JP2010220970A - Process control indicator and process control method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a small process control indicator batch-controlling a plurality of data which are process control information such as completion of sterilization or disinfection and confirmation of not being a non-sterilized state after sterilization, and product management information such as lots, accurately performing process control with the clear change of color tones, easily manufactured with simple structure, and stably storable for a long period of time at an ordinary temperature. <P>SOLUTION: The process control indicator 1 is formed with at least a part of an identification code 2 or formed with a coat covering at least a part of a non-discolored identification code, on a base material 4 or on a product to be process-controlled, with an ink layer discolored under the sterilizing and disinfecting conditions of a sterilizing process of the product to be process-controlled or under overheating conditions of a storage process. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention sterilizes or sterilizes medical devices with high-pressure steam, ethylene oxide gas, formalin gas, etc., sterilizes foods such as retort foods, canned foods, and beverage cans by heating before long-term storage. When performing irradiation treatment that sterilizes or sterilizes with electromagnetic waves such as radiation, it is confirmed that sterilization or sterilization is completed, or that it is not in a non-sterile state after sterilization, or is stored at low temperature The present invention relates to a process management indicator used for confirming that an article is not exposed to an overheated state, and a process management method using the process management indicator.

  Pharmaceuticals, hygiene products, and medical equipment used in medical care are sterilized in advance so that they can be used in a nearly aseptic state, and processed foods such as retort foods, canned foods, and beverage cans prevent food poisoning damage and rot for a long time. Pre-sterilized so that it can be stored without Medical instruments such as scalpels and forceps, sanitary products such as gauze are used in a high-pressure steam atmosphere in an autoclave, and medical instruments such as catheters, injection needles, and probes for medical equipment are used in an ethylene oxide gas atmosphere or formalin. Under a gas atmosphere, they are sterilized and sterilized under heating conditions such as retort foods, canned foods and beverage cans. Drugs that should be stored at low temperatures, such as vaccines and blood products, are sterilized and stored at low temperatures under irradiation with electromagnetic waves such as ultraviolet rays and radiation.

  During sterilization and sterilization, a sufficient amount of high-pressure steam for sterilization and sterilization, ethylene oxide gas, electromagnetic waves such as ultraviolet rays and radiation, etc. In addition, a chemical indicator that changes color in response to formalin gas is interposed, and whether or not sterilization or sterilization is sufficiently performed is easily confirmed visually. As such a chemical indicator, for example, in Patent Document 1, a non-discoloration identification code that can be read by a barcode reader is attached to each basket in which a plurality of containers filled with contents are stored, and a monitoring tag attached to the basket is attached. A heat sterilization system is disclosed that is coated with a temperature indicating ink that is irreversibly discolored at the heating temperature during the heat sterilization process. Process information indicating whether or not sterilization has been sufficiently performed with such a chemical indicator is managed by changing the color tone, and container lot information is managed by digital data of barcodes using an identification code. In the unlikely event that a process management error occurs, health damage such as food poisoning may occur. Also, normal product management operations can be complicated. Moreover, only a single piece of information can be obtained from both the chemical indicator and the identification code in a wide range.

  In addition to pharmaceutical products that should be stored at low temperatures for a long period of time after sterilization, a bioindicator that discolors in response to products metabolized by microorganisms under viable breeding conditions such as room temperature in the medium is placed. It is easily confirmed visually that it is not exposed to the condition of breeding live bacteria. As such a bioindicator, for example, Patent Document 2 contains an acid-producing microorganism and a color indicator by an acid that it produces at room temperature, and perishable foods and the like have been exposed to deterioration conditions such as room temperature. An indicator that indicates this in a discolored manner is disclosed. The bioindicator has to be stored refrigerated so as not to change its color when not in use, and it is troublesome. In addition, the degree of color change is likely to be different due to a subtle temperature difference and may not be detected accurately.

JP 2002-131145 A Special table 2007-505614

  The present invention has been made to solve the above-described problems, and includes process management information such as confirmation that sterilization or sterilization has been completed or that the product has not become non-sterile after sterilization, and product management information such as a lot. It is possible to manage a plurality of data in a lump, and process control can be performed accurately with clear changes in color tone, and it can be easily manufactured with a simple structure and stable for a long time at room temperature. It is an object of the present invention to provide a small process management indicator that can be stored and a process management method using the same.

  The process control indicator according to claim 1, which has been made to achieve the above object, includes a sterilization condition of a sterilization process of a product to be controlled, a sterilization condition of a sterilization process, or an overheating of a storage process. In the ink layer that changes color under conditions, at least a part of the identification code is formed on the substrate or the product, or a film covering at least a part of the non-color change identification code is formed.

  The process control indicator according to claim 2 is the process control indicator according to claim 1, wherein the ink layer reacts with a metal salt or a heavy metal complex compound under a high-pressure steam sterilization condition, and a sulfur-containing compound that changes color irreversibly. An ink layer containing an azo dye and an organic acid or a salt thereof irreversibly discolored in response to ethylene oxide under high-pressure steam sterilization conditions, retort sterilization conditions or ethylene oxide gas sterilization conditions; formalin gas Ink layers containing azo dyes, hydrazines and / or pyrimidines that change irreversibly in response to formaldehyde under sterilization conditions; ink layers containing metal complex compounds that change irreversibly under superheat conditions; from ultraviolet rays and radiation High content having at least one of a halogen group and an acetal group and a hydroxyl group that is discolored by a selected electromagnetic wave A radiation-colorable composition comprising a compound, a color-forming electron donor organic compound, an active species-generating organic compound that colors the electron-donor organic compound, and a radiation absorber and / or a radiation fluorescent agent Or at least one selected from an ink layer formed of a radiation-colorable composition containing at least one of a polyacetylene compound and a diarylethene compound.

