JP2805233B2 - Curable penetrant and curable developer used in solvent removal test method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a curable solvent-removable dye or fluorescent penetrant and a curable quick-drying developer used in a solvent-removable penetrant test method.

[Conventional technology]

As is well known, a penetrant flaw detection test method applied to flaw detection of a surface opening defect (hereinafter, referred to as a “defect”) such as a fine crack or a fine pinhole present on the surface of a device or a member or a welding portion. Is standardized in `` JIS Z 2343-1982 '', and as shown in the standard, there are various penetrant testing methods using various kinds of penetrants, detergents and developers in combination. Penetrant flaw detection using a combination of solvent-removable dyeing or fluorescent penetrants, detergents (solvents), and quick-drying developers classified under the test method symbols "VC-S" and "FC-S" There is a test method (hereinafter, this test method is referred to as “solvent-removable penetration testing method”).

Now, a typical embodiment of the solvent removal penetrant testing method will be described below.

After applying a solvent-removable dye or a fluorescent penetrant to the surface of the test article and performing a permeation treatment for allowing the permeate to penetrate into the defective portion by leaving it for a predetermined time, the surface of the test article is washed with a detergent. To remove the excess permeate remaining on the surface of the specimen, and then apply a developer in which the fine white powder is dispersed in a volatile organic solvent to the surface of the specimen to apply a thin layer of the fine white powder. After performing development processing to form a defect indicating pattern by the penetrating liquid that has penetrated into the defect portion on the surface of the thin layer coating film, the surface of the test article is subjected to a solvent-removable dyeing penetrating liquid. A test method for observing the presence and position of a defective portion by observing under a white light or under an ultraviolet lamp when a solvent-removable fluorescent penetrant is used.

Next, the solvent removal penetrant testing method as described above,
A description will now be given of a solvent-removable dye or fluorescent penetrant and a quick-drying developer which are currently widely used.

The solvent-removable dye-penetrating solution uses a red oil-soluble dye (for example, Oil Red 5BN: manufactured by Shirad Chemical Co., Spitazol Fast Red: manufactured by Futaba Chemical Research Laboratories, etc.) as the dye, and 1 to 5 parts by weight of the dye is used. 20-50 parts by weight of a base solvent composed of a plasticizer (for example, DOP, TCP, etc.) or vegetable oil (for example, soybean oil), and a potency selected from xylene, alkylbenzene, trichloroethane, trifluorotrichloroethane, carbitol, butyl carbitol, etc. A highly permeable liquid dissolved in 50-90 parts by weight of a diluting solvent consisting of a low- and medium-boiling organic solvent. A typical commercially available product is Super Check UP-NU (trade name: Mark Tech Co., Ltd.) Made). The solvent-removable fluorescent penetrant is a fluorescent dye that emits yellow-green under ultraviolet light as a dye (for example, CI Solvent Yellow 43: manufactured by Morton USA, CI Florescent Bright Varnish Agent 68: manufactured by Nippon Kayaku, etc.) ), Which is a highly permeable liquid dissolved in a diluting solvent for the base solvent, as in the case of the solvent-removable dyeing infiltration liquid. A typical commercially available product is Super Glow OD- 6000
(Product name: Mark Tech Co., Ltd.).

The quick-drying developer is composed of 5 to 10 parts by weight of a white fine powder selected from a magnesium carbonate fine powder having a particle diameter of 1 to 2 μm, a hydrous silicic acid fine powder, a silicic anhydride fine powder, and the like, a rubber exhibiting oil, n-hexane, benzene , N-heptane, methyl alcohol, ethyl alcohol, isopropyl alcohol, trichloroethane, trifluorotrichloroethane, and the like are dispersed in a volatile low-boiling organic solvent selected from the group consisting of commercially available solvent-removable dyes or fluorescent penetrants Each time, a quick-drying developer in which the above-mentioned various fine powders and the above-mentioned organic solvents are mixed in an appropriate ratio is commercially available in combination. For example, UD-NU (trade name: mark) Super Glow OD-6000 is a Super Glow DN-600S (trade name: Mark Tech Co., Ltd.)
Are set respectively.

