WO2012043722A1 - Indicator for detection of hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization - Google Patents

Indicator for detection of hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization Download PDF

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Publication number
WO2012043722A1
WO2012043722A1 PCT/JP2011/072381 JP2011072381W WO2012043722A1 WO 2012043722 A1 WO2012043722 A1 WO 2012043722A1 JP 2011072381 W JP2011072381 W JP 2011072381W WO 2012043722 A1 WO2012043722 A1 WO 2012043722A1
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Prior art keywords
hydrogen peroxide
indicator
sterilization
package
dye
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PCT/JP2011/072381
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French (fr)
Japanese (ja)
Inventor
盛作 大城
藤澤　俊樹
美帆 岡田
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株式会社サクラクレパス
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Publication of WO2012043722A1 publication Critical patent/WO2012043722A1/en

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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
    • G01N31/22—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators
    • G01N31/226—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using chemical indicators for investigating the degree of sterilisation

Definitions

  • the present invention relates to a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator.
  • the hydrogen peroxide plasma sterilization treatment is advantageous in that it generates plasma in a hydrogen peroxide atmosphere and sterilizes the equipment with low-temperature gas plasma, and can be sterilized at a relatively low temperature.
  • Patent Documents 1 to 3 describe such an indicator and an ink composition for forming the indicator. Specifically, Patent Documents 1 and 2 describe ink compositions and indicators used for detection of hydrogen peroxide sterilization. Patent Document 3 describes an ink composition and an indicator used for detection of hydrogen peroxide plasma sterilization.
  • the above prior art indicators have the following problems. That is, the process of evacuating the chamber (sterilization device) during the sterilization process when the object to be processed and the indicator are loaded and sealed in a gas permeable package and subjected to hydrogen peroxide sterilization treatment or hydrogen peroxide plasma sterilization treatment. Therefore, the indicator may be in close contact with the gas permeable package during the vacuum process, resulting in a discoloration defect. For example, the indicator may be in close contact with a transparent window (film surface) provided in a part of the package, and hydrogen peroxide or hydrogen peroxide plasma may not be detected.
  • the indicator does not adhere to the gas permeable package. Therefore, the development of an indicator that can be detected accurately is required.
  • the indicator adheres to the gas permeable package.
  • the main objective is to provide an indicator that can be detected accurately.
  • the present invention relates to the following hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator.
  • a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator having a discoloration layer that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma on a substrate, wherein the surface roughness Ra of the discoloration layer is 2.5.
  • Indicator characterized by being in the range of ⁇ 15.0 ⁇ m.
  • Item 2 The indicator according to Item 1, wherein an opening of 0.2 to 20% of the substrate area is provided on the substrate. 3. Item 2.
  • the indicator according to Item 1 wherein at least one selected from the group consisting of embossed grooves, slits (linear holes), and perforations (dashed holes) is provided on the substrate. 4).
  • Item 5. The ink composition according to Item 4, wherein the particles are at least one of a polymer compound and an inorganic compound. 6). Item 6.
  • a package for hydrogen peroxide or hydrogen peroxide plasma sterilization wherein the indicator according to any one of Items 1 to 3 is provided on the inner surface of the gas permeable package. 10.
  • Item 10 The package according to Item 9, wherein a transparent window is provided on a part of the package so that the indicator can be confirmed from the outside. 11.
  • Item 11 The package according to Item 9 or 10, wherein the gas permeable package is formed of polyethylene fiber. 12
  • the step of loading the object to be processed in any of the above items 9 to 11 the step of sealing the package in which the object to be processed is loaded, and the package is sterilized with hydrogen peroxide or hydrogen peroxide plasma
  • a hydrogen peroxide or hydrogen peroxide plasma sterilization treatment method comprising a step of placing in a sterilizing atmosphere.
  • Item 13 The method according to Item 12, wherein the package is placed in an atmosphere of hydrogen peroxide or a hydrogen peroxide plasma sterilization until the color changing layer of the indicator changes color.
  • the indicator of the present invention is a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator having a discoloration layer that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma on a substrate, the surface roughness of the discoloration layer.
  • the thickness Ra is in the range of 2.5 to 15.0 ⁇ m.
  • the indicator of the present invention having the above-described features is particularly suitable for loading and sealing the object to be treated and the indicator on the gas permeable package by having the surface roughness Ra of the discoloration layer in the range of 2.5 to 15.0 ⁇ m. Even when the hydrogen peroxide sterilization process or the hydrogen peroxide plasma sterilization process is performed, the indicator does not adhere to the gas-permeable package, and accurate detection is possible.
  • the indicator of the present invention can have the same configuration as the conventionally known indicator as long as the discoloration layer has the surface roughness Ra and changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma.
  • the indicator it is preferable to more reliably prevent the indicator from adhering to the gas permeable package by providing an opening of 0.2 to 20% of the substrate area on the substrate.
  • One or two or more openings may be provided on the substrate (including a portion where the color-changing layer is formed), and preferably two or more openings are provided in the portion where the color-changing layer is formed.
  • the shape of the opening is not particularly limited, and various shapes such as a circle, a square, and a triangle can be adopted.
  • the opening include, for example, a mode in which circular holes having a diameter of 2 mm to 4 mm are provided on both sides of the color changing layer, a mode in which the central portion of the color changing layer is provided, and a part on which the color changing layer is formed And the like provided randomly.
  • the total area of the openings is preferably within the range of 0.3 to 13% of the substrate area.
  • the indicator is gas permeable by providing at least one selected from the group consisting of embossed grooves, slits (linear holes) and perforations (dashed holes) on the substrate. It is preferable to more reliably prevent adhesion to the adhesive package.
  • the embossed grooves can be provided with vertical stripes, horizontal stripes or the like alone or in combination so as to cross the opposite sides of the indicator.
  • Such an embossing groove can be provided by a known embossing machine.
  • the depth of the groove is preferably set to about 25 to 35 ⁇ m.
  • the direction in which the embossing grooves are formed is not particularly limited, and the surface having the discoloration layer may be provided as a concave portion or may be provided as a convex portion.
  • a slit it is preferable to provide one or more on the color changing layer as shown in Example 3 of FIG.
  • the slit can be replaced with a perforation (not shown) in consideration of the strength of the indicator.
  • the indicator it is preferable to fold and use the indicator to more reliably prevent the indicator from sticking to the gas permeable packaging.
  • the shape of the indicator is a rectangle
  • the bending may be performed so as to bend across the opposite side, or bend the end of the indicator into a triangle. Specific examples of such bending are shown in a-1 to b-1 in FIG.
  • the direction of folding is not particularly limited, and the surface having the discoloration layer may be mountain-folded or valley-folded.
  • the base material of the indicator those which can form a discoloration layer by coating or printing are good, for example, metal or alloy, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, etc.), fiber (Nonwoven fabric, woven fabric, other fiber sheets), composite materials of these, and the like can be used.
  • synthetic resin fiber paper synthetic paper
  • synthetic paper such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.
  • the discoloration layer in the present invention includes not only those whose color changes to other colors in the presence of hydrogen peroxide or hydrogen peroxide plasma, but also those whose colors fade or disappear.
  • the discoloration layer can be formed by a printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, etc., using an ink composition described later. Also, it can be formed by other than printing.
  • the discoloration layer can be formed by immersing the substrate in the ink composition. This method is particularly suitable for a material into which ink penetrates, such as a nonwoven fabric.
  • the ink composition for forming the color changing layer preferably contains particles having an average particle size of 1 to 30 ⁇ m in addition to the component that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma.
  • the surface roughness Ra of the discoloration layer can be easily set to 2.5 to 15.0 ⁇ m (preferably 2.5 to 5.0 ⁇ m).
  • surface roughness Ra in this specification is Ra prescribed
  • a mechanical method for example, roughening by sandpaper or sandblasting, color changing layer by silk screen printing
  • the average particle size of the particles is preferably 1 to 30 ⁇ m, more preferably 5 to 15 ⁇ m.
  • the material of the particles is not limited, but is preferably at least one of a polymer compound and an inorganic compound that does not react with or adsorb hydrogen peroxide or hydrogen peroxide plasma.
  • polymer compound examples include polyethylene, polypropylene, acrylic copolymer, polyester, polyamide, polyurethane, phenol resin, and melamine resin.
  • the polymer compound may be not only resin spheres but also hollow resin spheres, microcapsules, and the like. Moreover, it does not need to be colorless and may be colored with dyes or pigments.
  • low molecular weight polyethylene resin spheres are preferable.
  • commercially available Chemipearl W308 average particle size 6 ⁇ m, softening point 132 ° C.
  • Chemipearl W200 average particle size 6 ⁇ m, softening point 113 ° C.
  • Chemipearl W310 Average particle size 9.5 ⁇ m, softening point 132 ° C., 40% aqueous dispersion manufactured by Mitsui Chemicals) and the like are preferable.
  • inorganic compounds include calcium carbonate and glass.
  • the inorganic compound is not limited to a spherical shape, but may be a plate-like material (flake-like material), a needle-like material, or the like, if necessary.
  • particles, plates, and needles are collectively referred to as “particles”.
  • the color change layer can be used in combination so that the surface roughness Ra falls within the range of 2.5 to 5.0 ⁇ m.
  • the diameter is preferably 1 to 30 ⁇ m in terms of a sphere equivalent diameter measured by a laser diffraction method.
  • the content of the particles and the like in the ink composition is not limited, but it is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the ink excluding the particles and the like. .
  • the content of the particles and the like in the ink composition is not limited, but it is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the ink excluding the particles and the like. .
  • known components can be used as components that change color in the presence of hydrogen peroxide or hydrogen peroxide plasma contained in the ink composition.
  • an ink composition for detecting hydrogen peroxide sterilization an ink composition containing at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye (see JP-A-2006-78463).
  • 1) at least one styrene acrylic resin and styrene maleic acid resin, and 2) an ink composition containing a methine dye (described in JP-A-2007-40785) can be used.
  • the ink composition for detecting hydrogen peroxide plasma sterilization contains 1) at least one anthraquinone dye, azo dye, and methine dye, 2) a nitrogen-containing polymer, and 3) a cationic surfactant.
  • An ink composition (described in JP-A-2005-315828) can be preferably used. These ink compositions will be briefly described below.
  • Ink composition for hydrogen peroxide sterilization detection An ink composition containing at least one of an azo dye, a methine dye, a triarylmethane dye and a thiazine dye (described in JP-A-2006-78463) Can be mentioned.
  • the azo dye is not limited as long as it has an azo group —N ⁇ N— as a chromophore.
  • examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, the dye numbers are CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue, 44, CIDisperse Red 58, CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIsisperse Orange 5, CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, and the like. These can be used alone or in combination of two or more.