  A process management indicator according to a third aspect is the one according to the first aspect, wherein the identification code and the non-color-changing identification code are a one-dimensional barcode or a two-dimensional code.

  A process management indicator according to a fourth aspect is the process management indicator according to the first aspect, wherein the identification code is identifiable by a code reader or visually by the discoloration.

  The process management indicator according to claim 5 is the process management indicator according to claim 1, wherein the non-color-changing identification code is concealed by the discoloration of the coating and cannot be identified with a code reader or visually. It is characterized by.

  The process management indicator according to claim 6 is the one described in claim 1, wherein at least a part of the middle of the coating, a character or a graphic that displays the sterilization condition or the overheating condition when the ink layer comes off, It is characterized by forming.

  The process management method according to claim 7 is an ink layer that changes color under the sterilization condition of the sterilization process of the product to be process controlled, the sterilization process of the sterilization process, or the overheating condition of the storage process, on the substrate or the product. Forming a coating in which at least part of the identification code or at least part of the non-discoloring identification code is concealed, and the resulting process control indicator is displayed under said sterilization condition, sterilization process condition or overheating condition When exposed to sterilization, the identification code detects a history of completion of sterilization or a history of overheating.

  The process control indicator of the present invention is used for sterilization or sterilization processes such as high-pressure steam sterilization, ethylene oxide gas sterilization, formalin gas sterilization, and radiation sterilization of products to be sterilized such as pharmaceuticals, medical instruments, and retort foods. It is possible to display the completion of sterilization or sterilization, display that it can be maintained in a sterilized state after sterilization, or confirm that the cryopreserved product is not exposed to an overheated state It is. Since this process management indicator is displayed with an identification code that can be read instantaneously by a code reader, process management information such as a sterilization process, storage process, and distribution process is managed as digital data corresponding to the identification code. be able to.

  Furthermore, since this process control indicator can be directly attached to a product to be process controlled, it is possible to simultaneously display a plurality of data such as product management information such as the product number, lot and quality, and process management information. And can be used to collectively manage multi-factor information. In addition, since this process management indicator can display such information with a clear change in color tone, there is no risk of process management while misidentifying.

  This process control indicator can be stably stored without deterioration at room temperature for a long time before use, and can be maintained for a long time without being discolored in an irreversible discolored state or undiscolored state after use. Can be stored as evidence of sterilization or sterilization detection.

  The process management indicator is small because it can display a plurality of information in a narrow area such as a barcode. In addition, since it has a simple structure, it can be easily manufactured at low cost and in large quantities.

  According to the process control method using this process control indicator, when a large number of products to be controlled are sterilized or sterilized at one time, products that could be sterilized or sterilized only insufficiently or only a part of them when stored in large numbers Since the product having deteriorated can be quickly and accurately distinguished by reading the identification code by the code reader, the work time for inspection can be greatly reduced.

It is a top view which shows the use middle of the process control indicator to which this invention is applied. It is a top view which shows the middle of use of another process control indicator to which this invention is applied. It is a top view which shows the middle of use of another process management indicator to which this invention is applied. It is a top view which shows the middle of use of another process control indicator to which this invention is applied. It is a top view which shows the middle of use of another process control indicator to which this invention is applied. It is a top view which shows the middle of use of another process control indicator to which this invention is applied.

  Hereinafter, modes for carrying out the present invention will be described in detail, but the scope of the present invention is not limited to these modes.

  A preferred example of the process control indicator of the present invention will be described with reference to FIG.

  The process management indicator 1 has a square label shape. A white high-pressure vapor-color-changing ink layer containing a metal salt or a heavy metal complex compound and a sulfur-containing compound that reacts irreversibly with a high-pressure steam sterilization condition and changes color to black, for example, on a white label substrate 4 An identification code 2 such as a one-dimensional bar code such as a JAN (Japanese Article Number) code or an EAN-128 code is formed. The white identification code 2 is not confused with the white background of the substrate 4. Along with the identification code 2, character information 3 corresponding to the identification code 2 is formed by a black non-color-changing ink layer.

  This process control indicator 1 is produced as follows. First, a metal salt or heavy metal complex compound, a sulfur-containing compound, a binder resin, and a solvent are kneaded to prepare a white high-pressure vapor discoloration indicator ink. This indicator ink is printed on the white substrate 4 as a one-dimensional barcode corresponding to specific data such as a product number that can be read by a barcode reader, and an identification code 2 formed of a white water vapor discoloring ink layer. And Next, when barcode data 3 is printed with black non-color-changing ink, a label-like process management indicator 1 is obtained.