The solvent-removable dye or fluorescent penetrant and the quick-drying developer are often set and handled, as seen in the above examples of Super Check UP-NU and UD-NU,
Those skilled in the art refer to these two agents collectively as "penetration flaw detection agents". Therefore, in the following, unless these two members need to be distinguished, they are collectively referred to as "penetration agents". We call it "a flaw detector."

Incidentally, the cleaning agent is generally used a demonstrative organic solvent such as rubber oil, n-hexane, benzene, n-heptane, mineral terpene, xylene, ethanol, isopropyl alcohol, trichloroethane, and trichloroethylene. If nonflammability is required,
JP-A-54-125090 discloses that a mixed solvent obtained by diluting 113 or Freon 112 or a mixed solvent thereof with another organic solvent can be used.
No. 6,086,045.

[Problems to be solved by the invention]

In order to perform the solvent removal penetrant inspection method as described above with high accuracy, the emerging defect indication pattern must be clearly observable visually, and therefore the defect indication pattern must be clear. Is required. The sharpness of the defect indicating pattern mainly depends on the performance of the solvent-removable dye or fluorescent penetrant and the quick-drying developer.

In other words, the higher the concentration of the dye in the penetrating liquid penetrating the defective part in the above-mentioned permeation process, the more uniform and smooth the thin coating film of the white powder formed in the above-mentioned development process. The more clearly, the clearer the defect indication pattern can be obtained.

However, there is an upper limit to the proportion of the dye that can be mixed with the solvent-removable dye or the fluorescent penetrant, and when more than 5 parts by weight is mixed, the permeability is adversely affected. Has limitations.

In the past, in order to form a uniform and smooth thin layer coating, a synthetic resin soluble in an organic solvent used in the developer is added during the formulation of a quick-drying developer (for example,
Attempts have been made to add a polyvinyl alcohol-based or butyral-based synthetic resin when the organic solvent is isopropyl alcohol. In this case, however, it is extremely difficult to remove the coating film from the surface of the test sample after the development processing. Is not currently being implemented.

The present invention provides a solvent-removable dye or fluorescent penetrant that can increase the concentration of the dye in the penetrant that has penetrated into the defective part, even though the proportion of the dye incorporated in the product is not different from that of the general-purpose product described above. A quick-drying developer that can form a uniform and smooth thin coating film even though the synthetic resin is not added to the liquid and the product and the removal of the coating film after development processing is the same as that of the general-purpose product described above. It is an object of the present invention to provide a clear defect indication pattern.

[Means for Solving the Problems] The above technical problems can be solved by providing the following curable penetrant testing agent.

That is, in a solvent-removable dyeing or fluorescent infiltration solution containing a dye, a base solvent and a diluting solvent as essential components, the diluting solvent has a fluorocarbon 112 of 60 to 90% by weight and a boiling point of 92.8 ° C (760 mmHg).
-Same below-) A curable solvent-removable dye or fluorescent penetrant, which is a non-azeotropic mixture with 10 to 40% by weight of a volatile organic solvent having less than 10% by weight of a volatile organic solvent, and a white fine powder and a dispersion solvent. Wherein the dispersing solvent is a non-azeotropic mixture of 60 to 90% by weight of Freon 112 and 10 to 40 parts by weight of a volatile organic solvent having a boiling point of less than 92.8 ° C. Curable quick-drying developer used in the test method.

When the solvent-removable penetrant testing method is performed using the curable penetrant according to the present invention as described above in accordance with the above-described JIS standard, a clear defect indicating pattern may be produced. And accurate detection results can be obtained.

 The configuration of the present invention will be described in detail as follows.

First, the most important thing in the present invention is Freon 112: 1.1.2.2.
Tetrachloro1.2 difluorotaene: CC ₂ F—CCl ₂ F is a substance having a boiling point of 92.8 ° C. (760 mmHg-the same applies hereinafter) and a freezing point of 26 ° C., and is in a solid state at normal temperature (about 26 ° C.). When it is mixed with an organic solvent, it has a characteristic that its freezing point is lowered to be in a liquid state even at room temperature.

