JP6177302B2 - Hydrogen peroxide gas detection indicator - Google Patents

Description

  The present invention relates to a hydrogen peroxide gas detection indicator.

  Various equipment and instruments used in hospitals, laboratories and the like are sterilized for disinfection and sterilization. A typical sterilization method is sterilization with hydrogen peroxide gas. In this sterilization process, it is necessary to install an indicator for confirming whether the sterilization process is completed. Specifically, it is necessary to install in the sterilizer an indicator that changes color according to the atmospheric gas concentration in the processing system and the exposure time.

  As a conventional technique related to the above indicator, for example, when monitoring a sterilization process in low-temperature gas plasma sterilization using a gas containing peracetic acid and acetic acid as main components, an indicator using bromophenol blue, which is one of pH indicators, is excessive. A method of detecting sterilization by changing the color from bright blue to light yellow by the action of acetic acid or acetic acid gas (Patent Document 1) is known.

  In addition, an indicator characterized by comprising a dye, a color change aid, and a binder and causing a change in color tone by a plasma sterilization method and a hydrogen peroxide gas sterilization method is known (Patent Document 2, Patent). Reference 3). An ink composition for detection of plasma sterilization containing an anthraquinone dye having at least one amino group of a primary amino group and a secondary amino group is known (Patent Document 2).

  Furthermore, an indicator is known that is made of a specific resin or pigment, and that can visually recognize the color change according to the hydrogen peroxide gas concentration more reliably by the hydrogen peroxide gas sterilization method (Patent Document 3).

US Pat. No. 5,482,684 Japanese Patent No. 4151932 Japanese Patent No. 4606964

  However, if the indicator of Patent Document 1 is left as it is after discoloration due to sterilization, the color after discoloration may return to the original color, which is problematic in terms of stability after discoloration. When the discoloration of the indicator returns to the original color, it becomes unclear whether or not the equipment placed in the apparatus has undergone a sterilization process.

  Moreover, in patent documents 2-3, since the progress of the discoloration at the initial stage of hydrogen peroxide gas exposure is relatively slow, discoloration occurs according to the CT value, which is an integrated value of the hydrogen peroxide concentration and time, and sterilization of the object to be processed. It is noted that it is very useful for knowing the status of each individual. However, these indicators are unsuitable for a decontamination process for disinfecting and sterilizing a space or operating room where a pharmaceutical manufacturing apparatus is installed using hydrogen peroxide gas. A general hydrogen peroxide gas sterilizer is dehumidified in a vacuum process or a plasma process, and is performed at 40 ° C or higher. On the other hand, decontamination with a low sterilization guarantee level is lower than that of a medical device. The hydrogen peroxide gas concentration and exposure time are often shorter than sterilization. Therefore, the discoloration reaction does not proceed sufficiently with the indicator for confirming the sterilization process, and even if the decontamination is actually completed, a discoloration defect may occur. In addition, the discoloration reaction is promoted or inhibited by the influence of humidity, and there is a problem that the completion of decontamination and the discoloration of the indicator do not correlate. That is, an indicator that can be used even for decontamination needs to be completely discolored without being affected by humidity and under a lower hydrogen peroxide exposure condition in a lower temperature environment.

  Accordingly, a main object of the present invention is to provide a hydrogen peroxide gas detection indicator capable of adjusting the influence on discoloration due to humidity.

  As a result of intensive studies to solve the problems of the prior art, the present inventor has found that the above object can be achieved by employing an ink composition having a specific composition, and has completed the present invention. .

