JP5461019B2 - Autoclave indicator ink, coated product having autoclave indicator ink layer, autoclave indicator sheet and sterilization bag - Google Patents

Description

  The present invention relates to an autoclave indicator ink used for sterilization in the medical field, an autoclave indicator sheet and a sterilization bag using the same.

  In the medical field, sterilization of pharmaceuticals such as infusions, hygiene products such as gauze, medical equipment and instruments in an autoclave is widely used. At that time, the article to be sterilized is put in a sterilization bag and sterilized.

  The mainstream of films used for sterilization bags is a laminate of polyethylene terephthalate and a film having heat sealability.

  In the sterilization bag as described above, as described in Patent Documents 1 to 5 and the like, printing on the film is not performed, and all printing is performed on high-quality paper or sterilized paper.

  Patent Document 6 discloses a sterilization bag sheet in which a base film and a covering film are bonded via a laminate layer, and an indicator ink layer is formed on at least a part of an adhesive surface with the laminate layer. The composition of the indicator ink layer is unknown and there is no detailed description.

Japanese Patent Publication No.57-9025 JP-A 61-287972 Japanese Patent Laid-Open No. 2-211162 Japanese Patent Laid-Open No. 4-89565 JP 2002-336335 A JP 2001-70414 A

  In patent documents 1-5, since it is difficult to perform printing of the indicator ink which shows that sterilization processing was completed on a film, it printed on high quality paper and sterilized paper, and the smear of indicator ink was carried out at the time of autoclaving processing. Concerned. In Patent Document 1, the configuration of the indicator ink is unknown, and no investigation has been made on a composition having stable color development during printing and a remarkable color change effect of the indicator ink itself.

  Accordingly, the present invention provides a sterilization bag comprising an autoclave indicator ink and an autoclave indicator sheet that can be applied to a film substrate and has good color developability and clear discoloration in autoclaving and water resistance. To do.

  As a result of intensive studies in view of the problems of the prior art, the present inventor has found that the above object can be achieved by an autoclave indicator ink having a specific configuration, and has completed the present invention.

That is, the present invention
(1) a polyurethane resin,
A methine dye and / or a cyanine dye,
An autoclave indicator ink in which a rosin having an acid value of 20 or more or a hydrogenated rosin is uniformly dissolved or dispersed in an organic solvent ;
(2) The autoclave indicator ink according to (1) above, wherein the polyurethane resin is synthesized from a polyol, a polyisocyanate compound and a chain extender, and the number average molecular weight is 3,000 to 150,000.
(3) A coated product in which the autoclave indicator ink according to (1) or ( 2 ) is applied to a film substrate and has an autoclave indicator ink layer,
(4) An autoclave indicator sheet in which one or more films are laminated on the coated product of ( 3 ) above,
(5) A sterilization bag using the autoclave indicator sheet of ( 4 ) above,
It is.

  According to the present invention, an autoclave indicator ink containing a polyurethane resin, a color-changing dye, and a resin having a carboxyl group can be applied to a film substrate and has good color developability and clear color change. Further, it is possible to provide a sterilization bag having water resistance and non-contamination property, comprising an autoclave indicator sheet in which one or more films are further laminated.

  Hereinafter, the best mode for carrying out the present invention will be described in detail. Note that this embodiment is merely an embodiment for carrying out the present invention, and the present invention is not limited by this embodiment, and various modified embodiments can be made without departing from the gist of the present invention. Is possible.

  The sterilization bag according to the present invention comprises an autoclave indicator ink layer comprising an autoclave indicator ink containing a polyurethane resin, a color-changing dye and a resin having a carboxyl group, and further comprises a sheet in which one or more films are laminated. And

  The polyurethane resin is preferably synthesized from a polyol, a polyisocyanate compound and a chain extender and has a number average molecular weight in the range of 3,000 to 150,000. Especially, the range of 5,000-100,000 is especially preferable. If it is less than 3,000, the drying property of the indicator ink for autoclave and the blocking resistance of the coated material coated with the indicator ink for autoclave are lowered. If it exceeds 150,000, the storage stability, production suitability, and printability of the indicator ink for autoclave are lowered. The number average molecular weight in this specification is a measured value by GPC method (polystyrene conversion).