  • methine dye any dye having a methine group may be used. 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.
  • 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 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 triarylmethane dye is not limited, and a known or commercially available dye can be used.
  • CIBasic Blue 1, CIBasic Blue 26, CIBasic Blue 5, CIBasic Blue 8, CIBasic Green 1, CIBasic Red 9, CIBasic Violet 12, CIBasic Violet 14, CIBasic Violet 3, CISRol Green 15, CISolvent Violet 8 etc. can be used alone or in combination of two or more.
  • C.I.Solvent Violet 8 C.I.Basic Green 1, C.I.Basic Red 9, C.I.Basic Blue 1 and the like can be suitably used.
  • the thiazine dye is not particularly limited and can be selected from known or commercially available ones. Examples thereof include C.I.Basic Blue-9, C.I.Basic Blue-25, C.I.Basic Blue-24, C.I.Basic Blue-17, C.I.Basic Green-5, C.I.Solvent Blue-8, and the like. These can be used alone or in combination of two or more. Among these thiazine dyes, C.I.Basic Blue 9 can be suitably used.
  • the content of these dyes varies depending on the type of dye used, desired detection characteristics, etc., but is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.00% in the ink composition. It may be 1 to 2% by weight.
  • methine dye any dye having a methine group may be used. 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.
  • 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 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 0.1 to 1% by weight in the ink composition.
  • the types and properties of the styrene acrylic resin and styrene maleic acid resin are not limited, and known or commercially available ones can be used.
  • the content of the styrene acrylic resin and the styrene maleic acid resin can be appropriately determined according to the type of the colorant used and the like, but is generally about 50% by weight or less, particularly 1 to 35% by weight in the ink composition. Is desirable.
  • Ink composition for hydrogen peroxide plasma sterilization detection 1) Ink composition containing at least one kind of anthraquinone dye, azo dye and methine dye, 2) nitrogen-containing polymer and 3) cationic surfactant No. 2005-315828).
  • the anthraquinone dye is not limited as long as it has anthraquinone as a basic skeleton, and a known anthraquinone disperse dye or the like can also be used.
  • An anthraquinone dye having an amino group is particularly preferable. More preferred is an anthraquinone dye having at least one amino group of a primary amino group and a secondary amino group. In this case, each amino group may have two or more, and these may be the same or different from each other.
  • 1,4-diaminoanthraquinone (CIDisperse Violet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperse Red 4), 1-amino-4-methylaminoanthraquinone ( CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthraquinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red) 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperse Violet 8) and the like (dye number in parentheses) .
  • CISolvent Blue 14 CISolvent Blue 35, CISolvent Blue 63, CISolvent Violet 13, CISolvent Violet 14, CISolvent Red 52, CISolvent Red 114, CIVat Blue 21, CIVat Blue 30, CIVat Violet 15, CIVat Violet 17, CIVat Red 19, CIVat Red 28, CIAcid Blue 23, CIAcid Blue 80, CIAcid Violet 43, CIAcid Violet 48, CIAcid Red 81, CIAcid Red 83, CIReactive Dyes known as Blue 4, CIReactive Blue 19, CIdisperse Blue 7 etc. can also be used.
  • These anthraquinone dyes can be used alone or in combination of two or more.
  • the detection sensitivity can be controlled by changing the type (molecular structure, etc.) of these anthraquinone dyes.
  • the azo dye is not limited as long as it has an azo group —N ⁇ N— as a chromophore.
  • examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, the dye numbers are CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue 44, CIDisperse Red 58 CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIDisperse Orange 5, and the like. These can be used alone or in combination of two or more.
  • methine dye any dye having a methine group may be used. 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.
  • 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 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 type of dye, desired hue, etc., but is generally about 0.05 to 5% by weight, particularly 0.1 to 1% by weight in the ink composition. It is desirable.
  • the nitrogen-containing polymer for example, a synthetic resin such as polyamide resin, polyimide resin, polyacrylonitrile resin, amino resin, polyacrylamide, polyvinyl pyrrolidone, polyvinyl imidazole, or polyethyleneimine can be suitably used. These can be used alone or in combination of two or more.
  • the nitrogen-containing polymer serves as a sensitivity enhancer. That is, by using a sensitivity enhancer, the accuracy (sensitivity) of hydrogen peroxide plasma sterilization detection can be further increased. Thereby, since the color is surely changed even in the package for hydrogen peroxide plasma sterilization, it is very advantageous as an indicator used for the package.
  • a polyamide resin in the present invention.
  • the kind of polyamide resin, molecular weight, etc. are not specifically limited, A well-known or commercially available polyamide resin can be used.
  • a polyamide resin which is a reaction product (long chain linear polymer) of a dimer of linoleic acid and di- or polyamine can be preferably used.
  • the polyamide resin is a thermoplastic resin having a molecular weight of 4000 to 7000.
  • a commercially available product can also be used for such a resin.
  • the content of the nitrogen-containing polymer can be appropriately determined according to the type of the polymer, the type of colorant used, etc., but is generally about 0.1 to 50% by weight, particularly 1 to 20% in the ink composition. It is desirable to set the weight%.
  • the cationic surfactant is not particularly limited, but it is particularly desirable to use at least one of an alkyl ammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. These may be known or commercially available products. In the present invention, a superior detection sensitivity can be obtained by using these cationic surfactants in combination with the above dyes.
  • alkylammonium salts alkyltrimethylammonium salts, dialkyldimethylammonium salts and the like are preferable.
  • palm alkyltrimethylammonium chloride tallow alkyltrimethylammonium chloride, behenyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, lauryltrimethylammonium chloride, octadecyltrimethylammonium chloride, dioctyldimethylammonium chloride, distearyldimethylammonium chloride, chloride
  • alkylbenzyldimethylammonium alkylbenzyldimethylammonium.
  • coconut alkyltrimethylammonium chloride and lauryltrimethylammonium chloride are preferable.
  • isoquinolinium salt examples include lauryl isoquinolinium bromide, cetyl isoquinolinium bromide, cetyl isoquinolinium chloride, lauryl isoquinolinium chloride and the like. Among these, lauryl isoquinolinium bromide is particularly preferable.
  • imidazolinium salt examples include 1-hydroxyethyl-2-oleylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium chloride, and the like. Of these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.
  • pyridinium salt examples 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 pyri Nitrobromide, 1- (amino
  • the content of the cationic surfactant can be appropriately determined according to the type of the surfactant, the type of the dye to be used, and the like, but is generally about 0.2 to 10% by weight in the ink composition, particularly about 0. It is desirable that the content be 5 to 5% by weight.
  • the ink composition may be appropriately blended with components used in known inks such as a resin binder, a filler, a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner, as necessary. Can do. What is necessary is just to follow a conventional method about content of these components.
  • the indicator of the present invention can be applied to any sterilization treatment performed in a hydrogen peroxide or hydrogen peroxide plasma atmosphere. Therefore, it is useful as an indicator in a sterilization apparatus (specifically, an apparatus that performs sterilization with hydrogen peroxide or hydrogen peroxide plasma).
  • a sterilization apparatus specifically, an apparatus that performs sterilization with hydrogen peroxide or hydrogen peroxide plasma.
  • 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 plasma sterilization process has been performed by changing the color of an indicator placed in the apparatus.
  • sterilization can be suitably performed using a package for hydrogen peroxide or hydrogen peroxide plasma sterilization in which an indicator is provided on the inner surface of the gas permeable package.
  • the gas-permeable packaging body is preferably a packaging body that can be sterilized while the object to be treated is sealed therein.
  • a known or commercially available product used as a sterilization package can be used.
  • a package formed of polyethylene fibers (polyethylene synthetic paper) can be suitably used. After putting an object to be processed into this package and sealing the opening by heat sealing or the like, the entire package can be sterilized in a sterilization apparatus.
  • the indicator may be disposed on the inner surface of the package.
  • the arrangement method is not limited, and the indicator can also be constituted by applying or printing the ink composition directly on the inner surface of the package, in addition to a method using an adhesive, heat sealing, or the like.
  • an indicator can be formed at the manufacturing stage of the package.
  • the package may be made of a transparent sheet and the polyethylene synthetic paper, and the indicator may be arranged on the inner surface of the package at a position where it can be visually recognized through the transparent sheet.
  • a method having a step of placing in a sterile atmosphere may be used. More specifically, after an object to be processed (medical instrument, food, etc.) is put in a package, it is sealed according to a known method such as heat sealing. Next, the entire package is placed in a sterile atmosphere. For example, it is placed in a sterilization chamber of a known or commercially available sterilizer and sterilized. After the sterilization process is completed, the whole package can be taken out and stored in the package until it is used. In this case, the sterilization is preferably performed by placing the package in a sterilizing atmosphere until the discoloration layer of the indicator changes color.
  • the surface roughness Ra of the discolored layer is in the range of 2.5 to 5.0 ⁇ m. Even when the treatment or the hydrogen peroxide plasma sterilization treatment is performed, the indicator is not in close contact with the gas permeable package, and accurate detection is possible.
  • Examples 1 to 3 and Comparative Example 1 Each component shown in Table 1 was uniformly mixed with a stirrer to prepare an ink composition. Specifically, components other than particles (Chemical) were sufficiently stirred first, then Chemipearl was added and stirred for 30 minutes.
  • Each ink composition was screen-printed on a PET sheet (Toyobo's Crisper K2323: 125 ⁇ m) using a 250 mesh plate to form a discolored layer. After natural drying for 30 minutes, forced drying was performed at 70 ° C. for 5 minutes. This produced the indicator.
  • each indicator and 5m x 2 PVC electric wires are placed in a package (sterilized pouch, product name "Sterad Sterilized Pouch Regular"), and the opening is sealed by heat sealing.
  • the sample was placed in a hydrogen oxide low temperature gas plasma sterilization system “STERRAD 50” manufactured by Johnson & Johnson Medical Co., Ltd.) and sterilized under standard conditions programmed in advance by the manufacturer, and examined for the presence or absence of discoloration. The results are shown in Table 1.

Abstract

Provided is an indicator whereby it becomes possible to prevent the adhesion of the indicator to a gas-permeable packaging material and it becomes also possible to achieve accurate detection even when a material of interest and the indicator are packed/sealed into the gas-permeable packaging material and a hydrogen peroxide sterilization treatment or a hydrogen peroxide plasma sterilization treatment is carried out using the packaging material. The indicator is a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator, which comprises a base and a color-changing layer formed on the base, wherein the color of the color-changing layer is changed in the presence of hydrogen peroxide or hydrogen peroxide plasma, and wherein the indicator is characterized in that the color-changing layer has a surface roughness (Ra) of 2.5-15.0 μm.

