destructive Inspection Association, February 1, 1995, "Limits for Detection of Surface Defects in Magnetic Particle Testing and Penetrant Testing, Kazuo Miyagawa (Former Professor, Nihon University) "... (1) Preface In a penetrant flaw detection test (hereinafter referred to as PT) ... For a nickel-chromium plating cracking test piece (hereinafter referred to as Ni-CrT.P.) Whose volume changes most quantitatively, Describe what is understood from the test results conducted so far.
It should be noted that the TP has some operational problems that affect the detection performance, but it is assumed that all of them are completely operated and the best test is performed. (2) In the case of dyeing penetrant a. For solvent removal, the detection limit is a flaw depth of 3
It is 0 μm. 20 μm Ni-CrT. P. In some cases, an extremely thin linear pattern may appear, but it is not a pattern that can be recognized as a flaw in an actual flaw detection test.
b. The detection limit does not change depending on the brand of flaw detection agent. Depending on the type of dye used, the concentration, the volatility of the solvent, etc., the indication pattern may show some shades, but the detection limit itself is up to 30 μm. ... d. In case of removal by washing with water, the detection limit is 50 μm in depth. (3) In the case of fluorescent penetrant a. In the best condition, the detection limit is a flaw depth of 10 μm. ... b. The undeveloped method cannot detect 10 μm. ... "is reported.

In addition, in Japanese Patent Publication No. 34-9748, the use of the fluorescent penetrant disclosed in the above publication "can detect even scratches of 5 .mu. It is possible to clearly understand the shape of the crack without expanding it .. It is possible to use the developing operation together. In this case, it is possible to clearly know even a very shallow crack of 1 to 2 .mu.m. It is possible ... ", but" 5μ "described here,
It can be presumed that the numerical value of “1 to 2 μ” indicates not the flaw depth but the flaw width. Because the fluorescent penetrant does not contain a base solvent, it has a flaw depth of 5
This is because it is unlikely that a flaw depth of 1 μm or 2 μm is detected.

As can be seen from the above report, one of the factors that the detection limit of dyeing penetrant is 30 μm and the detection limit of fluorescent penetrant is 10 μm is It can be said that the amount of permeating liquid that permeates is small.

That is, some flaws existing on the surface of the inspection object to which the penetrant testing method is applied are penetrated and some are not penetrated, and the usual inspection object is often the latter. If the flaw existing in the inspection object does not penetrate the small opening, even if the dye penetrant or fluorescent penetrant is sufficiently adhered to the surface of the object to be inspected, The amount of the permeating liquid that permeates becomes small because the amount of the permeating liquid that replaces the air inside the flaw is small.

More specifically, since the volume of a certain amount of gas is inversely proportional to the pressure and directly proportional to the absolute temperature (Boyle-Charles' law), in the case of a flaw having a small opening and not penetrating, a bathtub is used. The same phenomenon occurs when the air inside the bath tub is not completely replaced with warm water when the bath tub is turned upside down, and the air inside the flaw does not completely replace the permeate, so the permeate that permeates inside the flaw. The amount of will be small.

Of course, in the art, it is technically possible to provide a penetrant liquid capable of forming a clear defect indicating film with a small amount of penetrant liquid penetrating inside the flaw and capable of reliably detecting finer flaws. Research and development is being promoted as an issue.

A typical technical means adopted to achieve the above technical problems is to form a clear defect-indicating pattern by increasing the amount of dye compounded in the composition of the penetrant liquid. Is.

However, when the amount of the dye blended in the composition of the penetrant liquid is increased, the problem of the dye sticking out occurs, and it is impossible to put into practical use the penetrant liquid in which the dye sticks out during storage.

Therefore, in the art, a penetrant liquid in which the amount of the dye is increased without causing the dye to stick out is obtained by variously selecting the type of the dye, the type of the base solvent and the type of the diluting solvent, and the mixing ratio thereof. Although it has been commercialized, the types of visible dyes and fluorescent dyes that can be used in the penetrant testing method are limited, so the limited dyes are used to increase the compounding amount without causing the dyes to break out. There is a limit to this, and when the commercially available penetrant is used, the results are as reported above.

In view of the present situation as described above, the present invention provides a small amount of permeation into flaws even though the amount of the dye in the permeation liquid composition is such that there is no risk of protrusion. A clear defect-indicating pattern can be formed by the liquid, and finer flaws (specifically, in the case of a dye penetrant, a flaw depth of about 20
It is a technical issue to provide an penetrant liquid capable of reliably detecting a flaw depth of up to μm, and a flaw depth of about 3 μm in the case of a fluorescent penetrant liquid.

[0018]

The above technical problems can be achieved by the present invention as follows. That is, the present invention comprises 5 to 10% by weight of a visible dye or a fluorescent dye, 10 to 40% by weight of a base solvent consisting of a high-boiling point organic solvent having a boiling point of 190 ° C. or higher to dissolve the dye, and a boiling point of 110 to be compatible with the base solvent. ℃
30 to 85% by weight of a diluting solvent comprising the following volatile organic solvent is blended, and during penetration treatment, 50 to 80% by weight of the diluting solvent blended is self-concentrated by evaporation. It is a highly sensitive penetrant used in the penetrant testing method.