  Examples of the polyol include polyester polyols, polyether polyols, polymer polyol compounds, saturated or unsaturated low molecular diols, low molecular polyols, and the like, which can be appropriately selected and used. Of these, polyester polyols and polyether polyols are preferred. It is best to use a mixture of polyester polyol and polyether polyol.

The polyester polyol is obtained, for example, by a condensation reaction between a diol and a dicarboxylic acid. Examples of the diol include ethylene glycol, diethylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , Triethylene glycol, trimethylene glycol, 1- or 2-methyl-1,3-butanediol, 1- or 2-methyl-1,4-pentyl glycol, 2-methyl-2,4-pentanediol, 3- Methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2, 5-dimethyl-2,5-hexanediol, 2,5-dimethyl-3,4-hexanediol, isobutylene glycol Coal, 2-methyl-1,3-propanediol, tripropylene glycol, 1,2-propylene glycol, neopentyl glycol, butylethylpropanediol, 2-ethyl-2-butyl-1,3-propanediol, 2- Examples thereof include methyl-2-propyl-1,3-propanediol, 1,4-butylenediol, 1,4-cyclohexanedimethanol, 1,4-butanediol, 1,4-butenediol and the like. In addition, a part of diol component can be changed to a polyfunctional polyol. Examples thereof include glycerin, trimethylolpropane, trimethylolethane, 1,2,6-hexanetriol, 1,2,4-butanetriol, sorbitol, pentaerythritol and the like.
Examples of dicarboxylic acids include adipic acid, succinic acid, sebacic acid, azelaic acid, fumaric acid, maleic acid, phthalic acid, terephthalic acid, isophthalic acid, malonic acid, oxalic acid, glutaric acid, and pimelic acid. A mixture of two or more types may be used. Of these, particularly preferred are adipic acid and sebacic acid.

  The number average molecular weight of the polyester polyol is preferably in the range of 600 to 7,000. Among these, a particularly preferable range is 1,000 to 5,000. If the number average molecular weight is less than 600, the polyurethane resin may be hard and brittle, and if it exceeds 7,000, the adhesion of the autoclave indicator ink to the film is lowered.

  The polyether polyol can be obtained by polymerization or copolymerization of ethylene oxide, propylene oxide, tetrahydrofuran or the like. Examples thereof include polypropylene glycol, polyethylene glycol, polyoxytetramethylene glycol and the like. Of these, particularly preferred is polypropylene glycol.

  The number average molecular weight of the polyether polyol is preferably in the range of 600 to 5,000. Of these, the range of 800 to 3,500 is particularly preferable. When the number average molecular weight is less than 600, the polyurethane resin may be hard and brittle, and when it exceeds 5,000, the blocking resistance of the coated product coated with the autoclave indicator ink is lowered.

  The ratio of the polyester polyol to the polyether polyol is preferably in the range of 98/2 to 20/80 by weight. When the polyester polyol exceeds 98% by weight in the ratio of the polyester polyol to the polyether polyol, the re-dissolution property of the urethane is lowered and the tone reproducibility of the printed matter is inferior. If the ratio of the polyester polyol to the polyether polyol exceeds 80% by weight, the anti-blocking property of the coated product coated with the autoclave indicator ink is lowered.

  Examples of the polyisocyanate compound include tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, 4,4′-dicyclohexyl diisocyanate. And modified products such as trimethylolpropane trimer, isocyanurate, burette, and allophanate, and the like can be used alone or in combination of two or more. Of these, 4,4'-diphenylmethane diisocyanate, isophorone diisocyanate and the like are particularly preferable.

  Examples of the chain extender include diamine compounds such as ethylenediamine, propylenediamine, hexamethylenediamine, triethylenetetramine, diethylenetriamine, isophoronediamine, dicyclohexylmethane-4,4′-diamine, dimeramine amine, and xylylenediamine, -Hydroxyethylethylenediamine, di-2-hydroxyethylpropylenediamine, di-2-hydroxyethylethylenediamine, diamine compounds having a hydroxyl group such as di-2-hydroxyethylpropylenediamine, neopentyl glycol, butylethylpropanediol, ethylene glycol, Diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,6-butanediol Xanthdiol, triethylene glycol, 1- or 2-methyl-1,3-butanediol, 1- or 2-methyl-1,4-pentyl glycol, 2,4-diethyl-1,5-pentanediol, tripropylene Diol compounds such as glycol, 1,2-propylene glycol, 3-methyl-1,5-pentanediol, 2-methyl-1,3-propanediol, N-methyldiethanolamine, N-methyldiisopropanolamine, phenyldiisopropanol Diol compounds having amine groups such as amine, 4-methylphenyldiethanolamine, 4-methylphenyldiisopropanolamine, alkylene oxides such as ethylene oxide, propylene oxide, and ethylene propylene oxide of bisphenol A Such as de adducts. Of these, isophoronediamine is particularly preferable.