Description

過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターHydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator
　本発明は、過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターに関する。 The present invention relates to a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator.
　病院、研究所等において使用される各種の器材、器具等は、消毒・殺菌のために滅菌処理が施される。この滅菌処理として、例えば、過酸化水素（蒸気）滅菌処理、過酸化水素プラズマ滅菌処理等が知られている。このうち、過酸化水素プラズマ滅菌処理は、過酸化水素雰囲気下でプラズマを発生させ低温ガスプラズマにより器材を滅菌するものであり、比較的低い温度で滅菌処理できるという点で有利である。 Various equipment and instruments used in hospitals, laboratories, etc. are sterilized for disinfection and sterilization. As this sterilization treatment, for example, hydrogen peroxide (steam) sterilization treatment, hydrogen peroxide plasma sterilization treatment, and the like are known. Among these, the hydrogen peroxide plasma sterilization treatment is advantageous in that it generates plasma in a hydrogen peroxide atmosphere and sterilizes the equipment with low-temperature gas plasma, and can be sterilized at a relatively low temperature.
　これらの滅菌処理においては、滅菌処理が完了したかどうかを確認するためのインジケーターの設置が必要となる。具体的には、処理系内に過酸化水素又は過酸化水素プラズマが十分に行き渡っているか否か及び曝露時間を知るためのインジケーターを滅菌装置内に設置することが必要である。このようなインジケーター及びそれを形成するためのインキ組成物が特許文献１～３に記載されている。具体的には、特許文献１及び２には、過酸化水素滅菌検知に用いるインキ組成物及びインジケーターが記載されている。また、特許文献３には、過酸化水素プラズマ滅菌検知に用いるインキ組成物及びインジケーターが記載されている。 In these sterilization processes, it is necessary to install an indicator for confirming whether the sterilization process is completed. Specifically, it is necessary to install an indicator in the sterilizer to know whether hydrogen peroxide or hydrogen peroxide plasma is sufficiently distributed in the treatment system and the exposure time. Patent Documents 1 to 3 describe such an indicator and an ink composition for forming the indicator. Specifically, Patent Documents 1 and 2 describe ink compositions and indicators used for detection of hydrogen peroxide sterilization. Patent Document 3 describes an ink composition and an indicator used for detection of hydrogen peroxide plasma sterilization.
　しかしながら、上記従来技術のインジケーターには次の問題がある。即ち、気体透過性包装体に被処理物とインジケーターを装填・密封し、過酸化水素滅菌処理又は過酸化水素プラズマ滅菌処理に供する際、滅菌工程中にチャンバー（滅菌処理器）を真空にする工程が含まれているため、真空工程の際にインジケーターが気体透過性包装体に密着し、変色不良が生じる場合がある。例えば、包装体の一部に設けられた透明窓部（フィルム面）にインジケーターが密着し、過酸化水素又は過酸化水素プラズマを検知できない場合がある。 However, the above prior art indicators have the following problems. That is, the process of evacuating the chamber (sterilization device) during the sterilization process when the object to be processed and the indicator are loaded and sealed in a gas permeable package and subjected to hydrogen peroxide sterilization treatment or hydrogen peroxide plasma sterilization treatment. Therefore, the indicator may be in close contact with the gas permeable package during the vacuum process, resulting in a discoloration defect. For example, the indicator may be in close contact with a transparent window (film surface) provided in a part of the package, and hydrogen peroxide or hydrogen peroxide plasma may not be detected.
　よって、気体透過性包装体に被処理物とインジケーターを装填・密封し、過酸化水素滅菌処理又は過酸化水素プラズマ滅菌処理を行う場合であっても、インジケーターが気体透過性包装体に密着せず、正確な検知が可能なインジケーターの開発が求められている。 Therefore, even if the object to be processed and the indicator are loaded and sealed in the gas permeable package, and the hydrogen peroxide sterilization process or the hydrogen peroxide plasma sterilization process is performed, the indicator does not adhere to the gas permeable package. Therefore, the development of an indicator that can be detected accurately is required.
特開2006-078463号公報JP 2006-078463 A 特開2007-040785号公報JP 2007-040785 A 特開2005-315828号公報JP 2005-315828 JP
　本発明は、気体透過性包装体に被処理物とインジケーターを装填・密封し、過酸化水素滅菌処理又は過酸化水素プラズマ滅菌処理を行う場合であっても、インジケーターが気体透過性包装体に密着せず、正確な検知が可能なインジケーターを提供することを主な目的とする。 In the present invention, even when a gas permeable package is loaded and sealed with an object to be processed and an indicator, and hydrogen peroxide sterilization treatment or hydrogen peroxide plasma sterilization treatment is performed, the indicator adheres to the gas permeable package. The main objective is to provide an indicator that can be detected accurately.
　本発明者は上記目的を達成すべき鋭意研究を重ねた結果、特定の変色層を有するインジケーターが上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor has found that an indicator having a specific color changing layer can achieve the above object, and has completed the present invention.
　即ち、本発明は、下記の過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターに関する。
１．基材上に過酸化水素又は過酸化水素プラズマの存在下で変色する変色層を有する過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターであって、前記変色層の表面粗さＲａが２．５～１５．０μｍの範囲であることを特徴とするインジケーター。
２．前記基材上に、基材面積の０．２～２０％の開口部が設けられている、上記項１に記載のインジケーター。
３．前記基材上に、型押し溝、スリット（線状の孔）及びミシン目（破線状の孔）からなる群から選択される少なくとも１種が設けられている、上記項１に記載のインジケーター。
４．上記項１に記載の変色層を形成するためのインキ組成物であって、過酸化水素又は過酸化水素プラズマの存在下で変色する成分に加えて、平均粒子径１～３０μｍの粒子を含有するインキ組成物。
５．前記粒子は、高分子化合物及び無機化合物の少なくとも１種である、上記項４に記載のインキ組成物。
６．アゾ系染料、メチン系染料、トリアリールメタン系染料及びチアジン系染料の少なくとも１種を含有する、上記項４又は５に記載の過酸化水素滅菌検知用インキ組成物。
７．１）スチレンアクリル樹脂及びスチレンマレイン酸樹脂の少なくとも１種及び２）メチン系染料を含有する、上記項４又は５に記載の過酸化水素滅菌検知用インキ組成物。
８．１）アントラキノン系染料、アゾ系染料及びメチン系染料の少なくとも１種、２）窒素含有高分子及び３）カチオン系界面活性剤を含有する。上記項４又は５に記載の過酸化水素プラズマ滅菌検知用インキ組成物。
９．気体透過性包装体の内面に上記項１～３のいずれかに記載のインジケーターが設けられている過酸化水素又は過酸化水素プラズマ滅菌用包装体。
１０．前記インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられている、上記項９に記載の包装体。
１１．前記気体透過性包装体が、ポリエチレン系繊維により形成されている、上記項９又は１０に記載の包装体。
１２．上記項９～１１のいずれかに記載の包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を過酸化水素滅菌又は過酸化水素プラズマ滅菌雰囲気下に置く工程を有する過酸化水素又は過酸化水素プラズマ滅菌処理方法。
１３．前記インジケーターの変色層が変色するまで過酸化水素又は過酸化水素プラズマ滅菌雰囲気下に包装体を置く、上記項１２に記載の方法。 That is, the present invention relates to the following hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator.
1. A hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator having a discoloration layer that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma on a substrate, wherein the surface roughness Ra of the discoloration layer is 2.5. Indicator characterized by being in the range of ~ 15.0 μm.
2. Item 2. The indicator according to Item 1, wherein an opening of 0.2 to 20% of the substrate area is provided on the substrate.
3. Item 2. The indicator according to Item 1, wherein at least one selected from the group consisting of embossed grooves, slits (linear holes), and perforations (dashed holes) is provided on the substrate.
4). An ink composition for forming a discoloration layer according to Item 1, which contains particles having an average particle diameter of 1 to 30 μm in addition to a component that discolors in the presence of hydrogen peroxide or hydrogen peroxide plasma. Ink composition.
5. Item 5. The ink composition according to Item 4, wherein the particles are at least one of a polymer compound and an inorganic compound.
6). Item 6. The ink composition for detecting hydrogen peroxide sterilization according to Item 4 or 5, which contains at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye.
7.1) The ink composition for hydrogen peroxide sterilization detection according to Item 4 or 5, which contains at least one of styrene acrylic resin and styrene maleic acid resin and 2) a methine dye.
8.1) At least one of anthraquinone dyes, azo dyes, and methine dyes, 2) a nitrogen-containing polymer, and 3) a cationic surfactant. Item 6. The ink composition for detecting hydrogen peroxide plasma sterilization according to Item 4 or 5.
9. A package for hydrogen peroxide or hydrogen peroxide plasma sterilization, wherein the indicator according to any one of Items 1 to 3 is provided on the inner surface of the gas permeable package.
10. Item 10. The package according to Item 9, wherein a transparent window is provided on a part of the package so that the indicator can be confirmed from the outside.
11. Item 11. The package according to Item 9 or 10, wherein the gas permeable package is formed of polyethylene fiber.
12 The step of loading the object to be processed in any of the above items 9 to 11, the step of sealing the package in which the object to be processed is loaded, and the package is sterilized with hydrogen peroxide or hydrogen peroxide plasma A hydrogen peroxide or hydrogen peroxide plasma sterilization treatment method comprising a step of placing in a sterilizing atmosphere.
13. Item 13. The method according to Item 12, wherein the package is placed in an atmosphere of hydrogen peroxide or a hydrogen peroxide plasma sterilization until the color changing layer of the indicator changes color.
　以下、本発明のインジケーターについて詳細に説明する。 Hereinafter, the indicator of the present invention will be described in detail.
　本発明のインジケーターは、基材上に過酸化水素又は過酸化水素プラズマの存在下で変色する変色層を有する過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターであって、前記変色層の表面粗さＲａが２．５～１５．０μｍの範囲であることを特徴とする。 The indicator of the present invention is a hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator having a discoloration layer that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma on a substrate, the surface roughness of the discoloration layer. The thickness Ra is in the range of 2.5 to 15.0 μm.
　上記特徴を有する本発明のインジケーターは、特に変色層の表面粗さＲａが２．５～１５．０μｍの範囲であることにより、気体透過性包装体に被処理物とインジケーターを装填・密封し、過酸化水素滅菌処理又は過酸化水素プラズマ滅菌処理を行う場合であっても、インジケーターが気体透過性包装体に密着せず、正確な検知が可能である。 The indicator of the present invention having the above-described features is particularly suitable for loading and sealing the object to be treated and the indicator on the gas permeable package by having the surface roughness Ra of the discoloration layer in the range of 2.5 to 15.0 μm. Even when the hydrogen peroxide sterilization process or the hydrogen peroxide plasma sterilization process is performed, the indicator does not adhere to the gas-permeable package, and accurate detection is possible.
