JP2869703B2 - Highly sensitive penetrant for penetrant testing - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an infiltration solution used in a penetrant testing method, which has an extremely fine depth of 20 .mu.m when a visible dye is incorporated and a depth of 3 .mu.m when a fluorescent dye is incorporated. Provided is a highly sensitive permeate that can reliably detect even a surface opening defect.

[0002]

2. Description of the Related Art Penetration inspection methods are based on surface defects such as fine cracks and pinholes (hereinafter referred to as "flaws") on the surface of various members (for example, automobile members) and various devices (for example, reactor equipment). ) Is widely used to detect
It is standardized in “JIS Z 2343-1992” (hereinafter referred to as “JIS standard”).

[0003] As seen in the JIS standard, a dye penetrant and a fluorescent penetrant are used in the penetrant detection test method, and both are commercially available.

[0004] As is well known, a dye permeate is a liquid having a high permeability in which a visible dye (usually a red dye such as Oil Red 5BN: Shirad Chemical Co., Ltd. or Sudan Red 462: BASF) is dissolved in an organic solvent. The fluorescent penetrant is a fluorescent dye (a dye that emits yellow-green fluorescence under an ultraviolet lamp, such as a fluorescent bright varnish agent 6).
8: Nippon Kayaku Co., Ltd. or Fluorol 7GA: GAF) is a highly permeable liquid that is dissolved in an organic solvent.

[0005] In the case of any of the penetrants, "Non-Destructive Inspection Handbook edited by the Japan Non-Destructive Inspection Association [New Edition]
-720 pages-Nikkan Kogyo Shimbun-First edition published on April 28, 1978-"... the solvent of the permeation liquid is required to have not only the ability to dissolve dye but also the permeability to defective parts. The formula is assembled by using several kinds of solvents and balancing the properties of each component.
Solvents are broadly divided into basic ones and those that work diluently. In basic solvents (applicant's note: called "base solvent" by those skilled in the art), it is essential that the dye be dissolved well and the fluorescent color and the hue of the colored dye be clearly exhibited. In addition, it is required that it has a high boiling point, does not easily volatilize, has no corrosiveness to metals, and has no or little odor. Generally, high-boiling esters, high-boiling alcohols, polyhydric alcohol derivatives and the like are used from the above viewpoints. The diluent solvent not only controls viscosity and fluidity but also reduces material costs. The requirements for this are that it is well compatible with the basic solvent, has no corrosiveness to metals, has no unpleasant odor, and has low toxicity. The permeate may be used in an open tank or withdrawn from a closed container each time it is used, and the volatility of the diluent is changed accordingly. In any case, a chain or cyclic hydrocarbon is generally used. The balance between the basic solvent and the diluent solvent determines the properties of the permeated solution (viscosity, surface tension, wettability, etc.) and determines the quality of the performance. ... ", two types of organic solvents, a base solvent and a diluent solvent, are combined and compounded.

[0006] Japanese Patent Laid-Open Publication No. 3-175345 discloses
Examples include a combination example of a combination of a base solvent and a diluting solvent. "... The solvent-removable dyeing and permeating solution uses a red oil-soluble dye (for example, Oil Red 5BN: manufactured by Shirad Chemical Co., Ltd.) as a dye, 1 to 5 parts by weight of the dye is mixed with 20 to 50 parts by weight of a base solvent composed of a plasticizer (for example, DOP: dioctyl phthalate) or vegetable oil (for example, soybean oil), and xylene, alkylbenzene, trichloroethane, trifluorotrichloroethane, carbitol, It is a highly permeable liquid dissolved in 50 to 80 parts by weight of a diluting solvent comprising 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 (Trade name: Marktec Co., Ltd.) In addition, the solvent-removable fluorescent penetrant is a fluorescent dye that develops yellow-green under an ultraviolet lamp 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 case of the solvent-removable dyeing and permeating solution, and has a high permeability. A typical commercially available product is Super Glow OD-6000 (trade name: manufactured by Mark Tech Co., Ltd.). ... ".

[0007] Japanese Patent Publication No. 34-3948 discloses a solid organic fluorescent material mainly composed of one of ... naphthylene oxide, tetracene, dihydrotetracene and pyrene or a mixture thereof. Boiling point solvent: for example, benzene,
Dissolved in toluene or the like at a concentration of about 0.1% or more ... "is disclosed, but as far as the present inventor knows,
This fluorescent penetrant has not been put to practical use, and the dye penetrants and the fluorescent penetrants that are currently in practical use are both compounds prepared by combining the above-mentioned two organic solvents, the base solvent and the diluting solvent. .