  In the production of the polyurethane resin, a reaction terminator or a catalyst can be used as necessary. Examples of the reaction terminator include monoalcohol compounds such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, 1-butanol, 2-butanol, butylamine, sec-butylamine, tert-butylamine, dibutylamine, monoethanolamine, diethanolamine, And monoamine compounds such as propanolamine. Examples of the catalyst include amine catalysts such as triethyleneamine and triethylenediamine, tin catalysts such as dibutyltin dilaurate, dioctyltin dilaurate and tin (II) octylate, and titanium catalysts such as tetrabutyl titanate.

  The polyurethane resin is preferably in the range of 2 to 50% by weight in the total amount of the indicator ink for autoclave. Among these, the range of 3 to 20% by weight is particularly preferable. If it is less than 2% by weight, the laminateability and / or the resistance to autoclave resistance of the autoclave indicator sheet is lowered. If it exceeds 50% by weight, viscosity or fluidity suitable for printing cannot be obtained.

  A diluted solvent can be used for the polyurethane resin (hereinafter, the polyurethane resin diluted with the solvent is referred to as “polyurethane resin solution” in this specification). For example, aromatic hydrocarbon solvents such as toluene and xylene, alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, butanol, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-acetate Examples include ester solvents such as butyl and tert-butyl acetate, and ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. These may be used alone or in combination of two or more. Of these, toluene, ethyl acetate, propyl acetate, isopropyl alcohol, methyl ethyl ketone and the like are particularly preferable.

  As a method for producing the polyurethane resin solution, a known method represented by a two-step reaction method, a one-step reaction method, or a method combining a one-step reaction method and a two-step reaction method can be used. The two-stage reaction method is a preferable production method in that it is easy to obtain a uniform polymer.

  The viscosity of the polyurethane resin solution is preferably in the range of 50 to 100,000 mPa · s / 25 ° C. for handling.

  The amine value of the polyurethane resin solution is preferably in the range of 0.1 to 10 mgKOH / g.

  Examples of the color-changing dyes include (poly) methine dyes and / or cyanine dyes having one or more methine groups exhibiting color developability or color change in the molecule. These may be used alone or in combination of two or more. Can be used.

  Examples of (poly) methine dyes and / or cyanine dyes having one or more methine groups in the molecule are, for example, Color Basic Red 12, 13, 14, 15, 27, 35, 36, 37, 45, 48, 49, 52, 53, 66 and 68, Color Basic Yellow (CI Basic Yellow) 11, 12, 13, 14, 21, 22, 23, 24, 28, 29 33, 35, 40, 43, 44, 45, 48, 49, 51, 52 and 53, CI Basic Violet 7, 15, 16, 20, 21, 39 and 40, color Index Orange (CI Basic Orange) 27, 42, 44 and 46, color in Such as box-Basic Blue (C.I.Basic Blue) 62 and 63, and the like. Of these, Color Index Basic Red 12, 13, 14, 15 and 37, Color Index Basic Yellow 11 and 13, Color Index Basic Violet 7 and 15 and the like are particularly preferable in discoloration.

  It is preferable that the color-changing dye is in the range of 0.1 to 5% by weight in the total amount of the indicator ink for autoclave. Especially, the range of 0.2 to 3 weight% is especially preferable. If it is less than 0.1% by weight, sufficient color development is not exhibited. If it exceeds 5% by weight, the hue change after discoloration is poor.