The constitution of the present invention will be described in more detail. First, as the visible dye and the fluorescent dye in the present invention, those used in the penetrant used in the penetrant flaw detection test method may be used. The former is Sudan Red 462 (BASF).
And Rhodamine B (Sumitomo Chemical Co., Ltd.) are preferred, and the latter are Fluorol 7GA (GAF) and Blancopho.
r AW (GAF) is preferred.

The blending ratio of each of the above dyes is 5 to 10% by weight, more preferably 6 to 8% by weight in the case of any dye.
Range. If it is less than 5% by weight, it is difficult to obtain the required high detection sensitivity, and if it exceeds 10% by weight, no remarkable improvement in the detection sensitivity is observed. Therefore, practically, the compounding amount up to 10% by weight is sufficient.

When each of the above visible dyes is blended, it becomes a dyeing penetrant, and when each of the above fluorescent dyes is blended, it becomes a fluorescent penetrant.

Next, a boiling point of 190 ° C. at which each of the above dyes is dissolved
As the base solvent composed of the above high boiling point organic solvent, tricresyl phosphate (TC) commercially available as a plasticizer is used.
P: boiling point 420 ° C.), di-2-ethylhexyl phthalate (DOP: boiling point 370 ° C.) and dibutyl phthalate (DB
P: boiling point 335 ° C) or polyoxyethylene alkyl ether commercially available as a surfactant (boiling point about 300 ° C)
The above) and polyoxyethylene alkylallyl ether (boiling point of about 300 ° C. or higher) are preferable, and further commercially available diethylene glycol monobutyl ether (boiling point 230 ° C.) and ethylene glycol monobutyl ether acetate (boiling point: 230 ° C.) which are used as stabilizers for paints. Boiling point 191.5
C.) can also be used suitably. In addition, these can mix 1 or 2 or more.

The mixing ratio of each of the above base solvents is 10 to 40.
It is in the range of% by weight. If the amount is less than 10% by weight, it is difficult to completely dissolve each of the above dyes, and the dye may break out during use (during the permeation treatment).
With the above blending, the above dyes are completely dissolved and do not break off during use (during the permeation treatment). The upper limit of 40% by weight is determined from the relationship with the blending ratio of the diluent solvent.

Next, the boiling point 1 which is compatible with each of the above base solvents
Diluents consisting of volatile organic solvents below 10 ° C include toluene (boiling point 110 ° C), ethanol (boiling point 7
8.3 ° C.), methanol (boiling point 65 ° C.) and acetone (boiling point 56.3 ° C.) are preferred, but isopropyl alcohol, methylene chloride, etc. can also be used.

The mixing ratio of each of the above diluent solvents is 30 to 85% by weight, more preferably 50 to 70% by weight. If it is less than 30% by weight, 50% by weight or more of the amount blended during use (during the permeation treatment) is difficult to evaporate. The upper limit of 85% by weight is determined from the relationship with the blending ratio of the base solvent.

The high-sensitivity penetrant liquid (hereinafter also referred to as "the product of the present invention") used in the penetrant flaw detection test method according to the present invention has the formulation as described above, but its preparation is easy, and the required materials are Each of them may be mixed and stirred so as to have the above blending ratio.

The method of using the prepared product of the present invention is no different from the commercially available various penetrant liquids used in the conventional penetrant flaw detection test methods, and the product of the present invention is appropriately applied to the surface of the inspection object by brushing or the like. It is adhered by means and is used for a certain time (usually 5
Allow 15 minutes) to perform "penetration treatment" to allow the product of the present invention to penetrate into the scratch, and then remove the excess product of the present invention remaining on the surface of the inspection object without penetrating into the scratch. After performing "treatment", a thin layer of white inorganic fine powder is applied to the surface of the inspection object by applying a commercial developer (white inorganic fine powder such as magnesium carbonate or calcium carbonate) used in the penetrant flaw detection test method. After performing the "development process" in which the defect-indicating pattern is revealed by sucking the product of the present invention that has been formed and penetrates into the scratches by the thin layer to the surface of the thin layer, the surface of the inspection object is observed. The presence / position of the flaw can be detected by the defect design pattern.

The above-mentioned "cleaning treatment" may be carried out by a conventional method as shown in Examples below, using a commercially available water-based cleaning agent or a commercially available solvent-based cleaning agent used in the penetrant flaw detection test method.

When observing the above defect indicating pattern, in the case of the product of the present invention containing a visible dye (dye penetrant liquid), the product of the present invention containing a fluorescent dye (fluorescent penetrant liquid under white light). In the case of (1), it may be performed visually under an ultraviolet lamp.