That is, the present invention relates to the following hydrogen peroxide gas detection indicator.
1. 1) a hydrogen peroxide gas detection indicator comprising a discoloration layer made of a hydrogen peroxide gas detection ink composition containing at least one kind of ketone-based resin and 2) at least one methine dye;
The ink composition for detecting hydrogen peroxide gas has a methine dye content of 0.1 to 1% by weight and a ketone resin content of 1 to 35% by weight of the methine dye and the ketone resin. When the composition is 9 to 18 parts by weight of a ketone resin with respect to 0.2 parts by weight of a methine dye, and when exposed to hydrogen peroxide gas at 12.5 mg / L in the discolored layer, the relative humidity before exposure Hydrogen peroxide gas detection indicator with a difference of ΔE * ab of 5 or less after exposure at 5% RH or less and after exposure at 95% RH or higher relative humidity.

  When the ink composition of the present invention and the indicator thereby employ a combination of 1) at least one ketone-based resin and 2) at least one methine-based dye, a discoloration layer is formed using the combination. The promotion of discoloration due to the influence of humidity can be adjusted. That is, in the prior art, discoloration was promoted in a high humidity environment and did not show discoloration according to the amount of hydrogen peroxide injected, whereas the discoloration layer of the present invention adjusted the influence of humidity on discoloration. Therefore, it can be used as an indicator for decontamination confirmation.

1. Hydrogen peroxide gas detecting ink composition The hydrogen peroxide gas detecting ink composition of the present invention comprises 1) at least one ketone-based resin and 2) at least one methine dye. .

Methine Dye In the composition of the present invention, at least a methine dye is used as a colorant (discoloration pigment). The methine dye may be a dye having a methine group. Therefore, in the present invention, polymethine dyes, cyanine dyes and the like are also included in the methine dyes. These can be appropriately selected from known or commercially available methine dyes. Specifically, CIBasic Red 12, CIBasic Red 13, CIBasic Red 14, CIBasic Red 15, CIBasic Red 27, CIBasic Red 35, CIBasic Red 36, CIBasic Red 37, CIBasic Red 45, CIBasic Red 48, CIBasic Yellow 11, CIBasic Yellow 12, CIBasic Yellow 13, CIBasic Yellow 14, CIBasic Yellow 21, CIBasic Yellow 22, CIBasic Yellow 23, CIBasic Yellow 24, CIBasic Violet 7, CIBasic Violet 15, CIBasic Violet 16, CIBasic Violet 20, CIBasic Violet 21, CIBasic Violet 39 CIBasic Blue 62, CIBasic Blue 63, and the like. These can be used alone or in combination of two or more.

  The content of the dye can be appropriately determined according to the desired hue and the like, but is generally about 0.05 to 5% by weight, particularly preferably 0.1 to 1% by weight in the composition of the present invention. . If it is less than 0.05% by weight, the color of the coating film is too light to distinguish the difference before and after the color change, and if it exceeds 5% by weight, the color is too dark and causes discoloration, which is more than the conditions for sterilization and decontamination. It becomes necessary to expose the accumulated concentration, and it cannot be used for judgment of sterilization or decontamination.

  In the present invention, dyes or pigments other than methine dyes may coexist. In particular, a pigment component that does not change color in a hydrogen peroxide gas atmosphere (referred to as “non-color-change pigment”) may be included. Thereby, the visual recognition effect can be further enhanced by a change in color tone from one color to another. A known ink (ordinary color ink) can be used as the non-color-changing dye. What is necessary is just to set suitably content of the non-color-change pigment | dye in this case according to the kind etc. of the non-color-change pigment | dye.

Ketone resin In the composition of the present invention, at least one ketone resin is used. By using these resins, it is possible to effectively adjust the reaction rate (discoloration rate) of the dye, adjust the influence of humidity on the discoloration rate, impart adhesiveness to the discoloration layer, and the like.

  The type and properties of the ketone resin are not limited, and known or commercially available products can be used. Specifically, Hilac 110H, 111, 901 (above, manufactured by Hitachi Chemical Co., Ltd.), Ketone Resin K-90 (Arakawa Chemical Industries, Ltd.), Halon 80, 110H (above, Honshu Chemical Co., Ltd.) Synthetic Resin AP, SK, 1201 (above, manufactured by Huls, Germany), etc. The content of the ketone resin can be appropriately determined according to the type of colorant used, etc. In general, it is preferably about 50% by weight or less, particularly 1 to 35% by weight in the ink composition of the present invention, and if it exceeds 50% by weight, the adhesiveness to the substrate is lowered.