  The acid value of the resin having a carboxyl group is preferably 20 or more. Among these, 30 or more is particularly preferable. Thereby, when the indicator ink for autoclave is applied, an excellent coloring effect of the color-changing dye is obtained. Moreover, it is preferable that the softening point of resin which has a carboxyl group is 60 degreeC or more. Among these, 80 ° C. or higher is particularly preferable. If the softening point is less than 60 ° C., the blocking resistance of the coated material coated with the autoclave indicator ink is lowered.

  The resin having a carboxyl group in the total amount of the indicator ink for autoclave is preferably in the range of 0.1 to 30% by weight. Among these, the range of 1 to 25% by weight is particularly preferable. If it is less than 0.1% by weight, a clear discoloration effect of the discolorable dye in the autoclave treatment cannot be obtained. When it exceeds 30% by weight, the blocking resistance of the coated material coated with the autoclave indicator ink is lowered.

  The ratio between the polyurethane resin and the resin having a carboxyl group is preferably in the range of 90/10 to 10/90 by weight. Of these, the range of 15/85 to 85/15 is particularly preferable. When the polyurethane resin exceeds 90% by weight in the ratio of the polyurethane resin to the carboxyl group-containing resin, the clear color-changing effect of the color-changing dye in the autoclave treatment cannot be obtained. When the ratio of the resin having a carboxyl group to the polyurethane resin and the resin having a carboxyl group exceeds 90% by weight, the laminate suitability and / or the autoclave resistance of the autoclave indicator ink is lowered.

  The indicator ink for autoclave of the present invention includes, in addition to polyurethane resin, a color-changing dye and a resin having a carboxyl group, if necessary, other resins, an invariant colorant (a dye whose hue does not change by autoclaving), Additives, other solvents, and the like can be used.

  Other resins can be used for the purpose of improving the performance and film properties of the indicator ink for autoclave. For example, nitrified cotton, acrylic resin, polyamide resin, vinyl chloride-vinyl acetate copolymer, polyester resin, chlorinated polypropylene resin, chlorinated ethylene-vinyl acetate resin, rosin modified resin, phenol resin, ethylene-vinyl acetate resin, alkyd resin , Butyral resin, ketone resin and the like.

  The invariant colorant is not particularly limited as long as it has heat resistance and migration resistance that can withstand autoclaving. Pigments and dyes can be appropriately selected and used within a range in which the hue of the color-changing pigment can be clearly recognized before and after the autoclave treatment.

  Additives include antifoaming agents, leveling agents, anti-blocking agents, waxes, pigment dispersants, etc. for the purpose of improving the printability and film properties of indicator inks for autoclaves, as long as the color-changing function of the color-changing dyes is not reduced. Can be appropriately selected and used.

  The autoclave indicator ink of the present invention can be produced by uniformly dissolving and / or dispersing a polyurethane resin solution, a color changing dye, a resin having a carboxyl group, other resins, an invariant color changing dye, an additive, and the like in a solvent. . A stirrer or a disperser can be used as a production machine for dissolving and / or dispersing, and examples thereof include a dissolver, a roll mill, a ball mill, a bead mill, and an attritor. When bubbles or coarse particles are contained in the autoclave indicator ink, it is preferably removed by using a known filter or the like in order to reduce printability and print quality.

  The viscosity of the autoclave indicator ink of the present invention is not particularly limited as long as it does not interfere with printing. Considering the production suitability and handling of the indicator ink for autoclave, it is preferably in the range of 10 to 1,000 mPa · s / 25 ° C.

  Although the indicator ink for autoclave of the present invention can be printed as it is, according to the printing method, printing conditions and printing effect, the Zahn Cup No. 3 (manufactured by Kosei Co., Ltd.) can be used by adjusting to a desired viscosity by diluting with a diluent solvent. The viscosity in this case is preferably in the range of 12 to 40 seconds.

  The dilution solvent may be any one as long as it can be used after adjusting the viscosity of the autoclave indicator ink, and examples thereof include organic solvents and water, and commercially available products can also be used.

  The indicator ink for autoclave of the present invention can be applied to a film substrate by a known method such as printing, coating or spraying. Examples thereof include a silk screen printing method, a gravure printing method, an offset printing method, a flexographic printing method, a roller coater method, a brush coating method, a spray method, and a knife jet coater method. Of these, the gravure printing method or the flexographic printing method is particularly preferable because of its high quality and high productivity.