[0008]

The limit of flaw detection when a penetrant testing method is carried out using a currently used (commercially available) dyeing penetrant and a fluorescent penetrant is described in "Magazines / Non-destructive Inspection. Vol. 44, No. 2, pp. 71-73, Japan Non-Destructive Inspection Association, February 1, 1995, "Surface Flaw Detection Limits in Magnetic Particle Testing and Penetrant Testing, Kazuo Miyagawa (Former Professor at Nihon University) "... (1) Preface In the penetrant inspection (hereinafter referred to as PT) ... nickel-chromium plating crack specimen (hereinafter referred to as Ni-CrTP) whose volume changes most quantitatively, State what you know from the test results you have done so far.
It should be noted that the TP has some operational problems that affect detection performance, but it is assumed that all of these have been fully operated and the best tests have been performed. ... (2) In the case of dye permeate a. In the case of solvent removal, the detection limit is flaw depth 3
0 μm. 20 μm Ni-CrT. P. In some cases, a very thin linear indicating pattern may appear, but it is not an indicating 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 detector. Depending on the type of dye to be used, the concentration, the volatility of the solvent, etc., the indication pattern may show slight shading, but the detection limit itself is up to 30 μm. ... d. In the case of washing with water, the detection limit is 50 μm for flaw depth. (3) In the case of fluorescent penetrant a. Under the best conditions, the detection limit is a flaw depth of 10 μm. ... b. With the non-development method, 10 μm cannot be detected. … ”Has been reported.

[0009] In Japanese Patent Publication No. 34-9748, the use of the fluorescent penetrant disclosed in the Japanese Patent Publication No. 34-9748 states that "... 5 µm or less flaws can be found with higher sensitivity and, unlike conventional ones, It is possible to know the shape of the crack without enlargement as it is .... Using the developing operation together does not matter at all.In this case, it is possible to clearly know even a very shallow crack close to, for example, 1 to 2 .mu.m. "...", but here, "5μ",
The numerical value “1-2 μ” can be estimated to indicate not the depth of the flaw but the width of the flaw. This is because the fluorescent penetrant does not contain a base solvent and has a flaw depth of 5
This is because it is almost impossible to detect a μm or a flaw depth of 1 to 2 μm.

[0010] As can be seen from the above-mentioned report, one of the factors that the detection limit of the dye penetrant is 30 μm and the detection limit of the fluorescent penetrant is 10 μm is that inside the defect. It can be said that the amount of the penetrating liquid that permeated was small.

[0011] That is, some of the flaws existing on the surface of the test object to which the penetrant inspection method is applied penetrate and some do not penetrate, and the latter is common in general test objects. If the flaws present in the test object are small and do not penetrate through the opening, even if the dyeing penetrant or the fluorescent penetrant is sufficiently adhered to the surface of the test object, the inside of the flaw may be present. The amount of the penetrating liquid that permeates becomes small, because the amount of the permeating liquid that is displaced by the air inside the wound 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 (Boiler-Charle's law), in the case of a small penetrating flaw having a small opening, it is necessary to use a bath. When the bath is turned upside down, a phenomenon similar to the phenomenon that the air inside the bath does not completely replace the warm water occurs, and the air inside the flaw does not completely replace the permeate, so the permeate penetrating inside the flaw Is small.

Needless to say, the technical field of the art is to provide a penetrating liquid which can form a clear defect indicating film with a small amount of penetrating liquid penetrating into the inside of a flaw and which can surely detect finer flaws. R & D is underway as an issue.

[0014] The typical technical means adopted to achieve the above technical problem is to increase the amount of dye in the permeate composition to form a clear defect indication pattern. It is.

However, when the amount of the dye in the composition of the permeate is increased, the problem of dye breakout occurs, and it is impossible to use a permeate in which the dye breaks out during storage.

[0016] Therefore, in the art, by selecting various kinds of dyes, base solvents and diluting solvents and their blending ratios, etc., it is possible to obtain a permeating solution in which the blending amount is increased without the dye being deposited. 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 use a limited dye and increase the amount of the dye without depositing the dye. There is a limit to this, and when using a commercially available permeate, the results are as reported above.