  A process management method using the process management indicator 1 is as follows. The process control indicator 1 is affixed to the product which should manage a sterilization process. At this time, since the identification code 2 is not visible and cannot be read by a bar code reader, it can be seen at a glance that the product to be process-controlled is in an unsterilized state. The product to be processed is inserted into the high-pressure steam sterilizer together with the process control indicator 1 and sealed, and then sterilized with high-pressure steam. When sterilized, the sulfur-containing compound in the ink layer of the identification code 2 reacts with the metal salt or the heavy metal complex compound and chemically changes to another black sulfur compound, and as a result, the black identification code 2 appears. Remove the product to be processed from the autoclave. The black identification code 2 whose color has changed can be visually checked, and can also be read by a barcode reader. When the identification code 2 is recognized visually or by a barcode reader, a history that sterilization is completed is displayed. Since this identification code 2 also displays specific data such as the product number, the process management information such as the sterilization completion history and the product management information such as the product number are displayed simultaneously with one identification code. Has been.

  Although the example in which the character information 3 is non-discolored has been shown, it may be discolored under high-pressure steam sterilization conditions by printing with indicator ink as with the identification code 2.

  As shown in FIG. 2 showing another embodiment of the process control indicator 1, the identification code 2 includes a color change identification code portion 6 formed of the same high-pressure vapor color change indicator ink layer as described above, and a black non-color change property. It may consist of a non-color-changing identification code part 5 formed of an ink layer. In this case, before the high-pressure steam sterilization, one discoloration identification code portion 6 in the barcode does not appear, so the identification code 2 is incomplete and cannot be read by the one-dimensional barcode reader. ing. After sterilization, the color-changing identification code portion 6 changes its color tone to black, so that the identification code 2 becomes complete and can be read by a barcode reader.

  As shown in FIG. 3, in the process management indicator 1, the identification code 2 may be a two-dimensional code, for example, a QR code (registered trademark). As shown in FIG. 3, the identification code 2 is formed of a color-changing identification code portion 8 that is a dot-shaped data cell region formed of the same high-pressure vapor color-changing indicator ink as described above, and a black non-color-changing ink. It may consist of a non-color-changing identification code portion 7 at three corners which is a finder pattern for detecting the cage position. In this case, since the discoloration identification code portion 8 does not appear before autoclaving, the identification code 2 is incomplete and cannot be read by the two-dimensional code reader. After sterilization, the color-changing identification code portion 8 changes its color to black, so that the identification code 2 becomes complete and can be read by a code reader. In addition, although the example in which the non-color-changing identification code part 7 that is a finder pattern is non-color-changing has been shown, as with the color-changing identification code part 8 that is a data cell area, by printing with indicator ink, The color may be changed under sterile conditions.

  As shown in FIG. 4, the process control indicator 1 may be entirely covered with a coating 10 formed of a water vapor color change indicator ink layer having the identification code 2 that is non-color changeable and similar to the above. . In this case, the identification code 2 appears before autoclaving and can be read by a bar code reader. After sterilization, the color of the coating 10 changes to black. As a result, the identification code 2 is concealed and cannot be viewed or read by a barcode reader. Since the ink layer is not formed in the middle part of the coating 10, white letters 9 and figures indicating completion of sterilization, such as white letters “OK” and “sterilized”, are formed. It may be.

  As shown in FIG. 5, the process management indicator 1 is a coating 10 formed of a water vapor color change indicator ink similar to the above in which the identification code 2 is non-color-changing, and is attached to each barcode of the identification code 2. Only a part may be covered so as to be inclined. In this case, after the sterilization, the coating 10 changes to a black color, and one or more crossing lines such as strike-through lines appear on the identification code 2 due to the coating 10.

  As shown in FIG. 6, the process control indicator 1 has a non-color-changeable barcode portion printed in advance, and a sticker 11 having an ink layer printed on the front surface with the same water-color-change color indicator ink as described above is affixed. It may be what has been done. In this case, since the seal 11 is light white, the barcode can be read before the color change. Since this ink layer is discolored by ultraviolet rays or radiation, when the ultraviolet rays or radiation is applied after applying the seal 11, the seal 11 is colored red. This makes the barcode unreadable.

  The discoloration coating that covers the discoloration identification code or non-discoloration identification code of the process control indicator contains a metal salt or heavy metal complex compound and a sulfur-containing compound, and discolors under high-pressure steam sterilization conditions or under retort sterilization An example formed with an ink layer is shown, but an ink layer containing an azo dye and an organic acid that changes color under high-pressure steam sterilization conditions or ethylene oxide gas sterilization conditions, an azo dye that changes color under formalin gas sterilization conditions, and / or Or an ink layer containing hydrazine, an ink layer containing an ink layer containing a metal complex compound that changes color under overheating, or irreversibly discolored by reacting under sterilization or sterilization conditions using electromagnetic waves such as ultraviolet rays or radiation. A polymer having at least one of a halogen group and an acetal group and a hydroxyl group, a color-forming electron donor organic compound, and an electronic child At least one of a radiation-colorable composition containing an active species-generating organic compound for coloring a body organic compound and a radiation absorber and / or a radiation fluorescent agent, or a polyacetylene compound and a diarylethene compound was included It may be formed with an ink layer containing a radiation coloring composition. The color change identification code may be separately applied with a plurality of different color change ink layers. The color-changing identification code may be readable by a code reader as separate data before and after sterilization.

  The preferred composition of the discoloration component formed of the metal salt or heavy metal complex compound used in the process control indicator for high-pressure steam sterilization and the sulfur-containing compound is 2 to 30 parts by weight of the metal salt or heavy metal complex compound, and the sulfur-containing compound. 5 to 30 parts by weight. As a result of the reaction between the metal salt and the sulfur-containing compound under high-pressure steam to produce a metal sulfide, the indicator develops color.