Cationic surfactant The ink composition of the present invention preferably contains a cationic surfactant. The cationic surfactant is not particularly limited, but at least one of alkylammonium salt, isoquinolinium salt, imidazolinium salt and pyridinium salt is preferably used. These may be known or commercially available products. In the present invention, a superior detection sensitivity can be obtained by using these cationic surfactants together with the colorant.

  Among the alkyl ammonium salts, alkyl trimethyl ammonium salts, dialkyl dimethyl ammonium salts, trialkyl methyl ammonium salts, benzyl trimethyl ammonium salts, tetramethyl ammonium salts, tetraethyl ammonium salts, tetrabutyl ammonium salts, tetrapropyl ammonium salts, and the like are preferable. Specifically, palm alkyltrimethylammonium chloride, tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, chloride Examples thereof include alkylbenzyldimethylammonium. In particular, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride and the like are preferable. Examples of the isoquinolinium salt include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, lauryl isoquinolinium chloride and the like. Among these, lauryl isoquinolinium bromide is particularly preferable.

  Examples of the imidazolinium salt include 1-hydroxyethyl-2-oleylimidazolinium chloride and 2-chloro-1,3-dimethylimidazolinium chloride. Among these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.

  Examples of the pyridinium salt include pyridinium chloride, 1-ethylpyridinium bromide, hexadecylpyridinium chloride, cetylpyridinium chloride, 1-butylpyridinium chloride, Nn-butylpyridinium chloride, hexadecylpyridinium bromide, N-hexadecylpyridinium bromide, 1-dodecylpyridinium chloride, 3-methylhexylpyridinium chloride, 4-methylhexylpyridinium chloride, 3-methyloctylpyridinium chloride, 2-chloro-1-methylpyridinium iodide, 3,4-dimethylbutylpyridinium chloride, pyridinium-n -Hexadecyl chloride-hydrate, N- (cyanomethyl) pyridinium chloride, N-acetonyl pyridi Umbromide, 1- (aminoformylmethyl) pyridinium chloride, 2-amidinopyridinium chloride, 2-aminopyridinium chloride, N-aminopyridinium iodide, 1-aminopyridinium iodide, 1-acetonylpyridinium chloride, N-acetonyl Examples include pyridinium bromide. Among these, hexadecylpyridinium chloride is particularly preferable.

  The content of the cationic surfactant can be appropriately determined according to the type of the surfactant, the type of the colorant used, and the like, but is generally about 0.01 to 15% by weight in the composition of the present invention, in particular. It is desirable to set it as 0.1 to 10 weight%. If it is less than 0.01% by weight, the detection sensitivity is lowered, and if it exceeds 15% by weight, the adhesion between the substrate and the coating film is deteriorated or the coating film is blocked.

Resin binder, extender, etc. In the ink composition of the present invention, if necessary, resin binder (excluding ketone-based resin), extender, solvent, leveling agent, antifoaming agent, ultraviolet absorber, surface conditioner Ingredients used in known inks such as these can be blended as appropriate.

  The resin binder may be appropriately selected according to the type of the base material and the like. For example, known resin components used in ink compositions for writing and printing can be employed as they are. Specific examples include polyamide resins, maleic resins, alkylphenol resins, rosin resins, polyvinyl butyral, cellulose resins, polyester resins, styrene maleic resins, styrene acrylic resins, acrylic resins, and the like. .

  The content of the resin binder can be appropriately determined according to the type of the resin binder, the type of the colorant to be used, etc., but is generally about 50% by weight or less, particularly 5 to 35% by weight in the composition of the present invention. Is desirable. If the amount exceeds 50% by weight, the solid content in the ink is too high and printability is deteriorated, causing scumming and clogging of the printing plate.