The present invention has been made in view of the above-mentioned situation, and it has been found that, despite the fact that the amount of the dye in the composition of the permeate is such that there is no danger of deposition, a small amount of permeation into the inside of the flaw is achieved. A clear defect indicating pattern can be formed by the liquid, and finer flaws (specifically, in the case of the dyeing penetrating liquid, a flaw depth of about 20
It is an object of the present invention to provide a penetrant which can reliably detect a permeate of up to μm, and in the case of a fluorescent permeate, a flaw depth of about 3 μm).

[0018]

The above technical objects can be achieved by the present invention as described below. That is, the present invention relates to triphosphoric acid, which is a high-boiling organic solvent having a boiling point of 190 ° C. or higher, which dissolves the dye and 6 to 10% by weight of a visible or fluorescent dye
Resyl, di-2-ethylhexyl phthalate, diphthalic acid
Butyl, polyoxyethylene alkyl ether, polio
Xylene ethylene allyl ether, diethylene glycol
Coal monobutyl ether and ethylene glycol mono
One or more selected from butyl ether acetate
Is based solvent 10 to 40 wt% and the base solvent and compatible to the boiling point 110 ° C. or less of volatile organic solvents having upper A
Selected from seton, ethanol, methanol and toluene
It is <br/> a diluting solvent 50-85 wt% consisting of one either formulation that, upon penetration treatment, that 50 to 80% by weight of the dilution solvent is blended to self concentrated by evaporation It is a highly sensitive penetrant used for the characteristic penetrant testing method.

The configuration 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 detection test method may be used, and 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 compounding ratio of each of the above dyes is in the range of 6 to 10 % by weight for any of the dyes. If it is less than 5% by weight, the required high detection sensitivity is hardly obtained, and if it exceeds 10% by weight, no remarkable improvement in the detection sensitivity is observed.
Up to 0% by weight is sufficient.

When each of the above-mentioned visible dyes is blended, a dye permeate is obtained, and when each of the above fluorescent dyes is blended, a fluorescent permeate is obtained.

Next, the above dyes are dissolved at a boiling point of 190 ° C.
As the base solvent composed of the above high boiling 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.)
Above) and polyoxyethylene alkyl allyl ether (boiling point of about 300 ° C. or more) are suitable, and furthermore, commercially available diethylene glycol monobutyl ether (boiling point of 230 ° C.) and ethylene glycol monobutyl ether acetate (boiling point of 230 ° C.) used as a stabilizer for paints and the like are preferable. Boiling point 191.5
° C) can also be suitably used. One or more of these can be blended.

The mixing ratio of each base solvent is 10 to 40.
% 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 be broken out during use (permeation treatment).
With the above compounding, each of the above dyes is completely dissolved and does not break out during use (during permeation treatment). The upper limit of 40% by weight is determined from the relationship with the mixing ratio of the diluting solvent.

Next, a boiling point of 1 which is compatible with each of the above base solvents.
Diluting solvents consisting of volatile organic solvents of 10 ° C. or lower 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.

The mixing ratio of each of the above-mentioned diluting solvents is in the range of 50 to 85 % by weight. If it is less than 30% by weight, 50% by weight or more of the amount blended at the time of use (during the permeation treatment) becomes 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 used in the penetrant testing method according to the present invention (hereinafter, also referred to as "the present invention") has the above-mentioned formulation, but its preparation is easy, and the required materials What is necessary is just to mix and stir each so that it may become the said compounding ratio.

The method of using the prepared product of the present invention is no different from any of various commercially available permeating solutions used in the conventional penetrant testing method, and the product of the present invention is appropriately applied to the surface of a test object by brushing or the like. Means for a certain period of time (usually 5
〜15 minutes) to perform “penetration treatment” in which the product of the present invention penetrates into the inside of the flaw, and then “cleaning” for removing excess product of the present invention remaining on the surface of the inspection object without permeating into the inside of the flaw. Treatment ”, apply a commercially available developer (white inorganic fine powder such as magnesium carbonate and calcium carbonate) used in the penetrant detection test method to the surface of the test object to form a thin layer composed of white inorganic fine powder. After performing the "development process" in which the product of the present invention formed and permeated into the inside of the scratch by the thin layer is drawn out to the surface of the thin layer to reveal a defect indicating pattern, the surface of the inspection object is observed. The presence and position of the flaw can be detected by the defect indicating pattern.

The above-mentioned "cleaning treatment" may be carried out according to a conventional method using a commercially available water-based cleaning agent or a commercially available solvent-based cleaning agent used in the penetrant detection test method, as will be described later in Examples.