[0030]

[Function] The product of the present invention is used at the time of its use
Time), 50 to 8 of the diluted solvent blended.
Since 0% by weight evaporates and self-concentrates to increase the dye concentration, a clear defect indicating pattern can be obtained even if the amount of the penetrant liquid (product of the present invention) that has penetrated inside the flaw is small. . Even during use (at the time of “penetration treatment”), the base solvent contained in the penetrant liquid (product of the present invention) permeating inside the flaw does not evaporate, and moreover, 20 to 20% of the diluent solvent is used. The dye does not break out because 50% by weight remains.

The blending ratio of each material in the present invention is important, and as long as the above-mentioned specific blending ratio is strictly adhered to, the penetrant flaw detection test method may be carried out using the product of the present invention according to a conventional method (the above-mentioned usage). For example, 5 of the above diluent solvents
It can be guaranteed that 0 to 80% by weight evaporates and self-concentrates to increase the dye concentration, and the dye does not break out.

The inventor has set the working environment temperature to about 15
C. to about 40.degree. C., and the penetration test method was carried out by using the product of the present invention according to the above-mentioned usage, and as a result, in any temperature environment, 50-80% of the diluted solvent blended. It has been confirmed that the weight% evaporates, self-concentrates, the dye concentration rises, and the dye does not break out.
The reason why a substantially constant amount of the diluent solvent evaporates without being affected by changes in the working environment temperature has not yet been elucidated.

[0033]

EXAMPLES The present invention will be described below with reference to Examples and Comparative Examples.

Example 1 (1) Preparation of dyeing penetrant; Sudan Red 462 (BASF
Company: Red dye: 6 wt%, DBP (Mitsubishi Gas Chemical Co., Ltd.): Boiling point 335 ° C .: 3 wt%, Polyoxyethylene alkylallyl ether (Nika Kagaku Co., Ltd.): Boiling point 300 ° C. or higher: 7 wt% %, Ethylene glycol monobutyl ether acetate (Osaka Organic Chemical Co., Ltd.): boiling point 191.5 ° C .... 3% by weight and acetone: boiling point 56.3
C ... 81% by weight.

The above-mentioned respective materials were mixed and stirred at the above-mentioned mixing ratio to prepare the dye penetrant liquid according to the present invention.

(2) Penetrant flaw detection test; JIS Z 234
On the test surface of the B type 3 comparison test piece (scratch depth 20 μm),
After applying 2.00 g of the above dyeing penetrant by brushing and leaving it at room temperature (about 20 ° C.) for 10 minutes, the excess penetrant remaining on the test surface is removed by dry wiping with a paper waste. Further, the test surface is an aqueous cleaning agent for a penetrant testing method (Super Check UR-ST / Aerosol type: Product name:
Wipe it with a paper waste soaked with Mark Tech Co., Ltd. to completely remove it and dry it. Then, on the test surface, the developer for the penetrant inspection test method (Super Check UD-ST / Aerosol type: Product name: Mark TEC Co., Ltd.) to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, it was found that the flaw (depth 2
A clear red defect indicating pattern showing 0 μm) was clearly recognized. The width of a flaw having a depth of 20 µm provided in the above-mentioned comparative test piece is about 1 to 2 µm.

(3) Measurement of evaporation amount: At room temperature (about 20 ° C.), a stainless test piece (100 × 100 mm square) was placed on a commercially available electronic balance (1 scale 0.01 g), and the scale of the balance was 0. After adjusting to 0.00 g, apply 2.00 g of the dye penetrant solution by brush coating on the surface of the stainless test piece in this state, and simultaneously start a stopwatch to observe changes in the scale of the balance and elapsed time. did.

The time at which the weight of the penetrant liquid applied to the stainless test piece reached 1.19 g (elapsed time from the time of application) was 1 minute 10 seconds, and 10 minutes after the time of application. The weight of the penetrating liquid applied to the stainless steel test piece was 0.40 g, and no protrusion of the dye was observed.

The amount of acetone in 2.00 g of the dye penetrant liquid applied to the stainless steel test piece was 1.62 g, and the evaporation amount was 0.81 g when 50% by weight thereof was evaporated. The amount of the dyeing penetrant liquid applied to the stainless test piece is the time when 50% by weight of acetone mixed with 1.19 g minus 0.81 g is evaporated.

Therefore, from the above observation results, it was found that the dyeing penetrant of this example had a time (elapsed time from the time of application) of evaporating 50% by weight of the blended acetone of 1 minute and 10 seconds. After 10 minutes from the time point, it can be seen that 80% by weight of acetone blended at the time of preparation was evaporated.

Since the evaporation amount of acetone in the penetrant flaw detection test of (2) can be estimated to be almost the same as the above amount, the dyeing penetrant solution of the present example was used in the penetrant flaw detection test method at the time of the permeation treatment. It can be said that about 80% by weight of these are evaporated and self-concentrated. In addition, in the penetration test of (2), it was visually confirmed that the color of the coated surface 10 minutes after brush coating was obviously darker than the color of the coated surface immediately after brush coating. are doing.

Comparative Example 1 (1) Preparation of dyeing penetrant; Solvent Red 27 (Orient Oil Red 5B: trade name: Orient Corporation):
Red dye: 2% by weight, DOP (Mitsubishi Gas Chemical Co., Ltd.): Boiling point 370 ° C .... 28% by weight, aromatic hydrocarbon (Solvesso 150: trade name: Exxon Chemical Co., Ltd.): Boiling point 188-210 ° C .... 70% by weight %.