  Examples of the metal salts include bismuth compounds such as bismuth oxalate, bismuth sulfate, bismuth chloride, bismuth oxide, basic bismuth carbonate, bismuth hydroxide, bismuth nitrate nitrate, basic bismuth acetate, basic bismuth nitrate, bismuth benzoate. , Bismuth molybdate, bismuth trititanate, etc., and cobalt compounds such as cobalt nitrate hexahydrate, cobalt chloride hexahydrate, anhydrous cobalt chloride, basic cobalt carbonate, cobalt carbonate, cobalt oxide, cobalt oxalate Dihydrate, cobalt sulfate heptahydrate and the like. As the nickel compound, nickel nitrate hexahydrate, anhydrous nickel chloride, nickel chloride hexahydrate, basic nickel carbonate, nickel acetate tetrahydrate, Nickel oxide, nickel sulfate hexahydrate, nickel sulfate heptahydrate, nickel oxalate Hydrates, etc., and chromium compounds include chromium nitrate nonahydrate, chromium chloride hexahydrate, chromium oxide, chromium sulfate n hydrate, etc., and iron compounds such as iron sulfate and iron nitrate 9 water. Japanese compounds are included, lead compounds include lead sulfate, lead chloride, lead oxide, lead hydroxide, etc., copper compounds include copper sulfate, copper chloride, copper oxide, copper hydroxide, etc., silver compounds Examples thereof include silver sulfate, silver chloride, silver oxide, and silver hydroxide. The metal salts may be any one of these or a mixture of plural kinds.

  The heavy metal complex compound may be a hydrate containing water of crystallization or a hydrated body. The heavy metal complex compound is, for example, a heavy metal-hexamethylenetetramine complex compound, a decahydrate or a hydrate of a complex of cobalt nitrate and hexamethylenetetramine, or a decahydrate of a complex of cobalt nitrate, nickel nitrate and hexamethylenetetramine. , Nickel nitrate and hexamethylenetetramine complex 10 hydrate, cobalt oxide and hexamethylenetetramine complex 9 hydrate, cobalt chloride and hexamethylenetetramine complex 10 hydrate, and the like. Examples of the heavy metal-phosphate complex compound include cobalt phosphate octahydrate and cobalt ammonium phosphate monohydrate, and examples of the heavy metal-ammonium complex compound include cobalt ammonium chloride hexahydrate, cobalt ammonium sulfate hexahydrate. And ammonium chrome sulfate dodecahydrate. . The heavy metal complex compound may be any one of these or a mixture of plural kinds.

  Examples of the sulfur-containing compound include thiourea compounds such as thiourea, 1,3-dimethyl-2-thiourea, 1,3-diethyl-2-thiourea, 1,3-ditolylthiourea, 2,2′-ditolylthiourea, 1,3-diphenyl-2-thiourea, 1-phenyl-2-thiourea, allylthiourea, 1-acetyl-2-thiourea, ethylenethiourea, trimethylthiourea, tolylthiourea, methylthiourea, ethylthiourea, 1- (3-acetylphenyl) -2-thiourea, 1-allyl-3,3-diethyl-2-thiourea, 1-benzoyl-2-thiourea, 1-benzyl-3-phenethyl-2-thiourea, 1 -(2-bromophenyl) -2-thiourea, 1- (2-chlorophenyl) -3-phenyl-2-thiourea, 1-phenyl-3- (2-thiazolyl) thiourea, 1, Examples include 1-dimethylthiourea, 1,3-dibenzylthiourea, 1-butylthiourea, 1-phenyl-3-thiosemicarbazide, 4-phenyl-3-thiosemicarbazide, thiocarbohydrazide, and the like. Examples include thiuram tetrasulfide, examples of the thiazole compound include 2-aminobenzothiazole, examples of the sulfur-containing amino acid compound include methionine, cysteine, and thiamine nitrate. Examples of the sulfur-containing protein include the aforementioned sulfur-containing amino acid compound. Examples of the sulfur-containing organic acid compound include thiosalicylic acid and thioglycolic acid. The sulfur-containing compound may be any one of these or a mixture of plural kinds. Since the sulfur-containing compound is harmless and highly safe, it is even more preferable to use food additives such as methionine, cysteine, thiamine nitrate, thiosalicylic acid, and thioglycolic acid.

  The composition of the discoloration component formed by the azo dye and the organic acid or salt thereof used in the process control indicator for high-pressure steam sterilization or ethylene oxide gas sterilization is 0.1 to 10 parts by weight of the azo dye, and the organic acid or salt thereof. 1 to 30 parts by weight. Protons generated under high pressure steam cationize the azo dye causing a change in its electron density, resulting in a color change of the indicator. Further, ethylene oxide reacts with the azo dye to change the resonance structure, and further, the reaction is further promoted by generation of protons due to the coexistence of the organic acid, so that the indicator changes color.