  The thickness of the indicator ink layer for autoclave applied to the film substrate of the present invention is not particularly limited as long as it is within a range where the sufficient concentration and hue of the color-changing dye can be clearly recognized before and after the autoclave treatment. , Preferably in the range of 0.01 to 10 μm. Especially, the range of 0.1-3 micrometers is especially preferable. If it is less than 0.01 μm, a sufficient concentration cannot be obtained. If it exceeds 10 μm, the blocking resistance of the coated product coated with the autoclave indicator ink is lowered.

  When the autoclave indicator ink of the present invention is printed using a multicolor machine, the pattern can be simultaneously printed inline in addition to the autoclave indicator ink. Examples include the manufacturer's company name, product name, contents, component display, sales promotion design, and pseudo hue display before and after discoloration of the autoclave indicator sheet.

  The indicator ink for autoclaves of the present invention can be printed under the one-component use conditions in which a diluent solvent is added as it is, but can also be printed under the two-component use conditions in which a polyisocyanate curing agent is added thereto. In printing with two liquids, the heat resistance, water resistance, adhesion and the like of the autoclave indicator ink are improved, and this is preferable in that an autoclave indicator sheet which is resistant under autoclave conditions can be obtained.

  The indicator sheet for autoclave of the present invention is a coated product having an autoclave indicator ink layer coated with an autoclave indicator ink, and further laminated one or more films on the coated material. Can be obtained.

  The film base material to which the autoclave indicator ink is applied need not be the outermost layer. When the intermediate layer is laminated by laminating, the autoclave indicator ink layer can be visually recognized. An autoclave indicator ink can be applied to form a coated product having an autoclave indicator ink layer.

  A film can be further laminated on the application side of the indicator ink layer for autoclave of the coated product, a known method can be used, and a method of laminating a film having heat sealability via an adhesive is preferred. For example, an extrusion laminating method, a dry laminating method, a wet laminating method, and a non-solvent laminating method can be mentioned, and a dry laminating method excellent in heat resistance is preferable. As a result, an autoclave indicator sheet having good color developability of the coated product and a clear discoloration effect in the autoclave treatment and having water resistance, autoclave suitability and good laminate suitability is obtained.

  Examples of the film substrate on which the indicator ink for autoclave is applied include polyester films such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), polyolefin films such as polyethylene and polypropylene, polystyrene films, ethylene-vinyl alcohol, and polyvinyl alcohol. Alcohol-based film, polyamide film or barrier-coated polyamide film with a barrier layer in the middle, polycarbonate film, polyacrylonitrile film, polyimide film, PET film or transparent vapor-deposited polyester film with a deposited layer of alumina, silica, etc. on a polyamide film Or transparent deposited polyamide film, polyvinylidene chloride resin, polyvinyl alcohol resin Various coating films and coated polyacrylic acid resin and the like, which stretch may be either unstretched, or may be laminated alone or two or more kinds. Appropriate ones can be selected in consideration of mechanical strength and dimensional stability. In addition, in order to improve the adhesion of the autoclave indicator ink, the surface on which the autoclave indicator ink layer is applied may be subjected to corona treatment, low temperature plasma treatment, flame treatment, solvent treatment, coating treatment, etc. Can be selected. Among these, a biaxially stretched PET film, a polyamide film, or a vapor deposition film in which a vapor deposition layer such as alumina or silica is provided thereon is particularly preferable.

  The thickness of the film substrate is not particularly limited as long as it is within the range that does not hinder printing suitability, winding suitability, etc., but is preferably in the range of 5 to 200 μm. Especially, the range of 6-30 micrometers is especially preferable.

  The said intermediate | middle layer can be provided as needed for provision of pinhole-proof property, light-shielding property, gas barrier property, fragrance retention, etc. For example, a polyester film such as polyethylene terephthalate (PET) or polyethylene naphthalate (PEN), a transparent deposited polyester or transparent deposited polyamide film, an alcohol-based film such as ethylene-vinyl alcohol or polyvinyl alcohol, a polyamide film or a barrier layer is disposed in the middle Examples include barrier polyamide films, polyvinylidene chloride resins, polyvinyl alcohol resins, various coating films coated with polyacrylic acid resins, metal foils such as aluminum foil, and paper. In order to improve the adhesion, a corona treatment, a low-temperature plasma treatment, a flame treatment, a solvent treatment, a coating treatment, or the like can be applied, or a pre-treated one can be selected. From the viewpoint of cost and versatility, the corona treatment is particularly preferable, and treatment is performed on both sides.

