JP6568568B2 - Dyeing penetrant for penetrant testing and method for producing the dyeing penetrant - Google Patents

Description

  The present invention relates to a dyeing and penetrating liquid used in a penetrant flaw detection test for detecting fine opening defects existing on the surfaces of various metals. Specifically, since the dyeing penetrant according to the present invention contains an azo-based red dye solution, a clear defect indication pattern appears, but the chlorine concentration is very low and the object to be inspected is difficult to corrode. The present invention relates to a dyeing and penetrating solution that can be suitably used for a penetrant flaw detection test of a metal member that easily corrodes, such as a magnesium alloy or a titanium alloy.

  As is well known, the penetrant flaw detection test is a kind of nondestructive inspection method and is standardized in JIS Z 2343-1-6. The basic aspect is that after a dyeing solution with strong penetrating dye or fluorescent penetrating liquid is adhered to the surface of the object to be inspected and infiltrated into the opening defect, the object is inspected without penetrating into the defect. Remove excess permeate remaining on the surface of the object, and then apply inorganic white powder (called “developer” to those skilled in the art) such as magnesium carbonate powder or calcium carbonate powder on the surface of the object to be inspected. A thin layer is formed, and a defect indicating pattern appears by sucking out the penetrating liquid penetrating into the opening defect portion by the developer layer to the surface of the developer layer. Observe the image taken with the naked eye or with a digital camera or the like, and in the case of fluorescent penetrating liquid, observe the image taken with a digital camera or the like under irradiation with a black light or the like. By opening defect Is that to detect the presence and position.

  As one type of dyeing penetrant used in the penetrant flaw detection test, a dyeing penetrating liquid containing an azo red dye is known.

  The penetrant containing the azo red dye has a clear defect indication pattern, can be observed with the naked eye under natural light or white light, and can be manufactured at a low cost.

  Generally, a dyeing penetrant containing an azo red dye is prepared by diluting an azo red dye solution prepared by dissolving an azo red dye in an organic solvent with an organic solvent, and adding a plasticizer or the like as necessary. Although it is manufactured by adding, azo red dye solution is inevitably mixed with chlorine in the manufacturing process, it is known that the dye penetrant containing azo red dye solution has a high chlorine concentration. .

  Chlorine is one of the substances that cause metal corrosion, and the dye penetrant is excellent in permeability. There is a risk that the object to be inspected may be corroded by the remaining dye penetrant.

  Therefore, dyeing penetrants containing azo-based red dye solutions can be used for general metal penetrant testing, but parts that must avoid corrosive substances as much as possible, such as reactor welds. In addition, there is a problem that it cannot be used for a penetration inspection test of a metal member made of a metal that easily corrodes, such as a magnesium alloy or a titanium alloy.

  Therefore, it is a dyeing penetrant containing an azo-based red dye solution, and the defect indication pattern is clear, but the chlorine concentration causing corrosion is low, and penetration inspection of the welded part of a nuclear reactor or a corroded metal member Development of a dye penetrant that can be used for testing and can be produced at low cost by a simple method is desired.

JP-A-3-175345

  Patent Document 1 discloses a dyeing / penetration produced by mixing and stirring a commercially available azo red dye solution (Oil Red 5BN / manufactured by Silado Chemical Co., Ltd.), a plasticizer, a base solvent, and a volatile low / medium boiling organic solvent. Liquid is described.

  However, since the commercially available azo red dye solution contains a large amount of chlorine, the dye penetrant using the commercially available azo red dye solution also has a high chlorine concentration. Although it can be used for a general metal penetration test, it cannot be used for a penetration test of a welded part of a nuclear reactor or a metal member that is easily corroded.

  The present inventors made it a technical subject to solve the above-mentioned problems, and as a result of many trial and error trial manufactures and experiments, the azo red dye solution was heated at 100 to 150 ° C. If the dyeing penetrating liquid contains a red dye solution, a plasticizer, and a diluent solvent, the chlorine concentration of the dyeing penetrating liquid can be reduced to 100 ppm or less even when the azo dye solution is contained. Since it appears clearly, it can be suitably used for welded parts of reactors and metal members that are easily corroded, and has achieved the above technical problem by obtaining remarkable knowledge that it can be manufactured easily and inexpensively. is there.