Next, the curable solvent-removable dyeing or fluorescent penetrating liquid according to the present invention is prepared by mixing 60 to 90% by weight of Freon 112 as a diluting solvent and 10 to 40% by weight of a volatile organic solvent having a boiling point of less than 92.8 ° C. The procedure is the same as that of the above-mentioned general-purpose solvent-removable dyeing or fluorescent penetrant except that a boiling mixture is used. Further, the curable quick-drying developer according to the present invention contains Freon 112 as a dispersing solvent.
Of volatile organic solvents with a boiling point of less than 92.8 ° C
The formulation is the same as that of the general-purpose quick-drying developer described above, except that a non-azeotropic mixture of about 40% by weight is used.

The volatile organic solvent having a boiling point of less than 92.8 ° C. used in the present invention can be selected from a wide variety of volatile organic solvents. Specifically, pentane (36.1
° C), hexane (68.7 ° C), 2-methylpentane (60.3 ° C)
° C), 2.2-dimethylbutane (49.7 ° C), 2.3-dimethylbutane (58.0 ° C), 2.4 dimethylpentane (80.5 ° C),
Petroleum ether (30-70 ° C), petroleum benzine (50-90
° C), cyclohexane (80.7 ° C), mixed pentene (32 ~
60 ° C), methylcyclopentane (71.8 ° C), cyclohexene (82.97 ° C), dichloromethane (39.75 ° C), trichloromethane (61.2 ° C), tetrachloromethane (76.7 ° C)
° C), 1.1-dichloroethane (57.28 ° C), 1.2-dichloroethane (83.48 ° C), 1.1.1 trichloroethane (74.0
° C), 1.2 dichloroethylene (60.6 ° C), trichloroethylene (87.19 ° C), 1-chloropropane (46.6 ° C),
2-chloropropane (35.7 ° C), 3-chloropropene (44.96 ° C), 1-chlorobutane (78.4 ° C), 2-chlorobutane (68.25 ° C), 1-chloro-2-methylpropane (68.85 ° C), fluorobenzene (84.7 ° C) ° C), hexafluorobenzene (80.26 ° C), 2.2 dichloro-1.1.1 trifluoroethane (27.5 ° C), 1.1-dichloro-1-fluoroethane (32.0 ° C), 1.2 dibromo-1.1.2.2 tetrafluoroethane (47.2 ° C ), Bromochlorotrifluoroethane (50.2 ° C), 1.1 dichloro-2.2.3.3.3 pentanefluoropropane (51.1 ° C), 1.3 dichloro-1.2.2.3.3 pentanefluoropropane (56.1 ° C), and propanol pentafluoride (81 ° C), methanol (64.5 ° C), ethanol (7
8.3 ° C), isopropyl alcohol (82.3 ° C), ethyl ether (34.6 ° C), isopropyl ether (68.27
° C), 1.2 propylene oxide (34.5 ° C), furan (31.
3 ° C.), 2-methylfuran (63.7 ° C.), tetrahydrofuran (66.0 ° C.), 1.2 dimethoxyethane (85.2 ° C.), methylal (42.3 ° C.), acetone (56.2 ° C.), methyl acetone (50-67 ° C.), methyl ethyl ketone ( 79.57 ° C),
Methyl formate (31.8 ° C), ethyl formate (54.2 ° C), propyl formate (81.3 ° C), methyl acetate (57.8 ° C), ethyl acetate (77.1 ° C), diethylamine (55.5 ° C), propylamine (48.0 ° C), isopropylamine (33.3 ° C), butylamine (77.0 ° C), 2.2.2 trifluoroethanol (73.
6 ° C). The value in parentheses attached to each solvent is the boiling point (760 mmHg).
It is desirable to select a solvent having a boiling point difference from the boiling point of about 10 ° C. or more.

The mixing ratio of the volatile organic solvent in the present invention is important, and if it is 40% by weight or more, the time required for evaporation during application becomes too long, and if it is 10% by weight or less, the solid content during storage at room temperature is unfavorable. It is not preferable because there is a risk of becoming a state.

60 to 90% by weight of Freon 112 and 10 of the volatile organic solvent
When mixed within the range of 4040% by weight, it is ensured that an appropriate evaporation time is obtained at the time of application and a liquid state can be maintained during storage. However, when mixed within the above range, the mixture is azeotropic. The mixture ratio of the mixture of Freon 112 and the volatile organic solvent to be an azeotrope should not be varied depending on the amount of Freon 112 and the type of the volatile organic solvent to be selected. Yes, but can be determined by simple experiments.