Each of the above materials was mixed and stirred at the above mixing ratio to prepare a comparative dyeing penetrant liquid.

(2) Penetrant flaw detection test: Under the same conditions as in Example 1 except that the penetrant was replaced with the comparative dyeing penetrant.
Penetration testing method was performed, but flaws (depth 20 μm)
It was not possible to clearly recognize a clear red defect designating pattern indicating. When a JIS B 2343 B-shaped comparative test piece (scratch depth: 30 μm) was used, a clear red defect indicating pattern showing a flaw (depth: 30 μm) was clearly recognized.

(3) Measurement of evaporation amount: In the same manner as in Example 1, with respect to the comparative dyeing permeation liquid, the permeation applied to the stainless test piece 10 minutes after the application of 2.00 g was conducted. When the weight of the liquid was measured, it was 1.9.
It was 9 g, and the amount of evaporation was 0.01 g (0.5%).

Example 2 (1) Preparation of dyeing permeate; Sudan Red 462 (BASF
Company): Red dye: ... 8% by weight, polyoxyethylene alkyl allyl ether (Nippon Emulsifier Co., Ltd.): Boiling point 30
0 ° C or higher ... 20% by weight, diethylene glycol monobutyl ether (Nippon Emulsifier Co., Ltd.): boiling point 230 ° C ... 2
0% by weight and ethanol: boiling point 78.3 ° C ... 52% by weight.

The above-mentioned respective materials were mixed and stirred at the above-mentioned mixing ratio to prepare the dye penetrant liquid according to the present invention.

(2) Penetrant flaw detection test: The same dyed penetrant solution 2.0 was applied to the test surface of the same test piece as in Example 1 by brushing.
After applying 0 g and leaving it at room temperature (about 25 ° C.) for 10 minutes, the excess penetrant remaining on the test surface is removed by dry wiping with a paper waste, and the test surface is subjected to a penetrant flaw detection test method. Wipe with a paper waste soaked with a water-based cleaning agent (Super Check AS-ST / Aerosol type: trade name: Mark Tech Co., Ltd.) to completely remove it and dry it. A developer (Super Check UD-ST / aerosol type: trade name: Marktec Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, a clear red defect indicating pattern showing flaws (depth: 20 μm) was clearly recognized.

(3) Measurement of evaporation amount: At room temperature (about 25 ° C.), a stainless steel test piece (100 × 100 mm square) was placed on a commercially available electronic balance (1 scale 0.01 g), and the scale of the balance was 0. After adjusting to 0.00 g, apply 2.00 g of the dye penetrant solution by brush coating on the surface of the stainless test piece in this state, and simultaneously start a stopwatch to observe changes in the scale of the balance and elapsed time. did.

The time at which the weight of the penetrant liquid applied to the stainless steel test piece reached 1.48 g (elapsed time from the time of application) was 7 minutes and 55 seconds, and 10 minutes after the time of application. The weight of the penetrant liquid applied to the stainless steel test piece was 0.96 g, and no protrusion of the dye was observed.

The amount of ethanol in 2.00 g of the dye penetrant solution applied to the stainless test piece was 1.04 g,
If 50% by weight of it evaporates, the amount of evaporation is 0.52 g. Therefore, 1.50 g of 2.00 g minus 0.52 g is blended with 1.48 g of ethanol. It is the amount of the dye penetrant liquid applied.

Therefore, from the above observation results, it was found that the dyeing penetrant of this example had a time (elapsed time from the time of application) of evaporating 50% by weight of the compounded ethanol of 7 minutes 55 seconds. After 10 minutes from the time point, it can be seen that 52% by weight of ethanol blended at the time of preparation was evaporated.

Since the evaporation amount of ethanol in the penetrant testing of (2) can be estimated to be almost the same as the above amount, the dyed penetrant liquid of the present example was prepared by the penetrant testing method in the penetrating treatment method. It can be said that about 52% by weight of this is evaporated and self-concentrated. In addition, in the penetration test of (2), it was visually confirmed that the color of the coated surface 10 minutes after brush coating was obviously darker than the color of the coated surface immediately after brush coating. are doing.

Comparative Example 2 (1) Preparation of dyeing penetrant liquid: Solvent Red 27 (Orient Oil Red 5B: trade name: Orient Corporation):
Red dye: ... 2% by weight, DOP (Sekisui Chemical Co., Ltd.):
Boiling point 370 ° C .... 8% by weight, polyoxyethylene alkyl ether (Japan Surfactant Co., Ltd.): Boiling point 30
0 ° C or higher ... 20% by weight, aromatic hydrocarbon (Solvesso 1
50: Product name: Exxon Chemical Co., Ltd.): Boiling point 188-
210 ° C .... 30% by weight, aliphatic hydrocarbon (No. O solvent L: trade name: Nippon Oil Co., Ltd.): boiling point 182-21
2 ° C ... 40% by weight.