  The thickness of the intermediate layer is not particularly limited as long as it is within a range that does not hinder workability, cost, and the like, but is preferably within a range of 3 to 200 μm. Especially, the range of 5-30 micrometers is especially preferable.

  Examples of the heat-sealable film include polypropylene film, polyethylene film, ethylene vinyl acetate film, ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-acrylic acid copolymer, ethylene-acrylic. Examples thereof include unstretched films such as acid ester copolymers and resins of such metal cross-linked products. Among them, unstretched polypropylene films and polyethylene films are preferable from the viewpoint of heat resistance such as autoclave, and particularly unstretched polypropylene. A film is preferred.

  The thickness of the film having heat-sealability is not particularly limited as long as it is within a range that does not hinder the winding property and cost, but is preferably within a range of 10 to 200 μm. Especially, the range of 20-80 micrometers is especially preferable.

  In the sterilization bag of the present invention, it is sufficient that the autoclave indicator sheet is used on both sides or on one side, but considering the permeability of sterilization gas such as high-pressure steam or ethylene oxide gas, one side is paper such as high-quality paper or sterilization paper. Or non-woven fabric, and the other is preferably a film. As long as it has the performance as a sterilization bag, the nonwoven fabric and paper are not particularly limited. However, considering the good permeability of heat, air, autoclave gas, drying property after autoclaving, and microbial barrier properties, the sterilized paper Is particularly preferred.

  The types of sterilized paper include a paper type, a polypropylene blended type, and a heat sealant coating type, but there is no particular limitation as long as it can be heat sealed with the autoclave indicator sheet of the present invention and has a performance as a sterilization bag.

The thickness of the sterilization sheet is not particularly limited, is preferably in the range of 30 to 500 g / ^{m 2.} Especially, the range of 40-300 g / m < ² > is especially preferable.

  The sterilization bag of the present invention can be used not only for autoclave applications but also for ethylene oxide gas sterilization, radiation sterilization, hydrogen peroxide low temperature plasma sterilization, and the like.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, it is not limited only to a following example etc. In Examples and the like, “parts” and “%” represent “parts by weight” and “% by weight” unless otherwise specified.

(Synthesis Example 1)
A four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube was charged with 600 parts of 3-methyl-1,5-pentaneadipatediol having a number average molecular weight of 3,000 and a number average molecular weight of 3,000. 150 parts of neopentyl glycol adipate diol, 250 parts of polypropylene glycol having a number average molecular weight of 3,000, and 144.8 parts of isophorone diisocyanate were charged and reacted at 105 ° C. for 6 hours while introducing nitrogen gas, and a urethane prepolymer (isocyanate content) 2.3%) was obtained. To this urethane prepolymer, 763 parts of methyl ethyl ketone was added to obtain a uniform urethane prepolymer resin solution A′1,907.8 parts. Subsequently, 1,000 parts of the urethane prepolymer resin solution A ′ is gradually added to a mixture comprising 25.5 parts of isophoronediamine, 5.2 parts of dibutylamine, 630.3 parts of methyl ethyl ketone, and 442 parts of isopropyl alcohol at room temperature. Then, the mixture was heated to 60 ° C. and reacted for 3 hours to obtain a polyurethane resin solution A. The obtained polyurethane resin solution A had a resin solid content of 30%, a viscosity of 1,050 mPa · s / 25 ° C., an amine value of 0.4 mgKOH / g, and a number average molecular weight of 9,500.