In addition, an appropriate amount of a rust inhibitor such as nitromethane or ethylenediamine can be added to the formulation of the curable penetrant flaw detector according to the present invention, if necessary.

Preparation of the curable penetrant flaw detector according to the present invention is easy,
Weigh each required material so that it has the required mixing ratio,
It can be prepared by mixing and stirring.

It is convenient to handle the prepared curable penetrant flaw detector according to the present invention together with a propellant at a filling pressure of about 3 to 5 kg / cm ^{2 in an} aerosol can according to a conventional method and use it as an aerosol type.

Next, the method of using the curable penetrant for testing according to the present invention is not different from that of the general-purpose penetrant for detection described above, and its use mode is completely the same as the typical mode of the above-described solvent-removable penetrant test method. Is the same.

[Action]

When the solvent-removable penetrant testing method is carried out at room temperature using the curable penetrant according to the present invention at room temperature according to the representative embodiment, a clear defect indication pattern appears by the following operation.

That is, in the curable solvent-removable dyeing or fluorescence penetrating solution according to the present invention, the diluting solvent was mixed with Freon 112 having a boiling point of 92.8 ° C and a volatile organic solvent having a boiling point of less than 92.8 ° C at a predetermined mixing ratio. Since it is a non-azeotropic mixture, if it adheres to the surface of the test sample in the above-mentioned permeation treatment, the boiling point 9
The volatile organic solvent having a temperature of less than 2.8 ° C. evaporates, the concentration of the dye dissolved in the permeate increases, and the permeate hardens (solidifies).

Further, in the curable quick-drying developer according to the present invention,
Since the dispersing solvent is a non-azeotropic mixture in which Freon 112 having a boiling point of 92.8 ° C and a volatile organic solvent having a boiling point of less than 92.8 ° C are mixed at a predetermined mixing ratio, the developer is applied to the surface of the test sample in the developing treatment. The dispersing solvent in the formulation dissolves the penetrating liquid that is being cured or cured in the defective portion, and the thin layer formed by the white fine powder in the developer prescription sucks up the penetrating liquid. As volatile organic solvents with a boiling point of less than 92.8 ° C evaporate from the dispersion solvent,
The remaining Freon 112 is cured (solidified) to form a uniform and smooth coating film having white fine powder particles as nuclei.

Therefore, in the present invention, a defect indicating pattern appears on a uniform and smooth coating film surface by a penetrating liquid having a high dye concentration, and the indicating pattern becomes clear.

Furthermore, in the present invention, since the penetrant and the thin coating film are cured, when the defect indication pattern is observed after the development processing, even when the time from the end of the development processing to the observation time is long, The defect indication pattern is not excessively blurred, and the detection performance can be kept constant.

〔Example〕

Next, the present invention will be described below with reference to formulation examples, evaluation results of the solvent removal penetrant testing and test examples.

1. Curable solvent-removable dye or fluorescent penetrant Formulation: A. Freon 112 73% by weight and n-hexane 10% by weight, TOP
5% by weight (made by Daihachi Chemical) and 10% by weight of TCP (made by Daihachi Chemical)
And 2% by weight of Spitazole Fast Red FW (manufactured by Futaba Chemical Laboratory) were sufficiently mixed to prepare a permeate. The freezing point of the permeate was 7 ° C.

B. Freon 112 65% by weight and methylene chloride 20% by weight, DOP
10% by weight (manufactured by Daihachi Chemical) and Sudan Red (manufactured by BASF)
5% by weight was sufficiently mixed to prepare a permeate. The freezing point of this permeate was 13 ° C.

C. Freon 112 73.5% by weight and n-heptane 10% by weight, DO
5% by weight of P (same as above), 10% by weight of TCP (same as above) and 1.5% by weight of Oil Red 5BN (manufactured by Shirad Chemical Co., Ltd.) were sufficiently mixed to prepare a permeate. The freezing point of this permeate was 9 ° C.

D. Freon 112 76% by weight and n-heptane 10% by weight, TCP
(Same as above) 10% by weight and 4% by weight of Sudan Red 462 (BASF) were sufficiently mixed to prepare a permeate. The freezing point of this permeate was 13 ° C.