The above materials were mixed and agitated in the above mixing ratio to prepare a comparative dyeing penetrant liquid.

(2) Penetrant flaw detection test: Under the same conditions as in Example 2 except that the penetrant was replaced with the comparative dyeing penetrant.
Penetration testing method was performed, but flaws (depth 20 μm)
It was not possible to clearly recognize a clear red defect designating pattern indicating. When a JIS B 2343 B-shaped comparative test piece (scratch depth: 30 μm) was used, a clear red defect indicating pattern showing a flaw (depth: 30 μm) was clearly recognized.

(3) Measurement of evaporation amount: In the same manner as in Example 2, with respect to the comparative dyeing permeation liquid, permeation applied to the stainless test piece 10 minutes after the application of 2.00 g When the weight of the liquid was measured, it was 1.9.
It was 8 g, and the amount of evaporation was 0.02 g (1.0%).

Example 3 (1) Preparation of dyeing penetrant liquid: Rhodamine B (Sumitomo Chemical Co., Ltd.): Red dye: 6% by weight, polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd.): Boiling point 300
℃ or more ... 20% by weight, ethylene glycol monobutyl ether acetate (Nippon Emulsifier Co., Ltd.): boiling point 192
C .... 14% by weight and methanol: Boiling point 65.degree. C .... 60% by weight.

The above materials were mixed and agitated at the above mixing ratio to prepare a dyeing penetrant liquid according to the present invention.

(2) Penetrant flaw detection test: The same dyeing penetrant solution 2.0 was applied by brush coating on the test surface of the same test piece as in Example 1.
After applying 0 g and leaving it at room temperature (about 24 ° C.) for 10 minutes, an aqueous cleaning agent for a penetrant testing method (Super Check AS-ST / Aerosol type: trade name: Marktec Co., Ltd.) is applied to the test surface. After spraying and then wiping with a paper waste to completely remove the excess penetrant remaining on the test surface and drying, the developer for the penetrant inspection test method (Super Check UD-ST / Aerosol type: Brand name: Mark Tech Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, a clear red defect indicating pattern showing flaws (depth: 20 μm) was clearly recognized.

(3) Measurement of evaporation amount: At room temperature (about 24 ° C.), a stainless steel test piece (100 × 100 mm square) was placed on a commercially available electronic balance (1 scale 0.01 g), and the scale of the balance was 0. After adjusting to 0.00 g, apply 2.00 g of the dye penetrant solution by brush coating on the surface of the stainless test piece in this state, and simultaneously start a stopwatch to observe changes in the scale of the balance and elapsed time. did.

The time at which the weight of the penetrant liquid applied to the stainless steel test piece reached 1.40 g (elapsed time from the time of application) was 5 minutes and 45 seconds, and 10 minutes after the time of application. The weight of the penetrating liquid applied to the stainless test piece of No. 2 was 0.80 g, and no protrusion of the dye was observed.

The amount of methanol in 2.00 g of the dye penetrant solution applied to the stainless test piece was 1.20 g,
If 50% by weight of it evaporates, the amount of evaporation is 0.60 g. Therefore, 1.40 g of 2.00 g minus 0.60 g is blended with 1.40 g of methanol. It is the amount of the dye penetrant liquid applied.

Therefore, from the above observation results, in the dyeing penetrant liquid of the present example, the time for evaporating 50% by weight of the blended methanol (elapsed time from the application time) was 5 minutes 45 seconds, and After 10 minutes from the time point, it can be seen that 60% by weight of the methanol compounded at the time of preparation was evaporated.

Since the evaporation amount of methanol in the penetrant flaw detection test of (2) can be estimated to be almost the same as the above, the dyed penetrant liquid of this example contained the amount of methanol blended at the time of preparation in the permeation treatment in the penetrant flaw test method. It can be said that about 60% by weight of these are evaporated and self-concentrated. In addition, in the penetration test of (2), it was visually confirmed that the color of the coated surface 10 minutes after brush coating was obviously darker than the color of the coated surface immediately after brush coating. are doing.

Comparative Example 3 (1) Preparation of dyeing penetrant: The comparative dyeing penetrant prepared in Comparative Example 2 was used.

(2) Penetrant flaw detection test: Under the same conditions as in Example 3, except that the penetrant was replaced with the comparative dyeing penetrant.
Penetration testing method was performed, but flaws (depth 20 μm)
It was not possible to clearly recognize a clear red defect designating pattern indicating. When a JIS B 2343 B-shaped comparative test piece (scratch depth: 30 μm) was used, a clear red defect indicating pattern showing a flaw (depth: 30 μm) was clearly recognized.

Example 4 (1) Preparation of fluorescent penetrant; Blancophor AW (GAF
Company: Fluorescent dye: 3% by weight, Fluorol 7GA (GAF)
(Company): Fluorescent dye: 5 wt%, TCP (Hodogaya Chemical Co., Ltd.): Boiling point 420 ° C .: 22 wt% and toluene: Boiling point 110 ° C .: 70 wt%.