  The extender is not particularly limited, and examples thereof include inorganic materials such as bentonite, activated clay, aluminum oxide, silica, and silica gel. In addition, materials known as known extender pigments can be used. Among these, at least one of silica, silica gel and alumina is preferable. In particular, silica is more preferable. By using silica or the like, it is possible to adjust the ink viscosity suitable for various printing methods.

  The content of the extender can be appropriately determined according to the type of extender used, the type of colorant used, and the like, but is generally about 0.1 to 30% by weight in the composition of the present invention, particularly 0.5 to 20% by weight is desirable. If the amount is less than 0.1% by weight, the ink viscosity is low. If the amount exceeds 30% by weight, the ink viscosity is high, so that the printability is deteriorated, causing scumming or clogging of the printing plate.

  As the solvent that can be used in the present invention, any solvent that is usually used in ink compositions for printing, writing, etc. can be used. For example, various solvents such as alcohols or polyhydric alcohols, esters, ethers, ketones, hydrocarbons, glycol ethers, etc. can be used, and they are appropriately selected according to the dye used, the solubility of the resin binder, etc. It ’s fine.

  The content of the solvent can be appropriately determined according to the type of solvent used, the type of colorant used, etc., but is generally about 40 to 95% by weight, particularly 60 to 90% by weight in the composition of the present invention. Is desirable. If the amount is less than 40% by weight, the ink viscosity is high. If the amount exceeds 95% by weight, the ink viscosity is low, so that the printability is deteriorated, causing scumming or clogging of the printing plate.

  These components may be blended simultaneously or sequentially and mixed uniformly using a known stirrer such as a homogenizer or a dissolver. For example, the colorant, a cationic surfactant, a resin binder, an extender and the like may be blended in the solvent in order, and mixed and stirred with a stirrer.

2. Hydrogen peroxide gas detection indicator The indicator of the present invention includes a discoloration layer comprising the above-described ink composition of the present invention. Generally, a discoloration layer can be formed by apply | coating or printing the ink composition of this invention on a base material. The substrate in this case is not particularly limited as long as it can form a discoloration layer. For example, metals or alloys, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, etc.), fibers (nonwoven fabric, woven fabric, other fiber sheets), composite materials of these, etc. are used. be able to. Moreover, synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.

  The color changing layer in the present invention includes not only the color changing to another color but also the color fading or erasing.

  The discoloration layer can be formed by using the ink composition of the present invention according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing and the like. It can also be formed by methods other than printing. For example, the discoloration layer can be formed by immersing the substrate in the ink composition. It is particularly suitable for a material into which ink penetrates, such as a nonwoven fabric.

  The discoloration layer is less affected by humidity during discoloration and exhibits discoloration corresponding to the amount of hydrogen peroxide injected. That is, it is possible to visually determine that the sterilization process has been passed regardless of conditions such as the humidity in the sterilization apparatus before hydrogen peroxide injection, the material and condition of the object to be processed, and the load on the sterilization apparatus. it can. Such discoloration performance can be obtained by a combination of 1) at least one ketone-based resin and 2) at least one methine dye.

  In the present invention, a non-discoloring layer that does not change color in a hydrogen peroxide gas sterilization atmosphere may be formed on the substrate and / or the discoloring layer. The non-discoloring layer can be usually formed with a commercially available ordinary color ink. For example, water-based ink, oil-based ink, solventless ink, and the like can be used. The ink used for forming the non-discoloring layer may contain components blended in known inks, such as resin binders, extenders, solvents, and the like.

  The non-discoloring layer may be formed in the same manner as in the discoloring layer. For example, normal color ink can be used according to a known printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, or flexographic printing. The order of printing of the color changing layer and the non-color changing layer is not particularly limited, and may be appropriately selected according to the design to be printed.