E. Freon 112 78.5% by weight and 1.1.1 Trichloroethane 10
Wt%, TCP (as above) 10 wt% and Solvent Yellow 4
3 (manufactured by Morton) and 0.5% by weight of White Fluoro B (manufactured by Sumitomo Chemical) were sufficiently mixed to prepare a permeate. The freezing point of this permeate was 13 ° C.

2. Curable quick-drying developer Formulation: 6.5% by weight of magnesium carbonate AM-50 (manufactured by Asahi Glass) in a mixture of 82% by weight of F. Freon 112 and 10% by weight of n-hexane
And 2% by weight of Ezoril # 200 (manufactured by Nippon Aerizil) were dispersed to prepare a developer.

A mixture of 70% by weight of G. Freon 112, 22% by weight of isopropyl alcohol, and 1% by weight of Orben (manufactured by Shiraishi Kogyo), 2% by weight of Carplex # 1120 (manufactured by Shionogi & Co., Ltd.) and TT magnesium carbonate (manufactured by Tokuyama Soda) 4 % By weight to prepare a developer.

6% by weight of calcium carbonate (manufactured by Shiraishi Kogyo) is dispersed in a mixture of 69% by weight of H. Freon, 10% by weight of n-heptane, 12% by weight of methylene chloride and 2% by weight of orben (same as above) to prepare a developer. did.

I. Freon 112 was dispersed in a mixture of 62% by weight of methylene chloride and 30% by weight of methylene chloride, and 6% by weight of Ezrol # 200 (same as above) and silver star of magnesium carbonate (manufactured by Kamishima Chemical Co., Ltd.) to prepare a developer.

A developer was prepared by dispersing 6% by weight of magnesium silver carbonate (same as above) and Ezril # 200 (same as above) in a mixture of 82% by weight of J. Freon 112 and 10% by weight of ethyl alcohol.

3. Performance evaluation results (1). The performance comparison between the curable solvent-removable dye-penetrating solutions of Formulations 1-A to D and the above-mentioned Super Check UP-NU was conducted at room temperature in accordance with the U.S. Army standard MIL-1-25135D.

That is, a 2024 aluminum alloy test piece prepared in accordance with the same standard (a 8 mm thick, 76 mm x 51 mm rectangular plate was provided with a 2 mm x 2 mm groove at the center of the surface, and one was divided into A
Side and the other side as B side), and on the A side, formula 1
Apply the curable solvent-removable dye-penetrating solution of A using a brush, apply Super Check UP-NU to the B surface using a brush, leave for 10 minutes, and then use a clean paper towel with both sides dried. Wipe off excess permeate and then use a commercially available solvent-removable penetrant testing method detergent (Super Check UR
-NU: (trade name: manufactured by Marktec Co., Ltd.) was wiped on both sides with a paper towel impregnated with it, and the excess permeate was further wiped off. Next, the above-mentioned Super Check UD-NU (aerosol type) was sprayed uniformly on both sides at a distance of about 30 cm from the test surface, left for 5 minutes, and visually inspected for defect indication patterns on both surfaces. It was slightly better.

The same performance comparison as above was performed for Formulations 1-B to D, but the sharpness of the defect indicating bleeding pattern was A in all cases.
The surface (the surface using the product of the present invention) was slightly better.

As for the curable solvent-removable fluorescent penetrant of Formula 1-E, the above-mentioned Super Glow OD-6000 was used as a comparative product, and Super Glow R-II (trade name: Marktec Co., Ltd.) was used as a cleaning agent. A performance comparison was performed in the same manner as described above (the visual comparison was performed under irradiation of an ultraviolet lamp). The definition 1-E was more excellent in the sharpness of the defect indicating bleeding pattern.

(2). According to the same standard as (1), the performance comparison between the curable quick-drying developer of Formulations 2-F to J and the above-mentioned Super Check UD-NU (aerosol type) was conducted at room temperature.