The above materials were mixed and stirred at the above mixing ratio to prepare the dye penetrant liquid according to the present invention.

(2) Penetrant flaw detection test; taper plating test panel type II 00-50M contrast test piece (scratch depth 0
To 50 μm: Mark Tech Co., Ltd. manufacture and sale)
After applying 2.00 g of the above-mentioned fluorescent penetrant to the test surface by brushing and leaving it at room temperature (about 27 ° C) for 10 minutes, the excess penetrant remaining on the test surface is wiped dry with a paper waste. Then, the test surface was wiped with a paper waste soaked with a solvent-based cleaning agent for a penetrant testing method (Super Check UR-II / Aerosol type: trade name: Marktec Co., Ltd.). After that, an ultraviolet flaw detection lamp (Super Light C-10A ・ III: product name:
Mark Tech Co., Ltd.) to observe the presence or absence of afterglow, wipe the test surface with a paper waste soaked with the above cleaning agent until no afterglow is observed, and then test the test surface with a penetrant flaw detection method. Developer (Super Glow DN-600
S. aerosol type: trade name: Mark Tech Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under irradiation of the ultraviolet flaw detection lamp, flaws up to a depth of 3 μm of the test piece could be clearly detected by a clear fluorescent defect indicating pattern. In addition, the flaw depths 0 to 5 provided in the above-mentioned comparative test piece
The width of a 0 μm flaw is about 1/10 to 1/20 of the depth.

(3) Measurement of evaporation amount: At room temperature (about 27 ° C.), a stainless steel test piece (100 × 100 mm square) was placed on a commercially available electronic balance (scale: 0.01 g), and the scale of the balance was set to 0. After adjusting to 0.00 g, apply 2.00 g of the fluorescent penetrant to the surface of the stainless test piece by brushing in this state, and simultaneously start a stopwatch to observe changes in the scale of the balance and elapsed time. did.

The time at which the weight of the penetrant liquid applied to the stainless steel test piece reached 1.30 g (elapsed time from the time of application) was 6 minutes and 50 seconds, and 10 minutes after the time of application. The weight of the penetrating liquid applied to the stainless test piece of No. 2 was 0.70 g, and no protrusion of the dye was observed.

The amount of toluene in 2.00 g of the fluorescent penetrant applied to the stainless steel test piece is 1.40 g, and if 50% by weight thereof evaporates, the amount of evaporation is 0.70 g. 1.30 g minus 0.70 g is the amount of the fluorescent penetrant applied to the stainless steel test piece at the time when 50% by weight of the blended toluene is evaporated.

Therefore, from the above observation results, it was found that the fluorescent penetrant of this example had a time (elapsed time from the time of application) of evaporating 50% by weight of the blended toluene of 6 minutes and 50 seconds. After 10 minutes from the time point, it can be seen that 65% by weight of toluene blended at the time of preparation was evaporated.

Since the evaporation amount of toluene in the penetrant testing of (2) can be estimated to be almost the same as the above amount, the fluorescent penetrant of the present example was prepared with the penetrating treatment in the penetrant testing method, and the amount of toluene blended at the time of preparation was adjusted. It can be said that about 65% by weight of these are evaporated and self-concentrated.

Comparative Example 4 (1) Preparation of fluorescent penetrant; Blancophor AW (GAF
Company): Fluorescent dye: 1.5% by weight, Fluorol 7GA (GA
Company F): Fluorescent dye: 3% by weight, DOP (Mitsubishi Gas Chemical Co., Ltd.): Boiling point 370 ° C .: 28% by weight, aromatic hydrocarbon (Solvesso 150: trade name: Exxon Chemical Co., Ltd.): Boiling point 188-210 ° C ... 67.5% by weight.

The above-mentioned materials were mixed and stirred at the above-mentioned mixing ratio to prepare a comparative fluorescent penetrant liquid.

(2) Penetrant flaw detection test: Under the same conditions as in Example 4, except that the penetrant was replaced with the comparative fluorescent penetrant.
When the penetrant testing method was performed, the depth of the test piece was 7μ
It was the limit that m flaws could be clearly detected by the clear fluorescent defect indicating pattern.

(3) Measurement of evaporation amount: In the same manner as in Example 4, with respect to the comparative fluorescent permeation liquid, the permeation applied to the stainless test piece 10 minutes after the application of 2.00 g was conducted. When the weight of the liquid was measured, it was 1.9.
It was 9 g, and the amount of evaporation was 0.01 g (0.5%).

Example 5 (1) Preparation of fluorescent penetrant; Blancophor AW (GAF
Company): Fluorescent dye: 2% by weight, Fluorol 7GA (GAF)
Company): Fluorescent dye: 4% by weight, DOP (Dahachi Chemical Co., Ltd.): Boiling point 370 ° C .: 5% by weight, polyoxyethylene alkylallyl ether (Nippon Emulsifier Co., Ltd.): Boiling point 300 ° C. or higher: 24% by weight , Diethylene glycol monobutyl ether (Japan Emulsifier Co., Ltd.): Boiling point 230 ° C
And ethanol: boiling point 78.3 ° C .... 55% by weight.