  The technical problem can be solved by the present invention as follows.

The present invention also relates to a dye penetrant for penetrant flaw detection test containing only an azo red dye as a dye, and an azo red dye solution in which the azo red dye is dissolved in an organic solvent at 100 to 150 ° C. A low chlorine azo red dye solution obtained by adding a high boiling point organic solvent having a boiling point of 150 to 220 ° C. for the weight reduced by heating to a heated azo red dye solution having a chlorine concentration of 1000 ppm or less by heating . A dyeing and penetrating solution for penetrant flaw detection tests, comprising 7% by weight , a plasticizer and a diluent solvent, and having a chlorine concentration of 100 ppm or less.

  Further, the present invention is a dyeing penetrant for penetrant flaw detection test wherein the low chlorine azo red dye solution is 2 to 7% by weight, the plasticizer is 10 to 50% by weight, and the balance is 100% by weight with a diluting solvent. .

Moreover, this invention is the dyeing | staining penetrant for a penetrant flaw test whose said dilution solvent is a high boiling point organic solvent with a boiling point of 150-250 degreeC, and / or surfactant with a boiling point of 250 degreeC or more .

  The present invention also relates to a method for producing a heated azo red dye solution in which an azo red dye solution in which an azo red dye is dissolved in an organic solvent is heated at 100 to 150 ° C. to reduce the chlorine concentration to 1000 ppm or less. .

  The present invention also provides a low chlorine azo red dye produced by adding a high boiling point organic solvent having a boiling point of 150 to 220 ° C. reduced in weight to the heated azo red dye solution produced by the above production method. It is a manufacturing method of a solution.

  Further, the present invention provides a dyeing penetrant for a penetrant flaw detection test characterized in that it is produced by stirring a solution containing a heated azo red dye solution, a plasticizer and a diluting solvent produced by the above production method. It is a manufacturing method.

  Moreover, this invention is a manufacturing method of the dyeing | staining penetrating liquid for a penetrant flaw test whose chlorine concentration of the dyeing | staining penetrating liquid manufactured with the said manufacturing method is 100 ppm or less.

The dyeing penetrating liquid of the present invention is a dyeing penetrating liquid in which a defect indicating pattern appears clearly because it contains a heated azo red dye solution obtained by heating an azo red dye solution at 100 to 150 ° C.

Since the chlorine concentration is as low as 100 ppm or less, it can also be suitably used for penetration testing of highly corrosive metal members such as reactor welds and magnesium alloys and titanium alloys.

  In addition, after heating the azo red dye solution at 100 to 150 ° C., a low-boiling azo system is returned to its original weight by adding a high boiling point organic solvent having a boiling point of 150 to 220 ° C. reduced by heating. If a red dye solution is used, a dyeing permeation solution having a chlorine concentration of 100 ppm or less can be produced at a low cost by a simple method.

  In addition, it is clearer if the dyeing penetrating solution has a low chlorine azo red dye solution concentration of 2 to 7% by weight, a plasticizer of 10 to 50% by weight and the balance of 100% by weight with a diluent solvent in the dyeing and penetrating solution. A defect indicating pattern is obtained, and a dyeing permeation solution having high permeability is obtained.

  Moreover, if a high boiling point organic solvent having a boiling point of 150 to 250 ° C. and / or a surfactant having a boiling point of 250 ° C. or higher is used as the dilution solvent, a dyeing penetrating solution having higher permeability can be obtained.

  In addition, the dyeing | staining penetrating liquid in this invention can be used for the detection of a 30-50 micrometers opening defect part.

2 is a photograph of the test piece immersion surface of Example 1. FIG. 6 is a photograph of a test piece immersion surface of Comparative Example 2.