When observing the above-mentioned defect indicating pattern, the present invention product (fluorescent infiltration solution) containing a fluorescent dye was used under the white light in the case of the present invention product (dyeing infiltration solution) containing a visible dye. In the case of ()), it may be performed visually under an ultraviolet lamp.

[0030]

The product of the present invention is used at the time of its use (the above-mentioned "penetration treatment").
Time), 50 to 8 of the diluted solvent
Since the dye concentration is increased by self-concentration by evaporating 0% by weight, a clear defect indicating pattern can be obtained even if the amount of the penetrating liquid (the present invention) penetrating into the flaw is small. . At the time of use (at the time of “penetration treatment”), the base solvent contained in the penetrating liquid (the product of the present invention) that has penetrated into the inside of the flaw does not evaporate. The dye does not break out because 50% by weight remains.

The mixing ratio of each material in the present invention is important. As long as the specific mixing ratio is strictly adhered to, the penetration testing method is carried out using the product of the present invention according to a conventional method (the above-mentioned usage method). For example, 5
From 0 to 80% by weight evaporates and self-concentrates, increasing the dye concentration and ensuring that the dye does not break out.

The inventor has set the working environment temperature at about 15
The temperature was changed in the range of about 40 ° C. to about 40 ° C., and as a result of performing the penetrant flaw detection test method using the product of the present invention by the above-mentioned method of use, under any temperature environment, 50 to 80 It has been confirmed that the weight% evaporates and self-concentrates, the dye concentration increases, and the dye does not break out.
The reason why the almost constant amount of the diluting solvent evaporates without being substantially affected by the change in the working environment temperature has not yet been elucidated.

[0033]

The present invention will be described below with reference to examples and comparative examples.

Example 1 (1) Preparation of dye permeate; Sudan Red 462 (BASF
6% by weight, DBP (Mitsubishi Gas Chemical Co., Ltd.): 335 ° C boiling point: 3% by weight, polyoxyethylene alkyl allyl ether (Nichika Chemical Co., Ltd.): 300 ° C or higher boiling point: 7% %, 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.

Each of the above materials was mixed and stirred at the above mixing ratio to prepare a dye permeate according to the present invention.

(2) Penetration test; JIS Z 234
On the test surface of B type contrast test piece (flaw depth 20 μm) of 3,
2.00 g of the above-mentioned dyeing penetrant is applied by brush coating, left at room temperature (about 20 ° C.) for 10 minutes, and excess penetrant remaining on the test surface is removed by dry wiping with a paper waste, Further, the test surface was completely removed by wiping with a paper waste impregnated with a water-based detergent (Super Check AS-T aerosol type: trade name: Marktec Co., Ltd.) for the penetrant testing method, and dried. Then, a developer (Super Check UD-ST, aerosol type: trade name: Marktec Co., Ltd.) was sprayed on the test surface to form a thin layer composed of white inorganic fine powder. When the surface of this thin layer is visually observed under white light, a flaw (depth: 20
μm) was clearly observed. In addition, the flaw depth 2 provided on the comparative test piece was
The width of the 0 μm flaw is about 1-2 μm.

(3) Measurement of evaporation amount: At room temperature (about 20 ° C.), a stainless steel test piece (100 × 100 mm square) was put on a commercially available electronic balance (0.01 g per scale), and the scale of the balance was set to 0. 2.00 g, and in this state, apply 2.00 g of the above-mentioned dyeing permeate by brush coating on the surface of the stainless steel test piece, and at the same time start a stopwatch, and observe the change in the scale of the balance and the elapsed time. did.

The time when the weight of the permeating liquid applied to the stainless steel test piece was 1.19 g (elapsed time from the time of application) was 1 minute and 10 seconds, and the time when 10 minutes had passed from the time of application. The weight of the permeate applied to the stainless steel test piece was 0.40 g, and no dye deposition was observed.

The amount of acetone in 2.00 g of the dye penetrant applied to the stainless steel test piece was 1.62 g, and the evaporation amount was 0.81 g if 50% by weight of the solution was evaporated. 0.81 g minus 1.19 g is the amount of dye permeate applied to the stainless steel test specimen at the time when 50% by weight of the acetone in which the acetone is mixed is evaporated.

Accordingly, from the above observation results, the dyeing infiltration solution of this example has a time (elapsed time from the time of application) of 50% by weight of the mixed acetone of 1 minute and 10 seconds. At the time when 10 minutes have passed from the time, it can be seen that 80% by weight of the acetone mixed at the time of preparation has evaporated.