  Examples of the azo dye include C.I. I. (Color index) Disper thread 4, C.I. I. Disperse thread 17, C.I. I. Disperse thread 54, C.I. I. Disperse thread 58, C.I. I. Disperse thread 72, C.I. I. Disperse thread 73, C.I. I. Disperse thread 88, C.I. I. Disperse thread 110, C.I. I. Disperse thread 111, C.I. I. Disperse thread 117, C.I. I. Disper thread 137, C.I. I. Disperse thread 152, C.I. I. Disperse thread 153, C.I. I. Disperse thread 154, C.I. I. Disper thread 202, C.I. I. Disperse thread 206, C.I. I. Disperse violet 38, C.I. I. Disperse violet 43, C.I. I. Disperse Violet 93, C.I. I. Disperse Blue 79, C.I. I. Disperse blue 102, C.I. I. Disperse Blue 165, Solbend Yellow 2, Solbend Yellow 14, Solbend Yellow 16, Solbend Yellow 56, Solbend Red 3, Solvent Red 18, Solvent Red 24, Acid Red 4, Acid Red 81, Acid Red 249, Acid Red 257, acid orange 7, acid yellow 49, acid blue 113, direct yellow 44, direct yellow 86, direct red 31, direct red 79, direct red 80, direct blue 71, direct black 19, direct orange 26, etc. .

  As other dyes, pH dyes and leuco dyes may be used.

  An organic acid or a metal salt thereof is a component that promotes discoloration and adjusts discoloration conditions. Examples of the organic acid include acrylic acid, adipic acid, L-aspartic acid, azelaic acid, benzoic acid, anthranilic acid, isophthalic acid, itaconic acid, undecylenic acid, citric acid, glutaconic acid, salicylic acid, cyanuric acid, diglycolic acid, DL-tartaric acid, sulfanilic acid, sebacic acid, sorbic acid, terephthalic acid, naphthenic acid, nicotinic acid, hippuric acid, barbituric acid, pivalic acid, pyruvic acid, phthalic acid, fumaric acid, benzylic acid, maleic acid, malonic acid, Examples include methacrylic acid and metanilic acid. Examples of the metal salt of the organic acid include calcium salts and zinc salts of the above organic acids. Of these, calcium salicylate, zinc salicylate, zinc benzoate and adipic acid are preferred.

  The preferred composition of the discoloration component formed by the same kind of azo dye, pyrimidines and hydrazines used in the process control indicator for sterilizing formalin gas is 0.4 to 1.5 parts by weight of the azo dye and the pyrimidines are 1 to 20 parts by weight and 2 to 30 parts by weight of hydrazines. When the azo dye, hydrazines or pyrimidines are exposed to formaldehyde and the pH changes, the indicator changes color.

  Examples of hydrazines include hydrazine hydrochloride, hydrazine sulfate, hydrazine benzoate, carbazine acid, acetohydrazide, benzhydrazide, isonicotinic acid hydrazide, 2,4-dinitrophenylhydrazide, maleic acid hydrazide, isophthalic acid hydrazide, p-toluenesulfonyl And hydrazide.

  Examples of pyrimidines include 4-amino-5-aminomethyl-2-methylpyrimidine dichloride, 4-amino-6-chloro-2-mercaptopyrimidine, 2-amino-4-chloro-6-methylpyrimidine, 2-amino -6-chloro-4-pyrimidinol, 2-amino-4,6-dichloropyrimidine, 2-amino-4,6-dihydroxypyrimidine, 4-amino-2,6-dihydroxypyrimidine, 2-amino-4,6- Dimethylpyrimidine, 4-amino-6-hydroxy-2-mercaptopyrimidine, 2-amino-4-hydroxy-6-methylpyrimidine, 4-amino-2-mercaptopyrimidine, 2-amino-4-methylpyrimidine, 2-amino -5-nitropyrimidine, 2-aminopyrimidine, 4-aminopyrimidine, 4-chloro-2 , 6-Diaminopyrimidine, 6-chloro-2,4-dimethoxypyrimidine, 4-chloro-2-methylthiopyrimidine, 2-chloropyrimidine, 5,6-diamino-2,4-dihydroxypyrimidine, 2,4-diamino- 6-hydroxypyrimidine, 2,4-diamino-6-mercaptopyrimidine, 4,5-diaminopyrimidine, 2,4-dichloro-6-methylpyrimidine, 4,6-dichloro-2-methylthio-5-phenylpyrimidine, 4 , 6-dichloro-5-nitropyrimidine, 2,4-dihydroxy-5,6-dimethylpyrimidine, 4,6-dihydroxy-2-mercaptopyrimidine, 4,6-dihydroxy-2-methylmercaptopyrimidine, 2,4- Dihydroxy-6-methylpyrimidine, 4,6-dihydroxy-5-nitropyrimidine 4,6-dihydroxypyrimidine, 2,4-dihydroxypyrimidine-5-carboxylic acid, 2,4-dimethyl-6-hydroxypyrimidine, 4,6-dimethyl-2-hydroxypyrimidine, 4,6-dimethyl-2 -Mercaptopyrimidine, 2-hydroxy-4-methylpyrimidine hydrochloride, 4-hydroxypyrazolo [3,4d] pyrimidine, 2,4,5-triaminopyrimidine, 2-mercaptopyrimidine, 5-nitro-4,6- And triaminopyrimidine.

  It is preferable that the metal complex compound used for the process control indicator for detecting overheating is used in an amount of 10 to 50 parts by weight of the total ink. When the structure of the metal complex compound changes due to overheating, the indicator changes color.

  Examples of the metal complex compound include a cobalt chloride / hexamethylenetetramine complex, a cobalt sulfate / hexamethylenetetramine complex, a cobalt nitrate / hexamethylenetetramine complex, and a nickel chloride / hexamethylenetetramine complex.