  In the present specification, a solution obtained by heating an azo red dye solution is referred to as a “heated azo red dye solution”, and a solution obtained by adding a high boiling point organic solvent after heating to return to the original weight is referred to as a “low chlorine azo red dye solution”. Sometimes referred to as “solution”.

  A commercially available azo red dye solution can be used for the production of the dye penetrant in the present invention.

  Commercially available azo red solutions include Liquid Red E (C.I. Solvent Red 164 CAS: 92257-31-3 / dye concentration: 50% / manufactured by Shirad Chemical Co., Ltd.), DYEGUARD RED E (C.I. Solvent Red 164 CAS: 92257-31-3 / dye concentration: 50% / manufactured by John Hogg), Solvent Red 164HF (C.I. Solvent Red 164 CAS: 92257-31-3 / dye concentration: 60 to 80% / Taisei Manufactured by Shoji Co., Ltd.), Liquid Red PB-40J (CI Solvent Red 19 / dye concentration: 60% / manufactured by Shirad Chemical Co., Ltd.), Sudan Red 462 (CI Solvent Red 19 / dye concentration: 60%) / BASF), Papillion Red S- R 40% (C.I. Solvent Red 19 / EASTWELL), DYEGUARD RED C (C.I. Solvent Red 19 CAS: 56358-09-9, 57712-94-4 / dye concentration: 60% / John Hogg For example).

  After measuring the desired weight of the azo red dye solution, the chlorine in the azo red dye solution can be reduced by heating at 100 to 150 ° C., more preferably 110 to 120 ° C.

  Chlorine is difficult to decrease even when heated at a temperature lower than 100 ° C., and if heated at a temperature exceeding 150 ° C., chlorine decreases, but the defect indication pattern becomes thin, and an opening defect portion cannot be accurately detected. There is a fear.

  Commercially available azo red dye solutions may vary in chlorine concentration even if they are the same product, so the heating time may be set appropriately to achieve the desired chlorine concentration, but it is preferably 1 hour or more, and 2-3 Time is enough.

  This is because, when heated for a long period of time, the amount of volatilization of the solvent component increases, so that the amount of the high-boiling organic solvent added later increases.

  It is preferable to heat until the chlorine concentration of the azo red dye solution is 1000 ppm or less.

  In the present invention, the weight of the heated azo red dye solution is measured, and a low chlorine azo red dye solution which is returned to its original weight by adding a high boiling point organic solvent corresponding to the weight of the reduced amount may be used. Good.

  The high boiling point organic solvent to be added to the heated azo red dye solution is an organic solvent having a boiling point of 150 to 220 ° C., a high boiling point solvent # 150 (boiling point 179 to 217 ° C./manufactured by Gordo Co., Ltd.), Shellsol A-100. (Boiling point 150-185 ° C./manufactured by Shell Chemicals Japan Co., Ltd.).

  The dyeing penetrant in the present invention can be produced by mixing a low chlorine azo red dye solution, a plasticizer and a diluting solvent and stirring at 30 to 100 rpm for 10 to 120 minutes.

  The dyeing penetrant in the present invention preferably contains 2 to 7% by weight of a low chlorine azo red dye solution.

  If the concentration of the azo red dye is less than 2% by weight, the defect indication pattern becomes thin, and if it exceeds 7% by weight, the excess dye penetrant that cannot be removed increases and noise increases. This is because there is a possibility that an accurate defect instruction pattern cannot be obtained.

  The plasticizer in the present invention is not particularly limited, but a phthalic acid plasticizer is suitable.

  Examples of the phthalic acid plasticizer include bis (2-ethylhexyl) phthalate (DEHP) dioctyl phthalate (DOP) and diisononyl phthalate (DINP).

The plasticizer is preferably contained in an amount of 10 to 50% by weight.
This is because a dyeing penetrating liquid having high penetrability can be obtained.

  The diluent solvent is preferably a high-boiling organic solvent having a low volatility and a boiling point of 150 to 250 ° C. and / or a surfactant having a boiling point of 250 ° C. or higher. This is because a dyeing penetrating solution having high penetrating power can be obtained.