The amount of acetone evaporated in the penetrant test of (2) can be estimated to be almost the same as the above. Therefore, the dyed penetrant of the present example was prepared by the following method. Can be said to be self-concentrating by evaporating about 80% by weight. In the penetrant detection test (2), it was visually confirmed that the color of the applied surface at 10 minutes after the brush application was clearly darker than the color of the applied surface immediately after the brush application. doing.

Comparative Example 1 (1) Preparation of Dye Infiltration Solution; Solvent Red 27 (Orient Oil Red 5B: trade name: Orient Co., Ltd.):
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 weight %.

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

(2) Penetration test: The same conditions as in Example 1 were used except that the permeate was replaced with the comparative dye permeate.
Penetration testing method was performed, but flaws (depth 20μm)
No clear red defect indicating pattern indicating was clearly recognized. When the test piece was replaced with a JIS Z2343 B type contrast test piece (depth of flaw 30 μm), a clear red defect indicating pattern indicating flaw (depth of 30 μm) was clearly recognized.

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

Example 2 (1) Preparation of dye permeate; Sudan Red 462 (BASF
8% by weight, polyoxyethylene alkyl allyl ether (Nippon Emulsifier Co., Ltd.): boiling point 30
0 ° C or more: 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.

Each of the above materials was mixed and stirred at the above mixing ratio to prepare a dye permeate according to the present invention.

(2) Penetration flaw detection test: The test surface of the same comparison test piece as in Example 1 was brush-coated on the test surface of the dyed penetrant 2.0.
0 g of the solution, left at room temperature (approximately 25 ° C.) for 10 minutes, and then remove the excess permeate remaining on the test surface by dry wiping with a paper rag. A water-based cleaning agent (Super Check AS- T aerosol type: trade name: Marktec Co., Ltd.) is wiped off with a paper waste impregnated, completely removed and dried, and then the test surface is subjected to a penetrant flaw detection test. Developer (Super Check UD-ST aerosol type: trade name: Marktec Co., Ltd.) was sprayed to form a thin layer composed of white inorganic fine powder. When the thin layer surface was visually observed under white light, a clear red defect indicating pattern showing a flaw (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 (0.01 g per scale), and the scale of the balance was set to 0. 2.00 g, and in this state, apply 2.00 g of the above-mentioned dyeing permeate by brush coating on the surface of the stainless steel test piece, and at the same time start a stopwatch, and observe the change in the scale of the balance and the elapsed time. did.

The time when the weight of the permeating liquid applied to the stainless steel test piece became 1.48 g (elapsed time from the time of application) was 7 minutes and 55 seconds. The weight of the permeate applied to the stainless steel test piece was 0.96 g, and no dye deposition was observed.

The amount of ethanol in 2.00 g of the dye permeate applied to the stainless steel test piece was 1.04 g,
When 50% by weight of the ethanol evaporates, the amount of evaporation is 0.52 g. Therefore, when 50% by weight of ethanol containing 1.48 g obtained by subtracting 0.52 g from 2.00 g is evaporated, the stainless steel test piece is evaporated. It is the amount of the dyeing permeate applied.

Therefore, from the above observation results, the dye infiltration solution of this example has a time (elapsed time from the time of application) of 50% by weight of the blended ethanol of 7 minutes and 55 seconds. At the time when 10 minutes have passed from the time, it can be seen that 52% by weight of the ethanol blended at the time of preparation has been evaporated.

Since the evaporation amount of ethanol in the penetrant test of (2) can be estimated to be almost the same as the above, the dyed penetrant of the present example was prepared by mixing the amount of ethanol blended at the time of preparation with the penetrating treatment in the penetrant test method. Can be said to be self-concentrated by evaporating about 52% by weight. In the penetrant detection test (2), it was visually confirmed that the color of the applied surface at 10 minutes after the brush application was clearly darker than the color of the applied surface immediately after the brush application. doing.

Comparative Example 2 (1) Preparation of dye permeate; Solvent Red 27 (Orient Oil Red 5B: trade name: Orient Co., Ltd.):
Red dye: 2% by weight, DOP (Sekisui Chemical Co., Ltd.):
Boiling point: 370 ° C .... 8% by weight, polyoxyethylene alkyl ether (Nippon Surfactant): Boiling point: 30
0 ° C. or more: 20% by weight, aromatic hydrocarbon (Solvesso 1
50: Trade 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 stirred at the above mixing ratio to prepare a comparative dyeing permeate.