Each of the above materials was mixed and stirred at the above mixing ratio to prepare the fluorescent penetrant liquid according to the present invention.

(2) Penetrant flaw detection test; the same fluorescent penetrant as described in Example 4 was applied to the test surface of the fluorescent test solution by applying a brush to the test surface of 2.0.
After applying 0 g and leaving it at room temperature (about 27 ° C.) for 10 minutes, an aqueous cleaning agent for a penetrant testing method (Super Check AS-ST / Aerosol type: Product name: Marktec Co., Ltd.) is applied to the test surface. After spraying and then wiping with a paper waste to remove excess penetrant remaining on the test surface, an ultraviolet flaw detection lamp (Super Light C-
10A · III: Product name: Marktec Co., Ltd. was irradiated to confirm that there was no afterglow, and then the test surface was developed with a developer for a penetration flaw detection test method (Super Glow DN-600S ·
Aerosol type: trade name: Mark Tech Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under irradiation of the ultraviolet flaw detection lamp, flaws up to a depth of 3 μm of the test piece could be clearly detected by a clear fluorescent defect indicating pattern.

(3) Measurement of evaporation amount: At room temperature (about 27 ° C.), a stainless steel test piece (100 × 100 mm square) was placed on a commercially available electronic balance (1 scale 0.01 g), and the scale of the balance was 0. After adjusting to 0.00 g, apply 2.00 g of the fluorescent penetrant to the surface of the stainless test piece by brushing in this state, and simultaneously start a stopwatch to observe changes in the scale of the balance and elapsed time. did.

The time at which the weight of the penetrant liquid applied to the stainless steel test piece reached 1.45 g (elapsed time from the time of application) was 7 minutes and 55 seconds, and 10 minutes after the time of application. The weight of the penetrating liquid applied to the stainless steel test piece was 0.90 g, and no protrusion of the dye was observed.

The amount of ethanol in 2.00 g of the fluorescent penetrant applied to the stainless test piece was 1.10 g,
If 50% by weight of it evaporates, the amount of evaporation is 0.55 g. Therefore, 1.50 g of 2.00 g minus 0.55 g is blended with 1.45 g of ethanol. It is the amount of the fluorescent penetrant applied.

Therefore, from the above observation results, it was found that the fluorescent penetrant of this example had a time (elapsed time from the application time) of evaporating 50% by weight of the compounded ethanol of 7 minutes 55 seconds. After 10 minutes from the time point, it can be seen that 55% by weight of ethanol blended at the time of preparation was evaporated.

Since the evaporation amount of ethanol in the penetrant flaw detection test of (2) can be estimated to be almost the same as the above, the fluorescent penetrant of the present example, the amount of ethanol blended at the time of preparation during the permeation treatment in the penetrant flaw test method. It can be said that about 55% by weight of these are evaporated and self-concentrated.

Comparative Example 5 (1) Preparation of fluorescent penetrant; Blancophor AW (GAF
Company): Fluorescent dye: 1.5% by weight, Fluorol 7GA (GA
Company F): Fluorescent dye: 3% by weight, DOP (Sekisui Chemical Co., Ltd.): Boiling point 370 ° C .: 5% by weight, Polyoxyethylene alkylallyl ether (Nippon Surfactant Co., Ltd.): Boiling point 300 ° C. or higher: 20% by weight, Diethylene glycol monobutyl ether (Nippon Emulsifier Co., Ltd.): boiling point 230 ° C .... 10.5% by weight, aromatic hydrocarbon (Solvesso 150: trade name: Exxon Chemical Co., Ltd.): boiling point 1
88 to 210 ° C .... 30% by weight, aliphatic hydrocarbon (No. O solvent L: trade name: Nippon Oil Co., Ltd.): boiling point 182
~ 212 ° C ... 30% by weight.

Each of the above materials was mixed and stirred in the above mixing ratio to prepare a comparative fluorescent penetrant liquid.

(2) Penetrant flaw detection test: under the same conditions as in Example 5 except that the penetrant was replaced with the comparative fluorescent penetrant.
When the penetrant testing method was performed, the depth of the test piece was 7μ
It was the limit that m flaws could be clearly detected by the clear fluorescent defect indicating pattern.

(3) Measurement of evaporation amount: In the same manner as in Example 5, with respect to the comparative fluorescent permeation liquid, the permeation applied to the stainless test piece 10 minutes after the application of 2.00 g When the weight of the liquid is measured, it is 2.0
It was 0 g, and there was no change, and the evaporation amount was 0.

[0092]

The product of the present invention, when used (at the time of permeation treatment),
Even if the amount penetrated inside the flaw is small, a clear defect indicating pattern can be obtained, and the conventional penetrant liquid proposed for high sensitivity (the penetrant liquid formulation shown as a comparative example is , All of which are recommended for high sensitivity), it is possible to detect extremely fine flaws, which was not possible with the dye, and the dye in the composition is not only stored but also used (during permeation treatment) during storage. It doesn't break out.