That is, after applying Super Check UP-NU on both sides A and B of the same test piece as in (1) and leaving it to stand for 10 minutes, wipe both sides with a dry clean paper towel to wipe off excess permeate. Both sides were wiped with a paper towel impregnated with Super Check UR-NU described above to further wipe off excess permeate. Next, mask the surface B so that the developer does not adhere thereto,
Formulation 2-F curable quick-drying developer with propellant about 4k
As an aerosol type sealed in an aerosol can with a filling pressure of g / cm ² according to a conventional method, sprayed uniformly on the A surface at a distance of about 30 cm from the test surface, immediately masked the A surface to prevent the developer from adhering, Peel off the mask on the B side and spray Super Check UD-NU (aerosol type) about 30 cm away from the test surface and spray it evenly on the B side. Then, remove the mask on the A side and leave it for 5 minutes. When the patterns were compared visually, the sharpness was slightly better on the A side.

The same performance comparison as above was performed for Formulations 2-G to J, but the sharpness of the defect indicating bleeding pattern was A in all cases.
The surface (the surface using the product of the present invention) was slightly better.

In addition, the same performance comparison as above was carried out for the composition in which 1% by weight of ethylenediamine was added to Formulation 2-F and the composition in which 1% by weight of nitromethane was added to Formulations 2-G to J, respectively. No particular change was observed with the addition of the agent.

4. Example of dye removal penetrant detection test for solvent removal at room temperature, A for JIS-Z-2343-1982 standard sensitivity test
In a mold contrast test piece, the curable solvent-removable dyeing and permeating solution of Formula 1-A was sealed together with a propellant in an aerosol can at a filling pressure of about 4 kg / cm ² according to a conventional method to form an aerosol type about 15 cm from the test surface. Separately, spray uniformly and leave for 5 minutes to perform a permeation treatment. Then, wipe the test piece with a dry rag, and then super-check UR-
The excess permeate is wiped off with a rag impregnated with NU, and then the test piece is cured with a curable quick-drying developer of formula 2-F together with a propellant at a filling pressure of about 5 kg / cm ² according to a conventional method. Enclosed in an aerosol can, as an aerosol type, sprayed uniformly at a distance of about 30 cm from the test surface, formed a thin coating film with a thickness of about 30 μm, and allowed to stand for 7 minutes. As a result of visual observation, a clear red defect indicating pattern was clearly recognized on a white background.

5. Solvent removal fluorescent penetrant test example At room temperature, A for JIS-Z-2343-1982 standard sensitivity test
In a mold contrast test specimen, the curable solvent-removable fluorescent penetrant of Formula 1-E was sealed together with a propellant in an aerosol can at a filling pressure of about 4 kg / cm ² according to a conventional method to form an aerosol type about 15 cm from the test surface. After spraying uniformly and leaving it for 5 minutes, the test piece was wiped dry with a dry rag.
The excess permeate is removed by wiping with a waste impregnated with II, and then the test piece is cured with a curable quick-drying developer of Formula 2-J together with a propellant at a filling pressure of about 4 kg / cm ² according to a conventional method. Enclosed in an aerosol can, as an aerosol type, sprayed uniformly at a distance of about 30 cm from the test surface, formed a thin layer coating of about 30 μm in thickness, left it for 7 minutes, and developed it in a dark place. When the test piece was visually observed under irradiation with an ultraviolet lamp, a clear yellow-green fluorescent defect indicating pattern was clearly recognized.

〔The invention's effect〕

The curable penetrant flaw detection according to the present invention, when used, causes a defect indicating pattern due to a penetrating liquid having a high dye concentration to appear on a uniform and smooth coating film surface. It is possible to accurately perform the solvent removal penetrant flaw detection test method without excessively blurring the pattern.

Claims (2)

(57) [Claims] 1. A solvent-removable dyeing or fluorescent penetrating solution comprising a dye, a base solvent and a diluting solvent as essential components used in a solvent-removing penetrant testing method, wherein the diluting solvent is fluorocarbon.
112 A non-azeotropic mixture of 60 to 90% by weight and 10 to 40% by weight of a volatile organic solvent having a boiling point of less than 92.8 ° C (760 mmHg). Sex dye or fluorescent penetrant. 2. A quick-drying developer containing a white fine powder and a dispersing solvent as essential components for use in a solvent-removing penetrant testing method, wherein the dispersing solvent is 60 to 90% by weight of Freon 112 and has a boiling point of 9%.
A curable quick-drying developer used in a solvent-removable penetrant testing method, which is a non-azeotropic mixture with 10 to 40 parts by weight of a volatile organic solvent having a temperature of less than 2.8 ° C (760 mmHg).