(2) Penetration test: Under the same conditions as in Example 2, except that the permeate was replaced with the comparative dye permeate.
Penetration testing method was performed, but flaws (depth 20μm)
No clear red defect indicating pattern indicating was clearly recognized. When the test piece was replaced with a JIS Z2343 B type contrast test piece (depth of flaw 30 μm), a clear red defect indicating pattern indicating flaw (depth of 30 μm) was clearly recognized.

(3) Measurement of Evaporation Amount: In the same manner as in Example 2, the permeation amount applied to the stainless steel test piece at the time point of 10 minutes after the application of 2.00 g was applied to the comparative dye permeate. When the weight of the liquid was measured, it was 1.9.
8 g, and the amount of evaporation was 0.02 g (1.0%).

Example 3 (1) Preparation of dyeing infiltration solution; rhodamine B (Sumitomo Chemical Co., Ltd.): Red dye:... 6% by weight, polyoxyethylene alkyl ether (Daiichi Kogyo Seiyaku Co., Ltd.): boiling point 300
° C or higher: 20% by weight, ethylene glycol monobutyl ether acetate (Nippon Emulsifier Co., Ltd.): boiling point 192
° C 14% by weight and methanol: boiling point 65 ° C 60% by weight.

Each of the above-mentioned materials was mixed and stirred at the above-mentioned mixing ratio to prepare a dyeing permeate according to the present invention.

(2) Penetration flaw detection test: The same test sample as in Example 1 was brush-coated on the test surface with the dyed penetrant 2.0
After applying 0 g and leaving at room temperature (about 24 ° C.) for 10 minutes, a water-based cleaning agent (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 completely remove the residual permeate remaining on the test surface and drying, the developer for the penetrant flaw detection test method (Super Check UD-ST, aerosol type: (Trade name: Marktech Co., Ltd.) was sprayed to form a thin layer composed of white inorganic fine powder. When the thin layer surface was visually observed under white light, a clear red defect indicating pattern showing a flaw (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 (0.01 g per scale), and the scale of the balance was set to 0. 2.00 g, and in this state, apply 2.00 g of the above-mentioned dyeing permeate by brush coating on the surface of the stainless steel test piece, and at the same time start a stopwatch, and observe the change in the scale of the balance and the elapsed time. did.

The time when the weight of the permeating solution 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 the time when 10 minutes passed from the time of application was reached. The weight of the permeate applied to the stainless steel test piece was 0.80 g, and no dye was found to be separated.

The amount of methanol in 2.00 g of the dye permeate applied to the stainless steel test piece was 1.20 g,
When 50% by weight of the methanol evaporates, the amount of evaporation is 0.60 g. Therefore, when 40% by weight of the methanol containing 1.40 g obtained by subtracting 0.60 g from 2.00 g is evaporated, the stainless steel test piece is evaporated. It is the amount of the dyeing permeate applied.

Therefore, from the above observation results, the dyeing infiltration solution of the present example has a time (elapsed time from the time of application) of 50% by weight of the blended methanol of 5 minutes and 45 seconds. At the time when 10 minutes have passed from the time point, it can be seen that 60% by weight of the methanol compounded at the time of preparation has evaporated.

Since the evaporation amount of methanol in the penetrant inspection test of (2) can be estimated to be substantially the same as the above, the dyed penetrant solution of the present example was prepared by using the amount of methanol mixed at the time of preparation during the penetration treatment in the penetrant inspection method. Can be said to be self-concentrated by evaporation of about 60% by weight. In the penetrant detection test (2), it was visually confirmed that the color of the applied surface at 10 minutes after the brush application was clearly darker than the color of the applied surface immediately after the brush application. doing.

Comparative Example 3 (1) Preparation of Dye Penetration Solution: The comparative dye permeate prepared in Comparative Example 2 was used.

(2) Penetration test: Under the same conditions as in Example 3, except that the permeate was replaced with the comparative dye permeate.
Penetration testing method was performed, but flaws (depth 20μm)
No clear red defect indicating pattern indicating was clearly recognized. When the test piece was replaced with a JIS Z2343 B type contrast test piece (depth of flaw 30 μm), a clear red defect indicating pattern indicating flaw (depth of 30 μm) was clearly recognized.

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

The above-mentioned materials were mixed and stirred at the above-mentioned mixing ratio to prepare a dyeing permeate according to the present invention.