　本発明のインジケーターは、変色層が上記表面粗さＲａを有し、過酸化水素又は過酸化水素プラズマの存在下で変色する限り、他の構成は従来公知のインジケーターと同じとすることができる。 The indicator of the present invention can have the same configuration as the conventionally known indicator as long as the discoloration layer has the surface roughness Ra and changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma.
　なお、本発明では、基材上に基材面積の０．２～２０％の開口部を設けることにより、インジケーターが気体透過性包装体に密着することをより確実に防止することが好ましい。この開口部は、基材上（変色層が形成されている部分も含む）に１つ又は２つ以上設けることができ、好ましくは変色層が形成されている部分に２つ以上設ける。開口部の形状は特に限定されず、円形、四角形、三角形等の各種形状が採用できる。開口部の具体例としては、例えば、直径２ｍｍ～４ｍｍの円形の孔を、変色層の両脇に設ける態様、変色層の中央部分に設ける態様、基材上（変色層が形成されている部分も含む）にランダムに設ける態様等が挙げられる。上記例の場合には、開口部の総面積は基材面積の０．３～１３％の範囲内であることが好ましい。 In the present invention, it is preferable to more reliably prevent the indicator from adhering to the gas permeable package by providing an opening of 0.2 to 20% of the substrate area on the substrate. One or two or more openings may be provided on the substrate (including a portion where the color-changing layer is formed), and preferably two or more openings are provided in the portion where the color-changing layer is formed. The shape of the opening is not particularly limited, and various shapes such as a circle, a square, and a triangle can be adopted. Specific examples of the opening include, for example, a mode in which circular holes having a diameter of 2 mm to 4 mm are provided on both sides of the color changing layer, a mode in which the central portion of the color changing layer is provided, and a part on which the color changing layer is formed And the like provided randomly. In the case of the above example, the total area of the openings is preferably within the range of 0.3 to 13% of the substrate area.
　更に、本発明では、基材上に、型押し溝、スリット（線状の孔）及びミシン目（破線状の孔）からなる群から選択される少なくとも１種が設けることにより、インジケーターが気体透過性包装体に密着することをより確実に防止することが好ましい。型押し溝は、例えば、図２の例１～３に示されるようにインジケーターの対辺を横切るように縦筋、横筋等を単独又は組み合わせて設けることができる。このような型押し溝は公知のエンボス機により設けることができ、例えば、図３に示されるように溝の深さは２５～３５μｍ程度に設定することが好ましい。なお、型押し溝を形成する向きは特に限定されず、変色層を有する面が凹部となるように設けてもよく、凸部となるように設けてもよい。スリットを設ける場合には、図２の例３に示されるように変色層上に１本又は複数本を設けることが好ましい。なお、インジケーターの強度等を考慮してスリットをミシン目（図示なし）に置き換えることもできる。このような型押し溝、スリット及びミシン目の少なくとも１種を設けることにより、過酸化水素の流動を確保することができるため、インジケーターが気体透過性包装体に密着することをより確実に防止することができる。 Furthermore, in the present invention, the indicator is gas permeable by providing at least one selected from the group consisting of embossed grooves, slits (linear holes) and perforations (dashed holes) on the substrate. It is preferable to more reliably prevent adhesion to the adhesive package. For example, as shown in Examples 1 to 3 in FIG. 2, the embossed grooves can be provided with vertical stripes, horizontal stripes or the like alone or in combination so as to cross the opposite sides of the indicator. Such an embossing groove can be provided by a known embossing machine. For example, as shown in FIG. 3, the depth of the groove is preferably set to about 25 to 35 μm. The direction in which the embossing grooves are formed is not particularly limited, and the surface having the discoloration layer may be provided as a concave portion or may be provided as a convex portion. When providing a slit, it is preferable to provide one or more on the color changing layer as shown in Example 3 of FIG. The slit can be replaced with a perforation (not shown) in consideration of the strength of the indicator. By providing at least one kind of such embossed grooves, slits and perforations, it is possible to ensure the flow of hydrogen peroxide, thereby more reliably preventing the indicator from sticking to the gas permeable packaging. be able to.
　更に、本発明では、基材上に四角形、三角形等の各種形状の切り込みを設けて基材の一部を平面から起こすことにより、インジケーターが気体透過性包装体に密着することをより確実に防止することが好ましい。このような切り込みは基材上に１つ又は２つ以上設けることができる。このような切り込みの具体例を図１のｂ－２～ｂ－５に示す。 Furthermore, in the present invention, it is possible to more reliably prevent the indicator from adhering to the gas permeable packaging body by providing cuts of various shapes such as squares and triangles on the base material and raising a part of the base material from the flat surface. It is preferable to do. One or more such cuts can be provided on the substrate. Specific examples of such cuts are shown in b-2 to b-5 in FIG.
　更に、本発明では、インジケーターを折り曲げて使用し、インジケーターが気体透過性包装体に密着することをより確実に防止することが好ましい。このような折り曲げは、例えばインジケーターの形状が長方形である場合に、対辺を横切るように折り曲げる態様やインジケーターの端部を三角形に折り曲げる態様などが挙げられる。このような折り曲げの具体例を図１のａ－１～ｂ－１に示す。なお、折り曲げる向きは特に限定されず、変色層を有する面が山折りであってもよく、谷折りであってもよい。 Furthermore, in the present invention, it is preferable to fold and use the indicator to more reliably prevent the indicator from sticking to the gas permeable packaging. For example, when the shape of the indicator is a rectangle, the bending may be performed so as to bend across the opposite side, or bend the end of the indicator into a triangle. Specific examples of such bending are shown in a-1 to b-1 in FIG. Note that the direction of folding is not particularly limited, and the surface having the discoloration layer may be mountain-folded or valley-folded.
　インジケーターの基材としては、塗布又は印刷によって変色層を形成できるものが良く、例えば、金属又は合金、セラミックス、ガラス、コンクリート、プラスチックス（ポリエチレンテレフタレート（ＰＥＴ）、ポリプロピレン、ナイロン、ポリスチレン等）、繊維類（不織布、織布、その他の繊維シート）、これらの複合材料等を用いることができる。また、ポリプロピレン合成紙、ポリエチレン合成紙等の合成樹脂繊維紙（合成紙）も好適に用いることができる。 As the base material of the indicator, those which can form a discoloration layer by coating or printing are good, for example, metal or alloy, ceramics, glass, concrete, plastics (polyethylene terephthalate (PET), polypropylene, nylon, polystyrene, etc.), fiber (Nonwoven fabric, woven fabric, other fiber sheets), composite materials of these, and the like can be used. Moreover, synthetic resin fiber paper (synthetic paper) such as polypropylene synthetic paper and polyethylene synthetic paper can also be suitably used.
　本発明における変色層は、過酸化水素又は過酸化水素プラズマの存在下で色が他の色に変化するもののほか、色が退色又は消色するものも包含される。変色層は、後述のインキ組成物を用い、例えば、シルクスクリーン印刷、グラビア印刷、オフセット印刷、凸版印刷、フレキソ印刷等の印刷方法で行うことができる。また、印刷以外でも形成できる。例えば、基材をインキ組成物に浸漬することによって変色層を形成することもできる。この方法は、不織布等のようにインキが浸透する材料には特に好適である。 The discoloration layer in the present invention includes not only those whose color changes to other colors in the presence of hydrogen peroxide or hydrogen peroxide plasma, but also those whose colors fade or disappear. The discoloration layer can be formed by a printing method such as silk screen printing, gravure printing, offset printing, letterpress printing, flexographic printing, etc., using an ink composition described later. Also, it can be formed by other than printing. For example, the discoloration layer can be formed by immersing the substrate in the ink composition. This method is particularly suitable for a material into which ink penetrates, such as a nonwoven fabric.
　本発明では、変色層を形成するためのインキ組成物は、過酸化水素又は過酸化水素プラズマの存在下で変色する成分に加えて、平均粒子径１～３０μｍの粒子を含有することが好ましい。この粒子を含有することにより、変色層の表面粗さＲａを２．５～１５．０μｍ（好ましくは２．５～５．０μｍ）に設定し易い。なお、本明細書における表面粗さＲａは、ＪＩＳ　Ｂ　０６０１で規定されるＲａである。なお、本発明では、上記粒子を用いることによって変色層の表面粗さを所定範囲に設定することに加えて、機械的手法（例えば、サンドペーパーやサンドブラストによる粗面化、シルクスクリーン印刷による変色層の膜厚印刷）を併用することもできる。 In the present invention, the ink composition for forming the color changing layer preferably contains particles having an average particle size of 1 to 30 μm in addition to the component that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma. By containing these particles, the surface roughness Ra of the discoloration layer can be easily set to 2.5 to 15.0 μm (preferably 2.5 to 5.0 μm). In addition, surface roughness Ra in this specification is Ra prescribed | regulated by JISB0601. In the present invention, in addition to setting the surface roughness of the color changing layer within a predetermined range by using the above particles, a mechanical method (for example, roughening by sandpaper or sandblasting, color changing layer by silk screen printing) Can also be used in combination.
　粒子の平均粒子径は１～３０μｍが好ましく、５～１５μｍがより好ましい。粒子の材質としては限定的ではないが、高分子化合物及び無機化合物の少なくとも１種であって、過酸化水素又は過酸化水素プラズマと反応したり吸着したりしないものが好ましい。 The average particle size of the particles is preferably 1 to 30 μm, more preferably 5 to 15 μm. The material of the particles is not limited, but is preferably at least one of a polymer compound and an inorganic compound that does not react with or adsorb hydrogen peroxide or hydrogen peroxide plasma.
　高分子化合物としては、ポリエチレン、ポリプロピレン、アクリル共重合体、ポリエステル、ポリアミド、ポリウレタン、フェノール樹脂、メラミン樹脂等が挙げられる。高分子化合物は、樹脂球だけでなく、中空樹脂球、マイクロカプセル等であってもよい。また、無色である必要はなく、染料や顔料により着色されていてもよい。 Examples of the polymer compound include polyethylene, polypropylene, acrylic copolymer, polyester, polyamide, polyurethane, phenol resin, and melamine resin. The polymer compound may be not only resin spheres but also hollow resin spheres, microcapsules, and the like. Moreover, it does not need to be colorless and may be colored with dyes or pigments.