  In the indicator of the present invention, one color changing layer and one non-color changing layer may be formed, or a plurality of layers may be formed. Further, discoloration layers or non-discoloration layers may be laminated. In this case, the discoloration layers may have the same composition or different compositions. Similarly, the non-discoloring layers may have the same composition or different compositions.

  Furthermore, the color-changing layer and the non-color-changing layer may be formed on the entire surface of the substrate or each layer, or may be partially formed. In these cases, in particular, in order to ensure the color change of the color change layer, the color change layer and the non-color change layer may be formed so that a part or all of at least one color change layer is exposed to the hydrogen peroxide gas atmosphere.

  In the present invention, the discoloration layer and the non-discoloration layer may be combined in any way as long as the completion of the hydrogen peroxide gas sterilization process can be confirmed. For example, a color-changing layer and a non-color-changing layer are formed so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only after the color-changing layer is changed, or a color difference between the color-changing layer and the non-color-changing layer disappears only after the color change It can also be formed. In the present invention, it is particularly preferable to form the color-changing layer and the non-color-changing layer so that the color difference between the color-changing layer and the non-color-changing layer can be discriminated only by the color change.

  In order to identify the color difference, for example, the color-changing layer and the non-color-changing layer may be formed so that at least one of a character, a pattern, and a symbol appears only when the color-changing layer changes. In the present invention, characters, designs, and symbols include all information that informs discoloration. What is necessary is just to design these characters etc. suitably according to the purpose of use.

  Further, the color changing layer and the non-color changing layer before the color change may be different from each other. For example, they may be substantially the same color so that the color difference (contrast) between the color-change layer and the non-color-change layer can be identified only after the color change.

  In the indicator of the present invention, the color changing layer and the non-color changing layer can be formed so that the color changing layer and the non-color changing layer do not overlap. As a result, the amount of ink used can be saved.

  Furthermore, in the present invention, a color changing layer or a non-color changing layer may be further formed on at least one of the color changing layer and the non-color changing layer. For example, if a color-changing layer having a different design is formed on a layer in which the color-changing layer and the non-color-changing layer are formed so as not to overlap the color-changing layer and the non-color-changing layer (referred to as “color-changing-non-color-changing layer”), Since the boundary line between the color changing layer and the non-color changing layer in the color changing-non-color changing layer can be made substantially indistinguishable, a more excellent design can be achieved.

  The indicator of the present invention can be applied to any sterilization treatment performed in a hydrogen peroxide gas atmosphere. Therefore, it is useful as an indicator in a hydrogen peroxide gas sterilization apparatus. For example, when the indicator is used, the indicator of the present invention may be placed in a commercially available sterilization apparatus and exposed to a sterilization atmosphere together with equipment to be sterilized. In this case, it is possible to detect that a predetermined sterilization process has been performed by changing the color of an indicator placed in the apparatus.

Examples , Comparative Examples and Reference Examples are shown below to further clarify the features of the present invention. In addition, this invention is not restrict | limited to the aspect of an Example.

Examples 1-2 and Reference Examples 1-2
Each ink composition was prepared by mixing each component shown in Table 1 uniformly with a stirrer. Specifically, first, a solvent, a dye, and a ketone resin were stirred and mixed with a dissolver. If the resin was difficult to dissolve, it was heated as necessary. Subsequently, after adding a non-color-change pigment | dye and a resin binder and stirring further, it returned to normal temperature, at least 1 sort (s) of surfactant was added, and the ink composition was obtained by stirring uniformly.

Comparative Example 1
An ink composition was prepared in the same manner as in Example 1 except that the ink composition was changed as shown in Table 1.

  The components shown in Table 1 are specifically as follows.