(2) Penetration inspection: taper plating test panel type II 00-50M Comparative test piece (flaw depth 0
To 50μm: Mark Tech Co., Ltd. manufacture and sales)
2.00 g of the above-mentioned fluorescent penetrant is applied to the test surface by brushing, left at room temperature (about 27 ° C.) for 10 minutes, and the excess penetrant remaining on the test surface is wiped dry with a paper waste. Further, the test surface was wiped off with a paper waste impregnated with a solvent-based cleaning agent (Super Check UR-II, aerosol type: trade name: Marktech Co., Ltd.) for the penetrant flaw detection test method. Then, in a dark room, the test surface was irradiated with an ultraviolet flaw detector (Superlight C-10A III: Trade name:
Mark Tech Co., Ltd.), observe the presence or absence of afterglow, wipe the test surface with a paper cloth impregnated with the above cleaning agent until afterglow is no longer observed, and then penetrate the test surface with a penetrant flaw detection test method. Developer (Super Glow DN-600)
(S. aerosol type: trade name: Marktec Co., Ltd.) was sprayed to form a thin layer composed of white inorganic fine powder. When the surface of this thin layer was visually observed under the irradiation of the ultraviolet ray inspection lamp, a flaw of the test piece up to a depth of 3 μm was clearly detected by a clear fluorescent defect indicating pattern. The depth of the flaw provided on the comparative test piece was 0 to 5
The width of the 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 (0.01 g per scale), and the scale of the balance was set to 0. 2.00 g, and in this state, apply 2.00 g of the above-mentioned fluorescent penetrant by brush coating on the surface of the stainless steel test piece, and at the same time start the stopwatch, and observe the change in the scale of the balance and the elapsed time. did.

The time when the weight of the permeating 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. The weight of the permeate applied to the stainless steel test piece was 0.70 g, and no dye deposition was observed.

The amount of toluene in 2.00 g of the fluorescent penetrant applied to the stainless steel test piece was 1.40 g, and the evaporation amount was 0.70 g if 50% by weight of the solution was evaporated. At the time when 50% by weight of the toluene containing 1.30 g minus 0.70 g is evaporated, the amount of the fluorescent permeate applied to the stainless steel test piece is obtained.

From the above observation results, it can be seen from the above observation that the fluorescence penetrating solution of this example has a time (elapsed time from the time of application) at which 50% by weight of the incorporated toluene evaporates is 6 minutes and 50 seconds. At the time when 10 minutes have passed from the time, it can be seen that 65% by weight of the toluene blended at the time of preparation has been evaporated.

Since the amount of toluene evaporated in the penetrant inspection test of (2) can be estimated to be almost the same as the above, the fluorescent penetrant of the present example was prepared by using Can be said to be self-concentrated by evaporation of about 65% by weight.

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

Each of the above materials was mixed and stirred at the above mixing ratio to prepare a comparative fluorescence infiltration solution.

(2) Penetration test: Under the same conditions as in Example 4 except that the permeate was replaced with the comparative fluorescent permeate,
When the penetrant testing method was performed, the depth of the test piece was 7μ.
m was at the limit where it could be clearly detected by a clear fluorescent defect indicator pattern.

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

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

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

(2) Penetration flaw detection test: The same test specimen as in Example 4 was coated on the test surface of the test piece with
After applying 0 g and leaving at room temperature (approximately 27 ° C.) for 10 minutes, a water-based cleaning agent (Super Check AS- T aerosol type: trade name: Mark Tech Co., Ltd.) is applied to the test surface. After spraying, and then wiping with a paper waste to remove excess permeate remaining on the test surface, the test surface is exposed to an ultraviolet light (Superlight C-1) in a dark room.
OA / III: Trade name: Marktech Co., Ltd.), and after confirming that there is no afterglow, the test surface developer (Super Glow DN-600S.
(Aerosol type: trade name: Marktec Co., Ltd.) was sprayed to form a thin layer composed of white inorganic fine powder. When the surface of the thin layer was visually observed under the irradiation of the ultraviolet ray inspection lamp, a flaw of the test piece up to a depth of 3 μm was 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 put on a commercially available electronic balance (0.01 g per scale), and the scale of the balance was set to 0. 2.00 g, and in this state, apply 2.00 g of the above-mentioned fluorescent penetrant by brush coating on the surface of the stainless steel test piece, and at the same time start the stopwatch, and observe the change in the scale of the balance and the elapsed time. did.

The time when the weight of the permeating solution applied to the stainless steel test piece became 1.45 g (elapsed time from the application time) was 7 minutes and 55 seconds, and the time when 10 minutes passed from the application time was elapsed. The weight of the permeate applied to the stainless steel test piece was 0.90 g, and no dye deposition was observed.