  High-boiling organic solvents having low volatility and surfactants having a boiling point of 250 ° C. or higher include butyl carbitol solvent (manufactured by DOW), Cactus (registered trademark) normal paraffin N-12D (manufactured by JXTG Energy), nonipol (Registered trademark) 95 (manufactured by Sanyo Chemical Industries, Ltd.), NAROACTY (registered trademark) CL-85 (manufactured by Sanyo Chemical Industries, Ltd.), normal paraffin N-11 (manufactured by JXTG Energy Co., Ltd.) can be exemplified. .

The chlorine concentration of the dyeing penetrant in the present invention is 100 ppm or less.
The chlorine concentration should be low, but it may be 100 ppm or less, more preferably 80 ppm or less.
This is because the dyeing penetrant used in the reactor weld is required to have a chlorine concentration of 100 ppm or less.

  The chlorine concentration of the azo red dye solution or dyeing penetrant can be measured by ion chromatography or the like according to NDIS3201 “Method for analyzing sulfur, chlorine and fluorine of penetrant flaw detector”.

  The present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited thereto.

Example 1
As the azo red dye solution, Liquid Red E (manufactured by Silad Chemical Co., Ltd.) was used. The chlorine concentration of Liquid Red E was 1810 ppm.

  Liquid Red E 50g was put into the glass container, and it heated at 100 degreeC for 1 hour with the thermostat (made by PR-1J / ESPEC).

  The chlorine concentration of Liquid Red E after heating was 953 ppm, and the weight was reduced by 6.87 g compared to before heating.

  Added 6.87 g of high boiling point solvent # 150 (manufactured by Gordo Co., Ltd.) to heated Liquid Red E and mixed to return to the weight before heating, followed by stirring, and a low chlorine azo red dye solution of Liquid Red E Was made.

  The produced liquid red E low chlorine azo red dye solution 6.0% by weight (dye concentration: 3.0% by weight), DOP (manufactured by CG Esta) as a plasticizer 15% by weight, and butylcar as a diluent solvent The dye permeation solution of Example 1 was prepared by mixing 10% by weight of bitol solvent (manufactured by DOW) and 69% by weight of Cactus (registered trademark) normal paraffin N-12D (manufactured by JXTG Energy).

  The chlorine concentration of the dyeing and penetrating solution of Example 1 was 57 ppm.

(Example 2)
The above-mentioned DYEGUARD RED E (manufactured by John Hogg) was used as the azo red dye. The chlorine concentration of DYEGUARD RED E was 1750 ppm.

  DYEGUARD RED E 50g was put into the glass container, and it heated at 150 degreeC in the thermostat for 1 hour.

  The chlorine concentration of DYEGUARD RED E after heating was 653 ppm, and the weight was reduced by 15.30 g compared to before heating.

  15.30 g of high boiling point solvent # 150 was added to heated DYEGUARD RED E to return to the weight before heating, and then stirred to prepare a low chlorine azo red dye solution of DYEGUARD RED E.

  The prepared low chlorine azo red dye solution of DYEGUARD RED E was 6.0% by weight (dye concentration: 3.0% by weight), DOP 15% by weight, butyl carbitol solvent 10% by weight, CACTUS (registered trademark) normal paraffin N The dye permeation solution of Example 2 was prepared by mixing -12D 69% by weight.

  The chlorine concentration of the dyeing penetrant of Example 2 was 40 ppm.

(Example 3)
The above-mentioned Liquid Red PB-40J (manufactured by Shirad Chemical Co., Ltd.) was used as the azo red dye. The chlorine concentration of Liquid Red PB-40J was 1580 ppm.

  50 g of Liquid Red PB-40J was put in a glass container and heated at 100 ° C. for 1 hour in a thermostatic bath.

  The chlorine concentration of Liquid Red PB-40J after heating was 850 ppm, and the weight was reduced by 5.45 g compared to before heating.

  5.45 g of high boiling point solvent # 150 was added to heated Liquid Red PB-40J to return to the weight before heating, and then stirred to prepare a low chlorine azo red dye solution of Liquid Red PB-40J.