1) CI Basic Red 14: methine dye 2) CI Solvent Yellow 29: non-discoloring dye 3) CI Pigment Green 7: non-discoloring dye, phthalocyanine pigment dispersion, manufactured by KLT 4) Jonkrill 690: styrene acrylic resin, BASF 5) Jonkrill 683: Styrene acrylic resin, BASF 6) MOWITAL PVB-B20H: Polyvinyl butyral resin, Kuraray 7) Hilac 111: Ketone resin, Hitachi Chemical 8) Hilac 110H: Ketone resin, Hitachi Chemical 9) Aerosil R-972: Silica, manufactured by Hitachi Aerosil 10) NIKKOL CA-2150: Alkyltrimethylammonium salt surfactant, manufactured by Nikko Chemicals 11) SH200 Oil 100CS: Silicon oil, manufactured by Toray Dow Corning

Test example 1
The discoloration of the ink compositions of each Example , Comparative Example and Reference Example was examined. A sample was prepared by forming a coating film on Krisper K2323 (188 μm) using a squeegee and sufficiently drying the ink composition.

  About discoloration property, 80L of decontamination warehouse made by Shibuya Industry was used.

  The conditions for the discoloration test were a hydrogen peroxide gas retention time of 5 minutes and an aeration time of 30 minutes. As the amount of 35% hydrogen peroxide solution injected into the chamber, 0.2 g, 0.4 g, 0.7 g, 1.0 g, 3.0 g, and 5.0 g were weighed. In an experiment under high humidity conditions, 10 g of ion exchange water was first injected and held for 5 minutes, and then hydrogen peroxide was injected to perform a discoloration test. After the completion of exposure, the color difference from the blank (sample before exposure) was measured. For the measurement of the color difference, the CIE1978 (L * a * b *) color system defined by JIS Z8729 was used, and the color difference ΔE * ab was determined from the obtained measurement value by the following equation [Equation 1]. As the color difference measuring apparatus, a micro color difference meter “CR-241 (manufactured by Konica Minolta)” was used. Table 1 shows the measurement results.

The value of ΔE * ab (L) −ΔE * ab (H) is a negative value in Comparative Example 1 , and discoloration is promoted in a high humidity environment. On the other hand, in Examples 1 and 2, the difference between the color change in the low-humidity environment and the color change in the high-humidity environment is small, and it can be seen that the color change according to the injection amount is exhibited without being affected by the humidity. In the case of performing sterilization and decontamination using the injection amount of hydrogen peroxide as an operation parameter, indicators as in Examples 1 and 2 are useful.

On the other hand, in Reference Examples 1 and 2 in which the amount of the ketone resin is large, contrary to Comparative Example 1 , a positive value is taken, and discoloration is suppressed in a high humidity environment. According to Non-Patent Document 1 (J. Antibact. Agents Vol.28., No.2, pp.95-97, 2000), if the relative humidity before hydrogen peroxide injection is high, the allowable concentration of hydrogen peroxide gas It is shown that dew condensation occurs when the concentration exceeds the allowable concentration, and the gas concentration in the atmosphere decreases at this time. It can be seen that the indicators of Reference Examples 1 and 2 detect a decrease in the hydrogen peroxide gas concentration because discoloration is suppressed by high humidity. That is, when performing sterilization and decontamination using the actual measurement value of hydrogen peroxide as an operation parameter, the indicators of Reference Examples 1 and 2 are useful.

Claims (1)

1) a hydrogen peroxide gas detection indicator comprising a discoloration layer made of a hydrogen peroxide gas detection ink composition containing at least one kind of ketone-based resin and 2) at least one methine dye;
The ink composition for detecting hydrogen peroxide gas has a methine dye content of 0.1 to 1% by weight and a ketone resin content of 1 to 35% by weight of the methine dye and the ketone resin. The composition is 9 to 18 parts by weight of a ketone resin with respect to 0.2 parts by weight of a methine dye,
In the discoloration layer, when exposed to hydrogen peroxide gas at a condition of 12.5 mg / L, after exposure at a relative humidity before exposure of 5% RH or less and after exposure at a relative humidity before exposure of 95% RH or more Hydrogen peroxide detection indicator with a difference of ΔE * ab of 5 or less.