The amount of ethanol in 2.00 g of the fluorescent penetrant applied to the stainless steel test piece was 1.10 g,
If 50% by weight of the ethanol evaporates, the amount of evaporation is 0.55 g. Therefore, when 50% by weight of ethanol containing 1.45 g obtained by subtracting 0.55 g from 2.00 g is evaporated, the stainless steel test piece is evaporated. This is the amount of the fluorescent penetrant applied.

Therefore, from the above observation results, the fluorescence penetrating liquid of this example has a time (elapsed time from the time of application) of 50% by weight of the blended ethanol of 7 minutes and 55 seconds. At the time when 10 minutes have passed from the time, it can be seen that 55% by weight of the ethanol blended at the time of preparation has evaporated.

Since the evaporation amount of ethanol in the penetrant inspection test of (2) can be estimated to be almost the same as the above amount, the fluorescent penetrant of this embodiment is used in the penetration test in the penetrant inspection test method in the amount of ethanol blended at the time of preparation. Can be said to be self-concentrated by evaporation of about 55% by weight.

Comparative Example 5 (1) Preparation of Fluorescent Infiltration Solution; Blancophor AW (GAF
: Fluorescent dye: 1.5% by weight, Fluorol 7GA (GA
F company): fluorescent dye: 3% by weight, DOP (Sekisui Chemical Co., Ltd.): boiling point 370 ° C .: 5% by weight, polyoxyethylene alkyl allyl ether (Nippon Surfactant Co., Ltd.): boiling point 300 ° C. or more: 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
88-210 ° C .... 30% by weight, aliphatic hydrocarbon (No. O solvent L: trade name: Nippon Oil Co., Ltd.): boiling point 182
~ 212 ° C ... 30% by weight.

The above materials were mixed and stirred in the above mixing ratio to prepare a comparative fluorescence infiltration solution.

(2) Penetration test: Under the same conditions as in Example 5 except that the permeate was replaced with the comparative fluorescent permeate,
When the penetrant testing method was performed, the depth of the test piece was 7μ.
m was at the limit where it could be clearly detected by a clear fluorescent defect indicator pattern.

(3) Measurement of amount of evaporation: In the same manner as in Example 5, with respect to the comparative fluorescence penetrating liquid, the permeation applied to the stainless steel test piece at the time when 10 minutes passed from the time when 2.00 g was applied. When the weight of the liquid was measured, it was 2.0
The amount was 0 g, there was no change, and the amount of evaporation was 0.

[0092]

The product of the present invention, when used (during permeation treatment),
Even if the amount penetrating into the inside of the flaw is small, a clear defect indicating pattern can be obtained, and the conventional penetrating solution proposed for high sensitivity (the formulation of the penetrating solution shown as a comparative example is , All of which are recommended for high sensitivity), it is possible to detect extremely small flaws that were not possible with the dyes in the composition during storage as well as during use (permeation treatment). It will not come out.

Therefore, it can be said that the present invention greatly contributes to the field where it is required to detect even minute defects (for example, the field of automobile parts and the field of nuclear reactor equipment).

Continuation of the front page (72) Inventor Kazuhiko Ayuba 641 Funakura-cho, Yokosuka City, Kanagawa Prefecture Marktech Co., Ltd. Kurihama Plant (56) References JP-A-3-175345 (JP, A) JP-A-51-3696 (JP) , A) (58) Field surveyed (Int. Cl. ⁶ , DB name) G01N 21/91

Claims (1)

(57) [Claims] 1. A high-boiling organic solvent having a boiling point of 190 ° C. or higher which dissolves a visible dye or a fluorescent dye at 6 to 10% by weight and dissolves the dye.
Certain tricresyl phosphate, di-2-ethylhexyl phthalate
Sil, dibutyl phthalate, polyoxyethylene alkyl
Ether, polyoxyethylene alkyl allyl ether
, Diethylene glycol monobutyl ether and ethyl
Selected from lenglycol monobutyl ether acetate
One or acetone is based solvent 10 to 40 wt% and the base solvent and compatible to the boiling point 110 ° C. or less of volatile organic solvents consisting of two or more substances, ethanol, methanol及
Diluent consisting of any one selected from toluene and toluene
50 to 85% by weight, and at the time of infiltration treatment,
A highly sensitive permeate for use in a penetrant testing method, wherein 50 to 80% by weight of the diluted solvent is evaporated and self-concentrated.