  A radiation-colorable composition used for an indicator that changes color by radiation includes a polymer compound having at least one of a halogen group and an acetal group and a hydroxyl group, a color-forming electron donor organic compound, and an electron donor A radiation-colorable composition containing an active species-generating organic compound that colors the body organic compound and a radiation absorber and / or a radiation fluorescent agent, or at least one of a polyacetylene compound and a diarylethene compound The radiation coloring composition is applied to at least a part of the substrate surface, and the radiation coloring composition comprises 5 to 50 parts by weight of the polymer compound and 0.01 to 50 parts by weight of the polymer compound. Color-forming electron donor organic compound, 0.1 to 50 parts by weight of the active species-generating organic compound, 0.1 to 500 parts by weight of radiation absorber and / or radiation fluorescent agent It is preferably a composition comprising a.

  This polymer compound has the following formula (1):

(In the above formula, X is a halogen atom, -R ₁ is a hydrogen atom, cyano group, alkyl group, aryl group, alkoxy group, alkoxycarbonyl group, aliphatic carbonyloxyl group, carboxyl group, aryloxy group, aralkyl group, or An aralkoxy group, wherein l, m, and n are arbitrary ratios), and may be a random copolymer or a block copolymer. The ratio of l: m: n is, for example, preferably 50 to 99: 1 to 30: 1 to 20 by weight of monomers constituting those repeating units.

  Also, the following formula (2)

(In the formula (2), -R ₂ and -R ₃ are the same or different and are an aliphatic carbonyloxy group such as a hydrogen atom, cyano group, alkyl group, aryl group, alkoxy group, alkoxycarbonyl group, acetoxy group, A carboxyl group, an aryloxy group, an aralkyl group, or an aralkoxy group, and p, q, and r are arbitrary ratios)), and may be a random copolymer or a block copolymer Also included are compounds. The equivalent ratio of p: q: r is preferably 5 to 90:10 to 50: 1 to 30 in terms of molar ratio.

  These polymer compounds may be used singly or as a mixture of two or more kinds, or another polymer compound may be mixed.

  The color-providing electron donor organic compound is usually colorless or light-colored and has a property of developing color by the action of an active species such as Bronsted acid or Lewis acid, that is, an electron acceptor. Specifically, triphenylmethanephthalides such as crystal violet lactone, malachite green lactone; fluorans such as 3-diethylaminobenzo-α-fluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-dibenzyl Aminofluorane, 3,6-dimethoxyfluorane; phenothiazines such as 3,7-bisdimethylamino-10- (4′-aminobenzoyl) phenothiazine; indolylphthalides such as 3,3-bis (1-ethyl- 2-methylindol-3-yl) phthalide, 3,3-bis (1-n-butyl-2-methylindol-3-yl) phthalide; leucooramines such as N- (2,3-dichlorophenyl) leucoora Min, N-phenylauramine; Rhodaminelac Rhodamine-β-o-chloroaminolactam; Rhodamine lactones such as Rhodamine-β-lactone; Indolines such as 2- (phenyliminoethanedilidene) -3,3′-dimethylindoline, p-nitrobenzylleucomethylene blue Benzoylleucomethylene blue; triarylmethanes such as bis (4-diethylamino-2-methylphenyl) phenylmethane and tris (4-diethylamino-2-methylphenyl) methane. They may be used alone or as a mixture of two or more.

  The active species-generating organic compound is one in which an active species is irreversibly generated by irradiation with radiation, and examples thereof include compounds having a halogen group such as carbon tetrabromide, tribromoethanol, and tribromomethylphenylsulfone.

  The radiation absorber is a metal of barium, yttrium, silver, tin, hafnium, tungsten, platinum, gold, lead, bismuth, zirconium, europium, cerium, and compounds containing these metals, such as sulfates and carbonates of these metals. And nitrates. They may be used alone or as a mixture of two or more.

The radiation-excited fluorescent agent is a salt represented by CaWO ₄ , MgWO ₄ , HfP ₂ O ₇ , ZnS: Ag, ZnCdS: Ag, CsI: Na, CsI: Tl, BaSO ₄ : Eu ²⁺ , Gd ₂ O ₂ S: Examples include Tb ³⁺ , La ₂ O ₂ S: Tb ³⁺ , Y ₂ O ₂ S: Tb ³⁺ , Y ₂ SiO ₅ : Ce, LaOBr: Tm ³⁺ , BaFCl: Eu ²⁺ , and BaFBr: Eu ^2+. . The fired product of ZnS: Ag is obtained by firing with zinc sulfide as a main component and adding silver as a heavy metal activator. Other fired products can be obtained in the same manner. They may be used alone or as a mixture of two or more.

  In addition to the above components, other colored pigments, extender pigments, binders, and solvents may be added to the indicator ink used when producing these process control indicators. For example, adding silica, calcium carbonate, titanium dioxide, talc, magnesium carbonate, barium sulfate, calcium stearate, Seica First Yellow, chrome yellow, phthalocyanine blue, phthalocyanine green, etc. improves storage stability and discoloration in the ink state Can be planned.

  Examples of the binder include butyl rubber, methyl cellulose, ethyl cellulose, nitrocellulose, vinyl acetate, vinyl chloride, hydroxymethyl cellulose, carboxymethyl cellulose, polyvinyl alcohol, polyvinyl butyral, acrylic resin, phenol resin, nylon, synthetic resin, natural resin, alkyd resin. , Polyester resin, polyamide resin, ketone resin, melamine resin, polyurethane resin, silicone resin, fluorine resin, urea resin, polyol resin, epoxy polyester resin, Alkit modified silicone, Alkit resin melamine resin mixed, vinyl chloride vinyl acetate Examples thereof include a coalesced resin and a vinyl acetate methyl methacrylate copolymer resin.