　上記高分子化合物の中でも、低分子量ポリエチレン樹脂球が好ましく、例えば、市販品のケミパールＷ３０８（平均粒子径６μｍ、軟化点１３２℃）、ケミパールＷ２００（平均粒子径６μｍ、軟化点１１３℃）、ケミパールＷ３１０（平均粒子径９．５μｍ、軟化点１３２℃、いずれも三井化学製の４０％水分散液）等が好ましいものとして挙げられる。 Among the above polymer compounds, low molecular weight polyethylene resin spheres are preferable. For example, commercially available Chemipearl W308 (average particle size 6 μm, softening point 132 ° C.), Chemipearl W200 (average particle size 6 μm, softening point 113 ° C.), Chemipearl W310 (Average particle size 9.5 μm, softening point 132 ° C., 40% aqueous dispersion manufactured by Mitsui Chemicals) and the like are preferable.
　無機化合物としては、炭酸カルシウム、ガラス等が挙げられる。無機化合物は、必要に応じて球状だけでなく、板状物（フレーク状物）、針状物等の物質を用いてもよい。以下、粒子、板状物、針状物を総称して「粒子等」と称する。いずれの場合も変色層の表面粗さＲａが２．５～５．０μｍに入るように併用することができる。板状及び針状の場合には、いずれもレーザー回折法で測定される球換算径で１～３０μｍの大きさが好ましい。 Examples of inorganic compounds include calcium carbonate and glass. The inorganic compound is not limited to a spherical shape, but may be a plate-like material (flake-like material), a needle-like material, or the like, if necessary. Hereinafter, particles, plates, and needles are collectively referred to as “particles”. In either case, the color change layer can be used in combination so that the surface roughness Ra falls within the range of 2.5 to 5.0 μm. In the case of a plate-like shape and a needle-like shape, the diameter is preferably 1 to 30 μm in terms of a sphere equivalent diameter measured by a laser diffraction method.
　インキ組成物中の上記粒子等の含有量は限定されないが、上記粒子等を除いたインキ１００重量部に対して１～５０重量部を加えることが好ましく、５～２０重量部加えることがより好ましい。粒子等の含有量が多すぎると、基材との接着性が低下したり、印刷解像度が低下したりするおそれがある。一方、粒子等の含有量が少なすぎると、所定の効果が得られ難くなる。 The content of the particles and the like in the ink composition is not limited, but it is preferably 1 to 50 parts by weight, more preferably 5 to 20 parts by weight, based on 100 parts by weight of the ink excluding the particles and the like. . When there is too much content, such as particle | grains, there exists a possibility that adhesiveness with a base material may fall or print resolution may fall. On the other hand, when there is too little content, such as particle | grains, it will become difficult to acquire a predetermined effect.
　本発明では、インキ組成物中に含まれる過酸化水素又は過酸化水素プラズマの存在下で変色する成分としては、公知のものが使用できる。例えば、過酸化水素滅菌検知用インキ組成物としては、アゾ系染料、メチン系染料、トリアリールメタン系染料及びチアジン系染料の少なくとも１種を含有するインキ組成物（特開2006-78463号公報に記載のもの）、１）スチレンアクリル樹脂及びスチレンマレイン酸樹脂の少なくとも１種及び２）メチン系染料を含有するインキ組成物（特開2007-40785号公報に記載のもの）等が使用できる。また、過酸化水素プラズマ滅菌検知用インキ組成物としては、１）アントラキノン系染料、アゾ系染料及びメチン系染料の少なくとも１種、２）窒素含有高分子及び３）カチオン系界面活性剤を含有するインキ組成物（特開2005-315828号公報に記載のもの）等が好適に使用できる。これらのインキ組成物について以下に簡単に説明する。 In the present invention, known components can be used as components that change color in the presence of hydrogen peroxide or hydrogen peroxide plasma contained in the ink composition. For example, as an ink composition for detecting hydrogen peroxide sterilization, an ink composition containing at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye (see JP-A-2006-78463). As described above), 1) at least one styrene acrylic resin and styrene maleic acid resin, and 2) an ink composition containing a methine dye (described in JP-A-2007-40785) can be used. The ink composition for detecting hydrogen peroxide plasma sterilization contains 1) at least one anthraquinone dye, azo dye, and methine dye, 2) a nitrogen-containing polymer, and 3) a cationic surfactant. An ink composition (described in JP-A-2005-315828) can be preferably used. These ink compositions will be briefly described below.
　過酸化水素滅菌検知用インキ組成物
　アゾ系染料、メチン系染料、トリアリールメタン系染料及びチアジン系染料の少なくとも１種を含有するインキ組成物（特開2006-78463号公報に記載のもの）が挙げられる。 Ink composition for hydrogen peroxide sterilization detection An ink composition containing at least one of an azo dye, a methine dye, a triarylmethane dye and a thiazine dye (described in JP-A-2006-78463) Can be mentioned.
　アゾ系染料は、発色団としてアゾ基－Ｎ＝Ｎ－を有するものであれば限定されない。例えば、モノアゾ染料、ポリアゾ染料、金属錯塩アゾ染料、スチルベンアゾ染料、チアゾールアゾ染料等が挙げられる。より具体的に染料番号で表記すれば、C.I.Disperse Red 13、C.I.Disperse Red 52、C.I.Disperse Violet 24、C.I.Disperse Blue、44、C.I.Disperse Red 58、C.I.Disperse Red 88、C.I.Disperse Yellow 23、C.I.Disperse Orange 1、C.I.Disperse Orange 5、C.I.Solvent Red 1、 C.I.Solvent Red 3、C.I.Solvent Red 23等を挙げることができる。これらは、１種又は２種以上で用いることができる。 The azo dye is not limited as long as it has an azo group —N═N— as a chromophore. Examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, the dye numbers are CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue, 44, CIDisperse Red 58, CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIsisperse Orange 5, CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, and the like. These can be used alone or in combination of two or more.
　メチン系染料としては、メチン基を有する染料であれば良い。従って、本発明において、ポリメチン系染料、シアニン系染料等もメチン系染料に包含される。これらは、公知又は市販のメチン系染料から適宜採用することができる。具体的には、C.I.Basic Red 12、C.I.Basic Red 13、C.I.Basic Red 14、C.I.Basic Red 15、C.I.Basic Red 27、C.I.Basic Red 35、C.I.Basic Red 36、C.I.Basic Red 37、C.I.Basic Red 45、C.I.Basic Red 48、C.I.Basic Yellow 11、C.I.Basic Yellow 12、C.I.Basic Yellow 13、C.I.Basic Yellow 14、C.I.Basic Yellow 21、C.I.Basic Yellow 22、C.I.Basic Yellow 23、C.I.Basic Yellow 24、C.I.Basic Violet 7、C.I.Basic Violet 15、C.I.Basic Violet 16、C.I.Basic Violet 20、C.I.Basic Violet 21、C.I.Basic Violet 39、C.I.Basic Blue 62、C.I.Basic Blue 63等を挙げることができる。これらは、１種又は２種以上で用いることができる。 As the methine dye, any dye having a methine group may be used. 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 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.
　トリアリールメタン系染料は限定的でなく、公知又は市販のものを使用することができる。例えば、C.I.Basic Blue 1、C.I.Basic Blue 26、C.I.Basic Blue 5、C.I.Basic Blue 8、C.I.Basic Green 1、C.I.Basic Red 9、C.I.Basic Violet 12、C.I.Basic Violet 14、C.I.Basic Violet 3、C.I.Solvent Green 15、C.I.Solvent Violet 8等を挙げることができる。これらは、１種又は２種以上で用いることができる。これらトリアリールメタン系染料の中でも、C.I.Solvent Violet 8、C.I.Basic Green 1、C.I.Basic Red 9、C.I.Basic Blue 1等を好適に用いることができる。 The triarylmethane dye is not limited, and a known or commercially available dye can be used. For example, CIBasic Blue 1, CIBasic Blue 26, CIBasic Blue 5, CIBasic Blue 8, CIBasic Green 1, CIBasic Red 9, CIBasic Violet 12, CIBasic Violet 14, CIBasic Violet 3, CISRol Green 15, CISolvent Violet 8 etc. These can be used alone or in combination of two or more. Among these triarylmethane dyes, C.I.Solvent Violet 8, C.I.Basic Green 1, C.I.Basic Red 9, C.I.Basic Blue 1 and the like can be suitably used.
　チアジン系染料は特に限定されることなく、公知又は市販のものから選ぶことができる。例えば、C.I.Basic Blue 9、C.I.Basic Blue 25、C.I.Basic Blue 24、C.I.Basic Blue 17、C.I.Basic Green 5、C.I.Solvent Blue 8等を挙げることができる。これらは、１種又は２種以上で用いることができる。これらチアジン系染料の中でも、C.I.Basic Blue 9等を好適に用いることができる。 The thiazine dye is not particularly limited and can be selected from known or commercially available ones. Examples thereof include C.I.Basic Blue-9, C.I.Basic Blue-25, C.I.Basic Blue-24, C.I.Basic Blue-17, C.I.Basic Green-5, C.I.Solvent Blue-8, and the like. These can be used alone or in combination of two or more. Among these thiazine dyes, C.I.Basic Blue 9 can be suitably used.
　これらの染料の含有量は、用いる染料の種類、所望の検知特性等により異なるが、インキ組成物中０．０１～１０重量％とし、好ましくは０．０５～５重量％、より好ましくは０．１～２重量％とすればよい。 The content of these dyes varies depending on the type of dye used, desired detection characteristics, etc., but is 0.01 to 10% by weight, preferably 0.05 to 5% by weight, more preferably 0.00% in the ink composition. It may be 1 to 2% by weight.
　また、１）スチレンアクリル樹脂及びスチレンマレイン酸樹脂の少なくとも１種及び２）メチン系染料を含有するインキ組成物（特開2007-40785号公報に記載のもの）が挙げられる。 Also, 1) at least one kind of styrene acrylic resin and styrene maleic acid resin and 2) an ink composition containing a methine dye (as described in JP-A-2007-40785) can be mentioned.
　メチン系染料としては、メチン基を有する染料であれば良い。従って、本発明において、ポリメチン系染料、シアニン系染料等もメチン系染料に包含される。これらは、公知又は市販のメチン系染料から適宜採用することができる。具体的には、C.I.Basic Red 12、C.I.Basic Red 13、C.I.Basic Red 14、C.I.Basic Red 15、C.I.Basic Red 27、C.I.Basic Red 35、C.I.Basic Red 36、C.I.Basic Red 37、C.I.Basic Red 45、C.I.Basic Red 48、C.I.Basic Yellow 11、C.I.Basic Yellow 12、C.I.Basic Yellow 13、C.I.Basic Yellow 14、C.I.Basic Yellow 21、C.I.Basic Yellow 22、C.I.Basic Yellow 23、C.I.Basic Yellow 24、C.I.Basic Violet 7、C.I.Basic Violet 15、C.I.Basic Violet 16、C.I.Basic Violet 20、C.I.Basic Violet 21、C.I.Basic Violet 39、C.I.Basic Blue 62、C.I.Basic Blue 63等を挙げることができる。これらは、１種又は２種以上で用いることができる。 As the methine dye, any dye having a methine group may be used. 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 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.