Therefore, it can be said that the present invention greatly contributes to the field (for example, the field of automobile parts and the field of nuclear reactor equipment) in which it is required to detect extremely fine flaws.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 11, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0036

[Correction method] Change

[Correction content]

(2) Penetrant flaw detection test; JIS Z 234
On the test surface of the B-shaped comparative test piece of 3 (scratch depth 20 μm),
After applying 2.00 g of the above dyeing penetrant by brushing and leaving it at room temperature (about 20 ° C.) for 10 minutes, the excess penetrant remaining on the test surface is removed by dry wiping with a paper waste. Further, the test surface was wiped with a paper waste soaked with a water-based cleaning agent for a penetrant testing method (Super Check AS-T / Aerosol type: trade name: Marktec Co., Ltd.) to completely remove it and dry it. After that, a developer for a penetrant inspection method (Super Check UD-ST / Aerosol type: trade name: Marktec Co., Ltd.) was sprayed on the test surface to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, it was found that the flaw (depth 20
A clear red defect indicating pattern indicating (μm) was clearly recognized. It should be noted that the flaw depth of 2 provided on the above-mentioned comparative test piece
The width of a 0 μm flaw is about 1 to 2 μm.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0048

[Correction method] Change

[Correction content]

(2) Penetrant flaw detection test: The same dyed penetrant solution 2.0 was applied to the test surface of the same test piece as in Example 1 by brushing.
After applying 0 g and leaving it at room temperature (about 25 ° C.) for 10 minutes, the excess penetrant remaining on the test surface is removed by dry wiping with a paper waste, and the test surface is subjected to a penetrant flaw detection test method. Wipe with a paper waste soaked with a water-based cleaning agent (Super Check AS- T / Aerosol type: trade name: Mark Tech Co., Ltd.) to completely remove it and dry it. A developer (Super Check UD-ST / aerosol type: trade name: Marktec Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, a clear red defect indicating pattern showing flaws (depth 20 μm) was clearly recognized.

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0060

[Correction method] Change

[Correction content]

(2) Penetrant flaw detection test: The same dyeing penetrant solution 2.0 was applied by brush coating on the test surface of the same test piece as in Example 1.
After applying 0 g and leaving it at room temperature (about 24 ° C.) for 10 minutes, an aqueous cleaning agent for a penetrant testing method (Super Check AS- T / Aerosol type: product name: Marktec Co., Ltd.) is applied to the test surface. After spraying and then wiping with a paper waste to completely remove the excess penetrant remaining on the test surface and drying, the developer for the penetrant inspection test method (Super Check UD-ST / Aerosol type: Brand name: Mark Tech Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under white light, a clear red defect indicating pattern showing a flaw (depth 20 μm) was clearly recognized.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0082

[Correction method] Change

[Correction content]

(2) Penetrant flaw detection test; the same fluorescent penetrant as described in Example 4 was applied to the test surface of the fluorescent test solution by applying a brush to the test surface of 2.0.
After applying 0 g and leaving it at room temperature (about 27 ° C.) for 10 minutes, a water-based cleaning agent for the penetrant testing method (Super Check AS- T / Aerosol type: trade name: Marktec Co., Ltd.) is applied to the test surface. After spraying and then wiping with a paper waste to remove excess penetrant remaining on the test surface, the test surface was exposed to an ultraviolet flaw detection lamp (Super Light C-1) in a dark room.
0A · III: Product name: Mark Tech Co., Ltd., and after confirming that there is no afterglow, the test surface is subjected to a penetrant testing method developer (Super Glow DN-600S ·
Aerosol type: trade name: Mark Tech Co., Ltd.) was sprayed to form a thin layer of white inorganic fine powder. When the surface of this thin layer was visually observed under irradiation of the ultraviolet flaw detection lamp, flaws up to a depth of 3 μm of the test piece could be clearly detected by a clear fluorescent defect indicating pattern.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kazuhiko Ayuha 641 Funakura-cho, Yokosuka City, Kanagawa Mark Tech Co., Ltd. Kurihama Factory

Claims (3)

[Claims] 1. A base solvent comprising 5 to 10% by weight of a visible dye or a fluorescent dye and a high-boiling organic solvent having a boiling point of 190 ° C. or higher for dissolving the dye, and a boiling point of 110 ° C. compatible with the base solvent. 30 to 85% by weight of a diluting solvent consisting of the following volatile organic solvents is mixed, and during the permeation treatment,
A highly sensitive penetrant liquid for use in a penetrant flaw detection test method, characterized in that 50 to 80% by weight of the diluted solvent contained therein is evaporated and self-concentrates. 2. A base solvent selected from tricresyl phosphate, di-2-ethylhexyl phthalate, dibutyl phthalate, polyoxyethylene alkyl ether, polyoxyethylene alkyl allyl ether, diethylene glycol monobutyl ether and ethylene glycol monobutyl ether acetate. Or two or more.
High-sensitivity penetrant used in the penetrant flaw detection test method described. 3. The highly sensitive penetrant liquid used in the penetrant flaw detection test method according to claim 1, wherein the diluting solvent is any one of acetone, ethanol, methanol and toluene.