  Solvents include water, methanol, ethanol, isopropanol, butyl alcohol, hexyl alcohol, methyl acetate, ethyl acetate, propyl acetate, isobutyl acetate, butyl acetate, acetone, 2-butanone, cyclohexane, isophorone, methyl ethyl ketone, 4-methyl-2 -Pentanone, ethyl ether, isopropyl ether, tetrahydrofuran, dioxane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, 2-hexane, isooctane, solvent naphtha, methylene chloride, propylene chloride, ethylene chloride, chloroform, dichloroethane, 1,1,2- Trichloroethane, carbon tetrachloride, benzene, toluene, xylene, chlorobenzene, N, N-dimethylformamide, N-methyl-2-pyrrole Emissions, dimethyl sulfoxide, acetic acid and the like. They may be used alone or as a mixture of two or more.

  The medium of the indicator ink mixed with a binder or a solvent may be a commercially available product, or may be a solvent type medium or a UV curable type medium.

  Indicator ink mixes these components using kneading machines, such as a ball mill, a roll mill, a sand mill, and a likai machine.

  The ink is printed as an identification code on a printed material. As a substrate for printing the process control indicator, a substrate made of paper such as high-quality paper or crepe paper, plastic, metal, synthetic paper, fabric, or non-woven fabric, such as a card, tape, sheet, bag, or these And a product packaging base material to be process-controlled formed of the base material, such as a paper packaging sheet and a paper packaging bag. The identification code may be formed by directly printing the indicator ink on the substrate or the product to be process-controlled by letterpress printing / offset printing, gravure printing, flexographic printing, screen printing, coater printing, inkjet printer, or the like. Instead of printing, the identification code may be formed by applying, spraying, or dipping indicator ink.

  Embodiments of the process management indicator and the process management method using the same according to the present invention will be specifically described below.

Example 1
A process control indicator used for sterilization under a high-pressure steam atmosphere was produced as follows. First, 100 g of bismuth hydroxide as a thermochromic substance, 50 g of 1-phenyl-2-thiourea, 10 g of calcium carbonate, 350 g of UV161 (trade name of T & K TOKA) as a binder and 300 g of ethyl acetate. The mixed medium was kneaded to prepare an indicator ink for high-pressure steam sterilization process management. With this ink, a barcode-like identification code as shown in FIG. 1 was printed on a high-quality tack paper piece by letterpress printing to obtain a label-like process control indicator. Since this identification code is white, it was not recognized by the barcode reader. This indicator was affixed to a sterilization bag as a product to be process-controlled, inserted into a high-pressure steam sterilizer that was an autoclave, and sterilized at 134 ° C. for 10 minutes. Sterilization is sufficiently performed under these conditions. After completion of sterilization, the identification code was colored and appeared as a barcode, and it was confirmed that the barcode could be read by a barcode reader, whereby data management of the sterilization process could be performed.

(Example 2)
A process control indicator used for sterilization in an ethylene oxide gas atmosphere was prepared as follows. First, as an ethylene oxide coloring material, C.I. I. Kneading 400 g of Disperse 177, 10 kg of salicylic acid, 700 g of talc, 20 kg of FBHD medium (trade name, manufactured by Toyo Ink Manufacturing Co., Ltd.) as a binder, and 6 kg of a mixed solvent of n-propanol and propyl acetate Thus, an indicator ink for ethylene oxide gas sterilization process management was prepared. With this ink, a barcode-like identification code as shown in FIG. 1 was printed on a high-quality tack paper piece by gravure printing to obtain a label-like process control indicator. The identification code was red, and it was not recognized by the barcode reader in this color tone. This indicator was attached to a sterilization bag, inserted into an ethylene oxide gas sterilizer, and sterilized for 4 hours under the conditions of an ethylene oxide gas concentration of 530 mg / l, a temperature of 50 ° C., and a relative humidity of 50% Rh. Sterilization is sufficiently performed under these conditions. After completion of sterilization, the identification code was colored and appeared as a blue barcode, and it was confirmed that the barcode could be read by a barcode reader, thereby enabling data management of the sterilization process.

Example 3
The process control indicator used in the case of retort sterilization by heating was produced as follows. First, 35 g of bismuth hydroxide as a thermochromic substance, 100 g of thiourea, 500 g of a mineral spirit solution of 13% butyl rubber and 300 g of mineral spirits as a binder are kneaded to control the retort sterilization process. An indicator ink was prepared. As shown in FIG. 4, the indicator ink is applied so as to cover the identification code, which is a bar code printed on a high-quality tack paper piece with non-color-changing ink, and a label-like shape coated with a white indicator ink layer is applied. A process control indicator was obtained. This identification code can be read by a bar code reader, and the digital data is managed as process start data. This process control indicator was attached to a retort pouch to be retorted and then retort sterilized at 110 ° C. for 20 minutes. Retort sterilization is sufficiently performed under these conditions. After the sterilization, the white indicator ink layer covering the identification code is colored to conceal the identification code, so the identification code indicating that the process has not started can not be visually confirmed and can be read with a barcode reader. I can't do it. As a result, the sterilization process could be managed.