　上記染料の含有量は、所望の色相等に応じて適宜決定できるが、一般的にはインキ組成物中０．０５～５重量％程度、特に０．１～１重量％とすることが望ましい。 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 0.1 to 1% by weight in the ink composition.
　スチレンアクリル樹脂及びスチレンマレイン酸樹脂の種類及び性状は限定的でなく、公知又は市販のものを使用することができる。スチレンアクリル樹脂及びスチレンマレイン酸樹脂の含有量は、用いる着色剤の種類等に応じて適宜決定できるが、一般的にはインキ組成物中５０重量％以下程度、特に１～３５重量％とすることが望ましい。 The types and properties of the styrene acrylic resin and styrene maleic acid resin are not limited, and known or commercially available ones can be used. The content of the styrene acrylic resin and the styrene maleic acid resin can be appropriately determined according to the type of the colorant used and the like, but is generally about 50% by weight or less, particularly 1 to 35% by weight in the ink composition. Is desirable.
　過酸化水素プラズマ滅菌検知用インキ組成物
　１）アントラキノン系染料、アゾ系染料及びメチン系染料の少なくとも１種、２）窒素含有高分子及び３）カチオン系界面活性剤を含有するインキ組成物（特開2005-315828号公報に記載のもの）が挙げられる。 Ink composition for hydrogen peroxide plasma sterilization detection 1) Ink composition containing at least one kind of anthraquinone dye, azo dye and methine dye, 2) nitrogen-containing polymer and 3) cationic surfactant No. 2005-315828).
　アントラキノン系染料はアントラキノンを基本骨格とするものであれば限定的でなく、公知のアントラキノン系分散染料等も使用できる。特にアミノ基を有するアントラキノン系染料が好ましい。より好ましくは、第一アミノ基及び第二アミノ基の少なくとも１種のアミノ基を有するアントラキノン系染料である。この場合、各アミノ基は、２以上有していても良く、これらは互いに同種又は相異なっても良い。 The anthraquinone dye is not limited as long as it has anthraquinone as a basic skeleton, and a known anthraquinone disperse dye or the like can also be used. An anthraquinone dye having an amino group is particularly preferable. More preferred is an anthraquinone dye having at least one amino group of a primary amino group and a secondary amino group. In this case, each amino group may have two or more, and these may be the same or different from each other.
　より具体的には、例えば１，４－ジアミノアントラキノン（C.I.Disperse Violet 1）、１－アミノ－４－ヒドロキシ－２－メチルアミノアントラキノン（C.I.Disperse Red 4）、１－アミノ－４－メチルアミノアントラキノン（C.I.Disperse Violet 4）、１，４－ジアミノ－２－メトキシアントラキノン（C.I.Disperse Red 11）、１－アミノ－２－メチルアントラキノン（C.I.Disperse Orange 11）、１－アミノ－４－ヒドロキシアントラキノン（C.I.Disperse Red 15）、１，４，５，８－テトラアミノアントラキノン（C.I.Disperse Blue 1）、１，４－ジアミノ－５－ニトロアントラキノン（C.I.Disperse Violet 8）等を挙げることができる（カッコ内は染料番号）。その他にも C.I.Solvent Blue 14、C.I.Solvent Blue 35、C.I.Solvent Blue 63、C.I.Solvent Violet 13、C.I.Solvent Violet 14、C.I.Solvent Red 52、C.I.Solvent Red 114、C.I.Vat Blue 21、C.I.Vat Blue 30、C.I.Vat Violet 15、C.I.Vat Violet 17、C.I.Vat Red 19、C.I.Vat Red 28、C.I.Acid Blue 23、C.I.Acid Blue 80、C.I.Acid Violet 43、C.I.Acid Violet 48、C.I.Acid Red 81、C.I.Acid Red 83、C.I.Reactive Blue 4、C.I.Reactive Blue 19、C.I.Disperse Blue 7 等として知られている染料も使用することができる。これらのアントラキノン系染料は、単独で又は２種以上併用することができる。これらアントラキノン系染料の中でも、C.I Disperse Blue 7、C.I Disperse Violet 1 等が好ましい。また、本発明では、これらのアントラキノン系染料の種類（分子構造等）を変えることによって検知感度の制御を行うこともできる。 More specifically, for example, 1,4-diaminoanthraquinone (CIDisperse Violet 1), 1-amino-4-hydroxy-2-methylaminoanthraquinone (CIDisperse Red 4), 1-amino-4-methylaminoanthraquinone ( CIDisperse Violet 4), 1,4-diamino-2-methoxyanthraquinone (CIDisperse Red 11), 1-amino-2-methylanthraquinone (CIDisperse Orange 11), 1-amino-4-hydroxyanthraquinone (CIDisperse Red) 15), 1,4,5,8-tetraaminoanthraquinone (CIDisperse Blue 1), 1,4-diamino-5-nitroanthraquinone (CIDisperse Violet 8) and the like (dye number in parentheses) . In addition, CISolvent Blue 14, CISolvent Blue 35, CISolvent Blue 63, CISolvent Violet 13, CISolvent Violet 14, CISolvent Red 52, CISolvent Red 114, CIVat Blue 21, CIVat Blue 30, CIVat Violet 15, CIVat Violet 17, CIVat Red 19, CIVat Red 28, CIAcid Blue 23, CIAcid Blue 80, CIAcid Violet 43, CIAcid Violet 48, CIAcid Red 81, CIAcid Red 83, CIReactive Dyes known as Blue 4, CIReactive Blue 19, CIdisperse Blue 7 etc. can also be used. These anthraquinone dyes can be used alone or in combination of two or more. Among these anthraquinone dyes, C.I Disperse Blue 7, C.I Disperse Violet 1 and the like are preferable. In the present invention, the detection sensitivity can be controlled by changing the type (molecular structure, etc.) of these anthraquinone dyes.
　アゾ系染料は、発色団としてアゾ基－Ｎ＝Ｎ－を有するものであれば限定されない。例えば、モノアゾ染料、ポリアゾ染料、金属錯塩アゾ染料、スチルベンアゾ染料、チアゾールアゾ染料等が挙げられる。より具体的に染料番号で表記すれば、C.I.Solvent Red 1、C.I.Solvent Red 3、C.I.Solvent Red 23、C.I.Disperse Red 13、C.I.Disperse Red 52、C.I.Disperse Violet 24、C.I.Disperse Blue 44、C.I.Disperse Red 58、C.I.Disperse Red 88、C.I.Disperse Yellow 23、C.I.Disperse Orange 1、C.I.Disperse Orange 5等を挙げることができる。これらは、１種又は２種以上で用いることができる。 The azo dye is not limited as long as it has an azo group —N═N— as a chromophore. Examples thereof include monoazo dyes, polyazo dyes, metal complex azo dyes, stilbene azo dyes, thiazole azo dyes, and the like. More specifically, the dye numbers are CISolvent Red 1, CISolvent Red 3, CISolvent Red 23, CIDisperse Red 13, CIDisperse Red 52, CIDisperse Violet 24, CIDisperse Blue 44, CIDisperse Red 58 CIDisperse Red 88, CIDisperse Yellow 23, CIDisperse Orange 1, CIDisperse Orange 5, and the like. These can be used alone or in combination of two or more.
　メチン系染料としては、メチン基を有する染料であれば良い。従って、本発明において、ポリメチン系染料、シアニン系染料等もメチン系染料に包含される。これらは、公知又は市販のメチン系染料から適宜採用することができる。具体的には、C.I.Basic Red 12、C.I.Basic Red 13、C.I.Basic Red 14、C.I.Basic Red 15、C.I.Basic Red 27、C.I.Basic Red 35、C.I.Basic Red 36、C.I.Basic Red 37、C.I.Basic Red 45、C.I.Basic Red 48、C.I.Basic Yellow 11、C.I.Basic Yellow 12、C.I.Basic Yellow 13、C.I.Basic Yellow 14、C.I.Basic Yellow 21、C.I.Basic Yellow 22、C.I.Basic Yellow 23、C.I.Basic Yellow 24、C.I.Basic Violet 7、C.I.Basic Violet 15、C.I.Basic Violet 16、C.I.Basic Violet 20、C.I.Basic Violet 21、C.I.Basic Violet 39、C.I.Basic Blue 62、C.I.Basic Blue 63等を挙げることができる。これらは、１種又は２種以上で用いることができる。 As the methine dye, any dye having a methine group may be used. 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 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.
　上記染料の含有量は、染料の種類、所望の色相等に応じて適宜決定できるが、一般的にはインキ組成物中０．０５～５重量％程度、特に０．１～１重量％とすることが望ましい。 The content of the dye can be appropriately determined according to the type of dye, desired hue, etc., but is generally about 0.05 to 5% by weight, particularly 0.1 to 1% by weight in the ink composition. It is desirable.
　窒素含有高分子は、例えばポリアミド樹脂、ポリイミド樹脂、ポリアクリロニトリル樹脂、アミノ樹脂、ポリアクリルアミド、ポリビニルピロリドン、ポリビニルイミダゾール、ポリエチレンイミン等の合成樹脂を好適に用いることができる。これらは１種又は２種以上で使用することができる。インク組成物において、窒素含有高分子は感度強化剤としての役割を果たす。すなわち、感度強化剤を用いることにより、過酸化水素プラズマ滅菌検知の精度（感度）をより高めることができる。これにより、過酸化水素プラズマ滅菌用包装体中においても確実に変色するので、上記包装体に用いるインジケーターとして非常に有利である。 As the nitrogen-containing polymer, for example, a synthetic resin such as polyamide resin, polyimide resin, polyacrylonitrile resin, amino resin, polyacrylamide, polyvinyl pyrrolidone, polyvinyl imidazole, or polyethyleneimine can be suitably used. These can be used alone or in combination of two or more. In the ink composition, the nitrogen-containing polymer serves as a sensitivity enhancer. That is, by using a sensitivity enhancer, the accuracy (sensitivity) of hydrogen peroxide plasma sterilization detection can be further increased. Thereby, since the color is surely changed even in the package for hydrogen peroxide plasma sterilization, it is very advantageous as an indicator used for the package.