  The prepared Liquid Red PB-40J low chlorine azo-based red dye solution 3.0 wt% (dye concentration: 1.8 wt%), DOP 20 wt%, butyl carbitol solvent 10 wt%, Cactus (registered trademark) normal paraffin 67% by weight of N-12D was mixed to prepare the dyeing permeation solution of Example 3.

  The chlorine concentration of the dyeing penetrant of Example 3 was 30 ppm.

Example 4
The above Liquid Red E was used as the azo red dye solution. The chlorine concentration of Liquid Red E was 1121 ppm.

  553 kg of Liquid Red E was placed in the tank and heated and stirred at 110 ° C. for 3 hours.

  The chlorine concentration of Liquid Red E after heating was 723 ppm, and the weight decreased by 44 kg compared to before heating.

  44 kg of high boiling point solvent # 150 was added to heated Liquid Red E to restore the original weight, and then stirred to prepare a low chlorine azo red dye solution of Liquid Red E.

  The prepared liquid red E low chlorine azo-based red dye solution was 6.0% by weight (dye concentration: 3.0% by weight), DOP 15% by weight, butyl carbitol solvent 10% by weight, CACTUS (registered trademark) normal paraffin N The dye permeation solution of Example 4 was prepared by mixing -12D 69% by weight.

  The chlorine concentration of the dyeing penetrant of Example 4 was 43 ppm.

(Example 5)
The same azo red dye solution as in Example 4 was used.

  370 kg of Liquid Red E was placed in the tank and heated and stirred at 110 to 120 ° C. for 3 hours.

  The chlorine concentration of Liquid Red E after heating was 902 ppm, and the weight was reduced by 16.6 kg compared with before heating.

  16.6 kg of high boiling point solvent # 150 was added to heated Liquid Red E to return to the original weight, and the mixture was stirred to prepare a low chlorine azo red dye solution of Liquid Red E.

  The prepared liquid red E low chlorine azo red dye solution was 6.0% by weight (dye concentration: 3.0% by weight), DOP 15% by weight, butyl carbitol solvent 10% by weight, Nonipol (registered trademark) 95 (Sanyo). 10% by weight (manufactured by Kasei Kogyo Co., Ltd.) and 59% by weight of Cactus (registered trademark) normal paraffin N-12D were mixed to prepare the dyeing permeation solution of Example 5.

  The chlorine concentration of the dyeing and penetrating solution of Example 5 was 64 ppm.

(Comparative Example 1)
The same azo red dye solution as in Example 1 was used.

  Liquid Red E 50g was put into the glass container, and it heated at 70 degreeC in the thermostat for 3 hours.

  The chlorine concentration of Liquid Red E after heating was 1778 ppm, and the weight was reduced by 0.48 g compared to before heating.

  0.48 g of high boiling point solvent # 150 was added to heated Liquid Red E to return to the original weight, and then stirred to prepare Liquid Red E (heating + addition of high boiling point solvent).

  Liquid Red E (heating + addition of high boiling point solvent) 5.0% by weight (dye concentration: 2.5% by weight), DOP 15% by weight, butyl carbitol solvent 10% by weight, Cactus (registered trademark) normal paraffin N- 12D 70 weight% was mixed and the dyeing | staining penetration liquid of the comparative example 1 was produced.

  The chlorine concentration in the dyeing and penetrating liquid of Comparative Example 1 was 106 ppm.

(Comparative Example 2)
The same azo red dye solution as in Example 1 was used.

  50 g of Liquid Red E was placed in a glass container and heated at 170 ° C. for 1 hour in a thermostatic bath.

  Liquid Red E 50 g chlorine concentration after heating was 450 ppm, and the weight was reduced by 17.45 g compared to before heating.

  17.45 g of the high boiling point solvent # 150 was added to the heated Liquid Red E and returned to the original weight, and then stirred to obtain Liquid Red E (heating + high boiling point solvent addition).