Example 4
A process control indicator used for sterilization in a formalin gas atmosphere was prepared as follows. C. I. 7 g of Disperse 177, 200 g of hydrazine sulfate, 40 g of n-propyl gallate, and a butyl cellosolve solution of ethyl cellulose as a binder were kneaded to prepare an indicator ink for managing a formalin gas sterilization process. With this indicator ink, a barcode-like identification code as shown in FIG. 1 was printed on a high-quality paper card by screen printing to obtain a card-like process control indicator. Since this identification code is red, it was not recognized by the barcode reader. This indicator was affixed to a product to be process-controlled, and left in a desiccator filled with formalin for 24 hours for formalin gas sterilization. Sterilization is sufficiently performed under these conditions. After completion of sterilization, the identification code was colored and appeared as a blue barcode, and it was confirmed that the barcode could be read by a barcode reader, whereby data management of the sterilization process could be performed.

(Example 5)
A process control indicator used to detect exposure to a certain overheating condition was produced as follows. 800 g of a cobalt chloride / hexamethylenetetramine complex (CoCl ₂ · 2 (CH ₂ ) ₆ N ₄ · 10H ₂ O) as a warm pigment, 1000 g of an ethyl cellulose solution (xylene) as a binder, and 1500 g of xylene as a solvent The indicator ink for superheat management was prepared by kneading. With this indicator ink, a barcode-like identification code as shown in FIG. 1 was printed on a high-quality paper piece, and the laminate was processed with a polypropylene film to obtain a label-like indicator. Since this identification code is light pink, it was not recognized by the barcode reader. When this indicator is heated at 50 ° C. for 5 minutes, it is confirmed that the identification code is discolored and appears as a blue barcode and can be read by a barcode reader. did it.

(Example 6)
A process control indicator used in sterilization by ultraviolet irradiation was produced as follows. As a discoloring component, 10 g of Parkerscript Red I-6B, 10 g of carbon tetrabromide, and 100 g of PAS800 (trade name: Jujo Chemical), which is an ink medium, were mixed and kneaded with a likai machine to make an ink. The ink was printed on a transparent film, and an adhesive material was pasted thereon. A light white label was made by cutting to 40 mm x 60 mm. The label was affixed on the barcode for process control. Thereafter, UVC ultraviolet rays were irradiated at 250 mJ / cm ² for ultraviolet sterilization. The affixed label changed to red after UV irradiation and the barcode could not be read.

  The process management indicator of the present invention and the process management method using the process management indicator are used when sterilizing pharmaceuticals, medical instruments, sanitary products, etc., or sterilizing foods such as retort foods, canned foods, and beverage cans. It can be used to manage or manage overheating history when storing medicines that should be stored at a low temperature.

  1 is a process management indicator, 2 is an identification code, 3 is character information, 4 is a base material, 5 is a non-discoloring identification code part, 6 is a discoloring identification code part, 7 is a finder pattern of the non-discoloring identification code part, Reference numeral 8 denotes a data cell area of the color change identification code portion, 9 is a white character, 10 is a coating, and 11 is a seal.

Claims (7)

  An ink layer that changes color under the sterilization condition of the sterilization process of the product to be process controlled, the sterilization condition of the sterilization process, or the overheating condition of the storage process, and the identification code on the substrate or the product A process control indicator characterized in that at least a part of the film is formed or a film covering at least a part of the non-color-changing identification code is formed.   An ink layer containing a metal salt or a heavy metal complex compound and a sulfur-containing compound which changes irreversibly when reacted under high-pressure steam sterilization conditions; high-pressure steam sterilization conditions or retort sterilization conditions or ethylene oxide gas An ink layer containing an azo dye that changes irreversibly in response to ethylene oxide under sterilization conditions and an organic acid or salt thereof; an azo dye or hydrazine that changes color irreversibly in response to formaldehyde under sterilization conditions of formalin gas And / or an ink layer containing pyrimidines; an ink layer containing a metal complex compound that changes color irreversibly under superheated conditions; at least one of a halogen group and an acetal group that change color with electromagnetic waves selected from ultraviolet rays and radiation; A polymer compound having a hydroxyl group, an electron donor organic compound having a color, and an electron donor organic compound; Radiation coloration composition containing at least one of a polyacetylene compound and a diarylethene compound, or a radiation-colorable composition containing an active species-generating organic compound that causes coloration and a radiation absorber and / or a radiation fluorescent agent The process control indicator according to claim 1, wherein the process control indicator is at least one selected from an ink layer formed of an adhesive composition.   The process control indicator according to claim 1, wherein the identification code and the non-color-changing identification code are a one-dimensional barcode or a two-dimensional code.   The process control indicator according to claim 1, wherein the identification code is identifiable by a code reader or visually by the color change.   The process control indicator according to claim 1, wherein the non-color-changing identification code is concealed by the color change of the coating and cannot be identified by a code reader or visual observation.   The process control indicator according to claim 1, wherein a character or a graphic that displays the sterilization condition or the overheating condition is formed by removing the ink layer in at least a part of the middle of the coating.   An ink layer that changes color under the sterilization condition of the sterilization process of the product to be controlled, the sterilization condition of the sterilization process, or the overheating condition of the storage process, and forms at least a part of the identification code on the substrate or the product Or forming a coating in which at least a part of the non-discoloring identification code is concealed, and when the obtained process control indicator is exposed to the sterilization condition, the sterilization process condition or the overheating condition, the identification code A process management method characterized by detecting a history of completion of sterilization or a history of overheating.

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