　かかる見地より、本発明では特にポリアミド樹脂を用いることが好ましい。ポリアミド樹脂の種類、分子量等は特に限定されず、公知又は市販のポリアミド樹脂を用いることができる。この中でも、リノール酸の二量体とジ－又はポリアミンとの反応生成物（長鎖線状重合物）であるポリアミド樹脂を好適に用いることができる。ポリアミド樹脂は、分子量４０００～７０００の熱可塑性樹脂である。このような樹脂も市販品を用いることができる。 From this viewpoint, it is particularly preferable to use a polyamide resin in the present invention. The kind of polyamide resin, molecular weight, etc. are not specifically limited, A well-known or commercially available polyamide resin can be used. Among these, a polyamide resin which is a reaction product (long chain linear polymer) of a dimer of linoleic acid and di- or polyamine can be preferably used. The polyamide resin is a thermoplastic resin having a molecular weight of 4000 to 7000. A commercially available product can also be used for such a resin.
　窒素含有高分子の含有量は、上記高分子の種類、用いる着色剤の種類等に応じて適宜決定できるが、一般的にはインキ組成物中０．１～５０重量％程度、特に１～２０重量％とすることが望ましい。 The content of the nitrogen-containing polymer can be appropriately determined according to the type of the polymer, the type of colorant used, etc., but is generally about 0.1 to 50% by weight, particularly 1 to 20% in the ink composition. It is desirable to set the weight%.
　カチオン系界面活性剤としては、特に制限されないが、特にアルキルアンモニウム塩、イソキノリニウム塩、イミダゾリニウム塩及びピリジニウム塩の少なくともを用いることが望ましい。これらは、公知もの又は市販品も使用できる。本発明では、これらカチオン系界面活性剤を前記の染料と併用することによって、より優れた検知感度を得ることができる。 The cationic surfactant is not particularly limited, but it is particularly desirable to use at least one of an alkyl ammonium salt, an isoquinolinium salt, an imidazolinium salt, and a pyridinium salt. These may be known or commercially available products. In the present invention, a superior detection sensitivity can be obtained by using these cationic surfactants in combination with the above dyes.
　アルキルアンモニウム塩の中でも、アルキルトリメチルアンモニウム塩、ジアルキルジメチルアンモニウム塩等が好ましい。具体的には、塩化ヤシアルキルトリメチルアンモニウム、塩化牛脂アルキルトリメチルアンモニウム、塩化ベヘニルトリメチルアンモニウム、塩化ヘキサデシルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム、塩化オクタデシルトリメチルアンモニウム、塩化ジオクチルジメチルアンモニウム、塩化ジステアリルジメチルアンモニウム、塩化アルキルベンジルジメチルアンモニウム等が挙げられる。特に、塩化ヤシアルキルトリメチルアンモニウム、塩化ラウリルトリメチルアンモニウム等が好ましい。 Among the alkylammonium salts, alkyltrimethylammonium salts, dialkyldimethylammonium 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, coconut alkyltrimethylammonium chloride and lauryltrimethylammonium chloride are preferable.
　イソキノリニウム塩としては、例えばラウリルイソキノリニウムブロマイド、セチルイソキノリニウムブロマイド、セチルイソキノリニウムクロライド、ラウリルイソキノリニウムクロライド等が挙げられる。この中でも、特にラウリルイソキノリニウムブロマイドが好ましい。 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.
　イミダゾリニウム塩としては、例えば１－ヒドロキシエチル－２－オレイルイミダゾリニウムクロライド、２－クロロ－１，３－ジメチルイミダゾリニウムクロライド等が挙げられる。この中でも、特に２－クロロ－１，３－ジメチルイミダゾリニウムクロライドが好ましい。 Examples of the imidazolinium salt include 1-hydroxyethyl-2-oleylimidazolinium chloride, 2-chloro-1,3-dimethylimidazolinium chloride, and the like. Of these, 2-chloro-1,3-dimethylimidazolinium chloride is particularly preferable.
　ピリジニウム塩としては、例えばピリジニウムクロライド、１－エチルピリジニウムブロマイド、ヘキサデシルピリジニウムクロライド、セチルピリジニウムクロライド、１－ブチルピリジニウムクロライド、Ｎ－ｎ－ブチルピリジニウムクロライド、ヘキサデシルピリジニウムブロマイド、Ｎ－ヘキサデシルピリジニウムブロマイド、１－ドデシルピリジニウムクロライド、３－メチルヘキシルピリジニウムクロライド、４－メチルヘキシルピリジニウムクロライド、３－メチルオクチルピリジニウムクロライド、２－クロロ－１－メチルピリジニウムアイオダイド、３，４－ジメチルブチルピリジニウムクロリド、ピリジニウム－ｎ－ヘキサデシルクロリド－水和物、Ｎ－（シアノメチル）ピリジニウムクロリド、Ｎ－アセトニルピリジニウムブロマイド、１－（アミノホルミルメチル）ピリジニウムクロライド、２－アミジノピリジニウムクロライド、２－アミノピリジニウムクロライド、Ｎ－アミノピリジニウムアイオダイド、１－アミノピリジニウムアイオダイド、１－アセトニルピリジニウムクロリド、Ｎ－アセトニルピリジニウムブロマイド等が挙げられる。この中でも、特にヘキサデシルピリジニウムクロライドが好ましい。 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 pyri Nitrobromide, 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.
　カチオン系界面活性剤の含有量は、上記界面活性剤の種類、用いる染料の種類等に応じて適宜決定できるが、一般的にはインキ組成物中０．２～１０重量％程度、特に０．５～５重量％とすることが望ましい。 The content of the cationic surfactant can be appropriately determined according to the type of the surfactant, the type of the dye to be used, and the like, but is generally about 0.2 to 10% by weight in the ink composition, particularly about 0. It is desirable that the content be 5 to 5% by weight.
　その他、インキ組成物には、必要に応じて樹脂バインダー、増量剤、溶剤、レベリング剤、消泡剤、紫外線吸収剤、表面調整剤等の公知のインキに用いられている成分を適宜配合することができる。これらの成分の含有量については、常法に従えばよい。 In addition, the ink composition may be appropriately blended with components used in known inks such as a resin binder, a filler, a solvent, a leveling agent, an antifoaming agent, an ultraviolet absorber, and a surface conditioner, as necessary. Can do. What is necessary is just to follow a conventional method about content of these components.
　本発明のインジケーターは、過酸化水素又は過酸化水素プラズマ雰囲気下で行う滅菌処理であればいずれにも適用できる。従って、滅菌処理装置（具体的には、過酸化水素又は過酸化水素プラズマにより滅菌を行う装置）におけるインジケーターとして有用である。例えば、インジケーターの使用に際しては、市販の滅菌装置内に本発明インジケーターを置き、滅菌処理すべき器材等とともに滅菌処理雰囲気下に晒せば良い。この場合、装置内に置かれたインジケーターの変色により所定のプラズマ滅菌処理が行われたこと検知することができる。 The indicator of the present invention can be applied to any sterilization treatment performed in a hydrogen peroxide or hydrogen peroxide plasma atmosphere. Therefore, it is useful as an indicator in a sterilization apparatus (specifically, an apparatus that performs sterilization with hydrogen peroxide or hydrogen peroxide plasma). For example, when using the indicator, 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 plasma sterilization process has been performed by changing the color of an indicator placed in the apparatus.
　本発明では、気体透過性包装体の内面にインジケーターが設けられている過酸化水素又は過酸化水素プラズマ滅菌用包装体を用いて好適に滅菌処理を行うことができる。 In the present invention, sterilization can be suitably performed using a package for hydrogen peroxide or hydrogen peroxide plasma sterilization in which an indicator is provided on the inner surface of the gas permeable package.
　気体透過性包装体は、その中に被処理物を封入したままで滅菌できる包装体が好ましい。これは、滅菌用包装体（滅菌パウチ）として使用されている公知又は市販のものを使用することができる。例えば、ポリエチレン系繊維（ポリエチレン合成紙）により形成されている包装体を好適に用いることができる。この包装体に被処理物を入れ、開口部をヒートシール等により密閉した後、包装体ごと滅菌処理装置中で滅菌処理することができる。 The gas-permeable packaging body is preferably a packaging body that can be sterilized while the object to be treated is sealed therein. As this, a known or commercially available product used as a sterilization package (sterile pouch) can be used. For example, a package formed of polyethylene fibers (polyethylene synthetic paper) can be suitably used. After putting an object to be processed into this package and sealing the opening by heat sealing or the like, the entire package can be sterilized in a sterilization apparatus.
　インジケーターは、上記包装体の内面に配置すればよい。配置する方法は限定的でなく、接着剤、ヒートシール等による方法のほか、インキ組成物を直接に包装体の内面に塗布又は印刷することによりインジケーターを構成することもできる。また、上記塗布又は印刷による場合は、包装体の製造段階でインジケーターを形成しておくこともできる。 The indicator may be disposed on the inner surface of the package. The arrangement method is not limited, and the indicator can also be constituted by applying or printing the ink composition directly on the inner surface of the package, in addition to a method using an adhesive, heat sealing, or the like. Moreover, in the case of the application or printing, an indicator can be formed at the manufacturing stage of the package.
　本発明では、インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられていることが望ましい。例えば、包装体を透明シートと前記ポリエチレン合成紙で作製し、その透明シートを通して視認できるような位置に包装体内面にインジケーターを配置すればよい。 In the present invention, it is desirable that a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside. For example, the package may be made of a transparent sheet and the polyethylene synthetic paper, and the indicator may be arranged on the inner surface of the package at a position where it can be visually recognized through the transparent sheet.
　上記包装体を用いて滅菌処理する場合、例えば包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を過酸化水素又は過酸化水素プラズマ滅菌雰囲気下に置く工程を有する方法によれば良い。より具体的には、被処理物（医療器具、食品等）を包装体に入れた後、ヒートシール等の公知の方法に従って密封する。次いで、その包装体ごと滅菌雰囲気下に配置する。例えば、公知又は市販の滅菌装置の滅菌室に配置し、滅菌処理を行う。滅菌処理が終了した後は、包装体ごと取り出し、そのまま使用時まで包装体中で保管することができる。この場合、滅菌処理は、インジケーターの変色層が変色するまで滅菌雰囲気下に包装体を置くことが好ましい。 When sterilization is performed using the package, for example, a process of loading an object to be processed into the package, a process of sealing the package loaded with the object to be processed, and hydrogen peroxide or hydrogen peroxide plasma A method having a step of placing in a sterile atmosphere may be used. More specifically, after an object to be processed (medical instrument, food, etc.) is put in a package, it is sealed according to a known method such as heat sealing. Next, the entire package is placed in a sterile atmosphere. For example, it is placed in a sterilization chamber of a known or commercially available sterilizer and sterilized. After the sterilization process is completed, the whole package can be taken out and stored in the package until it is used. In this case, the sterilization is preferably performed by placing the package in a sterilizing atmosphere until the discoloration layer of the indicator changes color.