  The prepared Liquid Red E (heating + addition of high boiling point solvent) was 5.0% by weight (dye concentration: 2.5% by weight), DOP 15% by weight, butyl carbitol solvent 10% by weight, Cactus (registered trademark) normal paraffin N -12D 70 weight% was mixed and the dyeing | staining penetration liquid of the comparative example 2 was produced.

  The chlorine concentration in the dyeing and penetrating liquid of Comparative Example 2 was 24 ppm.

(Measurement of chlorine concentration)
The chlorine concentration of each azo red dye solution and the dyeing and permeating solutions of each of Examples and Comparative Examples was determined by ion chromatography IC-2010 (manufactured by Tosoh Corporation) according to NDIS3201 ).

(Sensitivity test)
The sensitivity test of Example 1 and Comparative Example 2 was performed using a type 1 contrast test piece (30 μm).

  The test specimens were coated with the dye penetrant solution of Example 1 and Comparative Example 2 by a brush coating method, and after 5 minutes, the excess dye penetrant solution was wiped off with a waste cloth. Thereafter, remover Supercheck (registered trademark) UR-T (manufactured by Marktec Co., Ltd.) was sprayed on the waste cloth, and the excess dyeing penetrant was wiped off again with the waste cloth.

  Subsequently, Supercheck (registered trademark) UD-T (manufactured by Marktec Corporation) was applied as a developer by a spray method. The defect indication pattern that appeared after developing for 10 minutes was photographed with a digital camera under white light and observed visually.

The defect instruction pattern of Example 1 was clear and the detection rate was 100% (FIG. 1).
On the other hand, the defect indication pattern of Comparative Example 2 was thin, and the detection rate was 70% (FIG. 2).

  From the examples and comparative examples, it was proved that the dye permeation solution of the present invention was a dye permeation solution having a chlorine concentration of 100 ppm or less and a defect indicating pattern clearly appearing.

The dyeing penetrant according to the present invention contains an azo red dye solution, and is a dyeing penetrating liquid in which a defect indicating pattern appears clearly, but the chlorine concentration is very low at 100 ppm or less, and it is difficult to corrode the inspection object. A dyeing and penetrating solution that can be used for penetration testing of easily corroded metal parts such as nuclear reactor welds and magnesium alloys and titanium alloys, and can be easily and inexpensively manufactured. It is a liquid.
Therefore, the present invention has high industrial applicability.

Claims (7)

A penetrant dyeing permeate containing only azo red dye as the dye, the chlorine concentration by heating the azo red dye solution azo red dye is dissolved in an organic solvent at 100 to 150 ° C. 2-7 wt% of a low chlorine azo red dye solution obtained by adding a high boiling point organic solvent having a boiling point of 150-220 ° C. reduced by heating to a heated azo red dye solution reduced to 1000 ppm or less. And a dyeing permeation solution for penetrant flaw detection tests, wherein the chlorine concentration is 100 ppm or less. Before SL plasticizer 10 to 50 wt%, penetrant dyeing penetrant according to claim 1, wherein the balance being 100 wt% at a dilution solvent. The diluting solvent, a high boiling organic solvent and / or liquid penetrant dyeing penetrant according to claim 1 or 2 SL placing a boiling point of 250 ° C. or more surfactants having a boiling point of 150 to 250 ° C.. A method for producing a heated azo red dye solution in which an azo red dye solution in which an azo red dye is dissolved in an organic solvent is heated at 100 to 150 ° C. to make the chlorine concentration 1000 ppm or less. 5. Production of a low chlorine azo red dye solution produced by adding a high boiling point organic solvent having a boiling point of 150 to 220 [deg.] C. reduced in weight to the heated azo red dye solution produced by the production method according to claim 4. Method. A method for producing a dyeing penetrant for a penetrant flaw detection test, comprising: stirring a solution containing a heated azo red dye solution, a plasticizer and a diluting solvent produced by the production method according to claim 4 . The method for producing a dyeing penetrant for a penetrant flaw detection test according to claim 6 , wherein the chlorine concentration of the dyeing penetrant is 100 ppm or less.