　本発明のインジケーターは、特に変色層の表面粗さＲａが２．５～５．０μｍの範囲であることにより、気体透過性包装体に被処理物とインジケーターを装填・密封し、過酸化水素滅菌処理又は過酸化水素プラズマ滅菌処理を行う場合であっても、インジケーターが気体透過性包装体に密着せず、正確な検知が可能である。 In the indicator of the present invention, the surface roughness Ra of the discolored layer is in the range of 2.5 to 5.0 μm. Even when the treatment or the hydrogen peroxide plasma sterilization treatment is performed, the indicator is not in close contact with the gas permeable package, and accurate detection is possible.
本発明のインジケーターに切り込みを設けて基材の一部を平面から起こす態様及び本発明のインジケーターを折り曲げる態様の一例を示す模式図である。It is a schematic diagram which shows an example of the aspect which provides an incision in the indicator of this invention and raises a part of base material from a plane, and the aspect which bends the indicator of this invention. 本発明のインジケーターの基材上に、型押し溝及び／又はスリット（線状の孔）を設ける態様の一例を示す模式図である。It is a schematic diagram which shows an example of the aspect which provides a stamping groove and / or a slit (linear hole) on the base material of the indicator of this invention. 本発明のインジケーターの基材上に、型押し溝を設けた場合の基材断面図の一例を示す模式図である。It is a schematic diagram which shows an example of base-material sectional drawing at the time of providing the embossing groove | channel on the base material of the indicator of this invention.
　以下に実施例及び比較例を示し、本発明の特徴を一層明確にする。なお、本発明は、実施例の態様に制限されない。 Examples and comparative 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.
　実施例１～３及び比較例１
　表１に示す各成分を攪拌機にて均一に混合することによってインキ組成物を調製した。具体的には、粒子（ケミパール）以外の成分を先に十分に撹拌した後、ケミパールを加えて３０分撹拌した。 Examples 1 to 3 and Comparative Example 1
Each component shown in Table 1 was uniformly mixed with a stirrer to prepare an ink composition. Specifically, components other than particles (Chemical) were sufficiently stirred first, then Chemipearl was added and stirred for 30 minutes.
　各インキ組成物を、ＰＥＴシート（東洋紡製クリスパーＫ２３２３：１２５μｍ）に２５０メッシュ版を用いてスクリーン印刷して変色層を形成した。３０分間自然乾燥した後、７０℃で５分間強制乾燥した。これによりインジケーターを作製した。 Each ink composition was screen-printed on a PET sheet (Toyobo's Crisper K2323: 125 μm) using a 250 mesh plate to form a discolored layer. After natural drying for 30 minutes, forced drying was performed at 70 ° C. for 5 minutes. This produced the indicator.
　次に、各インジケーター及び塩ビ電線５ｍ×２本を包装体（滅菌パウチ、製品名「ステラッド滅菌パウチレギュラー」）に入れ、開口部をヒートシールにより密閉したものを包装体ごとプラズマ滅菌器装置（過酸化水素低温ガスプラズマ滅菌システム「STERRAD 50」ジョンソンアンドジョンソンメディカル社製）に入れ、予めメーカーによってプログラミングされた標準条件で滅菌処理を施し、その変色不良の有無を調べた。その結果を表１に示す。 Next, each indicator and 5m x 2 PVC electric wires are placed in a package (sterilized pouch, product name "Sterad Sterilized Pouch Regular"), and the opening is sealed by heat sealing. The sample was placed in a hydrogen oxide low temperature gas plasma sterilization system “STERRAD 50” manufactured by Johnson & Johnson Medical Co., Ltd.) and sterilized under standard conditions programmed in advance by the manufacturer, and examined for the presence or absence of discoloration. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示す成分は具体的には下記の通りである。
C.I.Basic Red 14：メチン系染料
Oil Yellow 129：ジアゾ系染料
SN-W407グリーン：（フタロシアニン系顔料分散液　ＫＬＴ社製）
ジョンクリル690：（樹脂バインダー、ジョンソンポリマー製、スチレンアクリル酸樹脂
）
MOWITAL PVB-B20H：（樹脂バインダー、クラレ製、ポリビニルブチラール）
NIKKOL CA-2150（カチオン系界面活性剤、日光ケミカルズ製）
ブチルセロソルブ：溶剤
プロピレングリコールモノメチルエーテル：溶剤
SH200オイル 100CS：（消泡剤、東レ・ダウコーニング製、シリコーンオイル）
　表１の結果から分かるように、変色層の表面粗さＲａが２．５～１５．０μｍである実施例１～３のインジケーターはフィルム密着による変色不良は認められないが、Ｒａが０．４７μｍである比較例１のインジケーターはフィルム密着による変色不良が認められる。 The components shown in Table 1 are specifically as follows.
CIBasic Red 14: Methine dye
Oil Yellow 129: Diazo dye
SN-W407 Green: (Phthalocyanine pigment dispersion manufactured by KLT)
Jonkrill 690: (resin binder, made of Johnson polymer, styrene acrylic resin)
MOWITAL PVB-B20H: (resin binder, Kuraray, polyvinyl butyral)
NIKKOL CA-2150 (cationic surfactant, manufactured by Nikko Chemicals)
Butyl cellosolve: Solvent Propylene glycol monomethyl ether: Solvent
SH200 Oil 100CS: (Antifoam, Toray Dow Corning, silicone oil)
As can be seen from the results in Table 1, the indicators of Examples 1 to 3 in which the surface roughness Ra of the discolored layer is 2.5 to 15.0 μm show no discoloration failure due to film adhesion, but Ra is 0.47 μm. In the indicator of Comparative Example 1, the color change failure due to film adhesion is recognized.

Claims (13)

  1. 　基材上に過酸化水素又は過酸化水素プラズマの存在下で変色する変色層を有する過酸化水素滅菌又は過酸化水素プラズマ滅菌検知インジケーターであって、前記変色層の表面粗さＲａが２．５～１５．０μｍの範囲であることを特徴とするインジケーター。 A hydrogen peroxide sterilization or hydrogen peroxide plasma sterilization detection indicator having a discoloration layer that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma on a substrate, wherein the surface roughness Ra of the discoloration layer is 2.5. Indicator characterized by being in the range of ~ 15.0 μm.
  2. 　前記基材上に、基材面積の０．２～２０％の開口部が設けられている、請求項１に記載のインジケーター。 The indicator according to claim 1, wherein an opening of 0.2 to 20% of the substrate area is provided on the substrate.
  3. 　前記基材上に、型押し溝、スリット（線状の孔）及びミシン目（破線状の孔）からなる群から選択される少なくとも１種が設けられている、請求項１に記載のインジケーター。 The indicator according to claim 1, wherein at least one selected from the group consisting of embossed grooves, slits (linear holes), and perforations (dashed holes) is provided on the substrate.
  4. 　請求項１に記載の変色層を形成するためのインキ組成物であって、過酸化水素又は過酸化水素プラズマの存在下で変色する成分に加えて、平均粒子径１～３０μｍの粒子を含有するインキ組成物。 The ink composition for forming a discoloration layer according to claim 1, comprising particles having an average particle diameter of 1 to 30 μm in addition to a component that changes color in the presence of hydrogen peroxide or hydrogen peroxide plasma. Ink composition.
  5. 　前記粒子は、高分子化合物及び無機化合物の少なくとも１種である、請求項４に記載のインキ組成物。 The ink composition according to claim 4, wherein the particles are at least one of a polymer compound and an inorganic compound.
  6. 　アゾ系染料、メチン系染料、トリアリールメタン系染料及びチアジン系染料の少なくとも１種を含有する、請求項４又は５に記載の過酸化水素滅菌検知用インキ組成物。 The ink composition for hydrogen peroxide sterilization detection according to claim 4 or 5, comprising at least one of an azo dye, a methine dye, a triarylmethane dye, and a thiazine dye.
  7. 　１）スチレンアクリル樹脂及びスチレンマレイン酸樹脂の少なくとも１種及び２）メチン系染料を含有する、請求項４又は５に記載の過酸化水素滅菌検知用インキ組成物。 The ink composition for hydrogen peroxide sterilization detection according to claim 4 or 5, comprising 1) at least one of a styrene acrylic resin and a styrene maleic resin and 2) a methine dye.
  8. 　１）アントラキノン系染料、アゾ系染料及びメチン系染料の少なくとも１種、２）窒素含有高分子及び３）カチオン系界面活性剤を含有する。請求項４又は５に記載の過酸化水素プラズマ滅菌検知用インキ組成物。 1) At least one kind of anthraquinone dye, azo dye and methine dye, 2) a nitrogen-containing polymer and 3) a cationic surfactant. The ink composition for detecting hydrogen peroxide plasma sterilization according to claim 4 or 5.
  9. 　気体透過性包装体の内面に請求項１～３のいずれかに記載のインジケーターが設けられている過酸化水素又は過酸化水素プラズマ滅菌用包装体。 A package for hydrogen peroxide or hydrogen peroxide plasma sterilization, wherein the indicator according to any one of claims 1 to 3 is provided on the inner surface of the gas permeable package.
  10. 　前記インジケーターを外部から確認できるように、包装体の一部に透明窓部が設けられている、請求項９に記載の包装体。 The package according to claim 9, wherein a transparent window is provided in a part of the package so that the indicator can be confirmed from the outside.
  11. 　前記気体透過性包装体が、ポリエチレン系繊維により形成されている、請求項９又は１０に記載の包装体。 The packaging body according to claim 9 or 10, wherein the gas permeable packaging body is formed of a polyethylene fiber.
  12. 　請求項９～１１のいずれかに記載の包装体に被処理物を装填する工程、被処理物が装填された包装体を密封する工程、及び当該包装体を過酸化水素滅菌又は過酸化水素プラズマ滅菌雰囲気下に置く工程を有する過酸化水素又は過酸化水素プラズマ滅菌処理方法。 A step of loading an object to be processed into the package according to any one of claims 9 to 11, a step of sealing the package loaded with the object to be processed, and hydrogen peroxide sterilization or hydrogen peroxide plasma for the package A hydrogen peroxide or hydrogen peroxide plasma sterilization treatment method comprising a step of placing in a sterilizing atmosphere.
  13. 　前記インジケーターの変色層が変色するまで過酸化水素又は過酸化水素プラズマ滅菌雰囲気下に包装体を置く、請求項１２に記載の方法。 The method according to claim 12, wherein the package is placed in an atmosphere of hydrogen peroxide or hydrogen peroxide plasma sterilization until the color changing layer of the indicator changes color.
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