(Synthesis Example 2)
A four-necked flask equipped with a stirrer, a condenser, a thermometer, and a nitrogen gas inlet tube was charged with 666 parts of 3-methyl-1,5-pentaneadipatediol having a number average molecular weight of 2,000 and 2,000 parts having a number average molecular weight of 2,000. 334 parts of polypropylene glycol and 200 parts of 4,4′-diphenylmethane diisocyanate were charged and reacted at 105 ° C. for 6 hours while introducing nitrogen gas to obtain a urethane prepolymer (isocyanate content 2.1%). To this urethane prepolymer, 800 parts of ethyl acetate was added to obtain 2,000 parts of a uniform urethane prepolymer resin solution B ′. Subsequently, 1,000 parts of the urethane prepolymer resin solution B ′ is gradually added to a mixture of 24.7 parts of isophoronediamine, 2.6 parts of dibutylamine, 625.7 parts of ethyl acetate, and 440 parts of isopropyl alcohol at room temperature. Then, the mixture was heated to 60 ° C. and reacted for 3 hours to obtain a polyurethane resin solution B. The obtained polyurethane resin solution B had a resin solid content of 30%, a viscosity of 950 mPa · s / 25 ° C., an amine value of 0.5 mgKOH / g, and a number average molecular weight of 10,200.

Example 1
20 parts of polyurethane resin solution A, 15 parts of hydrogenated rosin (acid number 170, softening point 85 ° C.), 1 part of basic red 37, 50 parts of propyl acetate, 4 parts of methyl ethyl ketone, 10 parts of isopropyl alcohol are mixed for 3 hours to obtain red Indicator ink for autoclave no. 1 was obtained. Indicator ink No. for autoclave 1 is gravure-printed on a 12 μm PET film, and then a 40 μm unstretched polypropylene film having heat-sealing properties with a two-component curable urethane adhesive A-525 / A-52 (Mitsui Chemical Polyurethane Co., Ltd.). Were laminated by a dry laminating method to obtain an autoclave indicator sheet. After aging at 50 ° C. for 4 days, the heat-sealing film surface of the autoclave indicator sheet was combined with 60 g / m ² of sterilized paper, and a sterilization bag was obtained by heat fusion.

(Example 2)
10 parts of polyurethane resin solution B, 15 parts of hydrogenated rosin (acid number 168, softening point 88 ° C.), 1 part of basic red 37, 50 parts of propyl acetate, 4 parts of methyl ethyl ketone and 20 parts of isopropyl alcohol are mixed for 3 hours to give red Indicator ink for autoclave no. 2 was obtained. Indicator ink No. for autoclave 2 is gravure-printed on a 12 μm PET film, and then a 40 μm unstretched polypropylene film having heat sealability with a two-component curable urethane adhesive A-525 / A-52 (Mitsui Chemical Polyurethane Co., Ltd.). Were laminated by a dry laminating method to obtain an autoclave indicator sheet. After aging at 50 ° C. for 4 days, the heat-sealing film surface of the autoclave indicator sheet and 70 g / m ² of sterilized paper were combined and heat-sealed to obtain a sterilized bag.

(Example 3)
39 parts of polyurethane resin solution A, 19.5 parts of rosin (acid value 170, softening point 85 ° C.), 1.5 parts of basic red 37, 20 parts of propyl acetate and 20 parts of isopropyl alcohol are mixed for 3 hours to produce a red autoclave. Indicator ink No. 3 was obtained. Indicator ink No. for autoclave 3 is a non-toluene-type dilution solvent PU515 (manufactured by Tokyo Ink Co., Ltd.), the viscosity is adjusted to 17 seconds with Zaan Cup # 3 (manufactured by Koiso Co., Ltd.), and gravure printing is performed on a 16 μm PET film. Next, with a two-component curable urethane adhesive A-525 / A-52 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.), a 30 μm unstretched polypropylene film having heat sealability is laminated by a dry laminating method for autoclave use. An indicator sheet was obtained. After aging at 50 ° C. for 4 days, the heat-sealing film surface of the autoclave indicator sheet was combined with 60 g / m ² of sterilized paper, and a sterilization bag was obtained by heat fusion.

Example 4
30 parts of polyurethane resin solution A, 15 parts of rosin (acid value 170, softening point 85 ° C.), 1.5 parts of cyanine blue pigment (Pigment Blue 15: 3), 2.5 parts of methyl ethyl ketone, 30 parts of ethyl acetate, 20 parts of isopropyl alcohol Disperse with a bead mill, add 1 part of Basic Red 37, mix for 3 hours, and use purple autoclave indicator ink No. 4 was obtained. Indicator ink No. for autoclave 4 is a non-toluene-type dilution solvent PU515 (manufactured by Tokyo Ink Co., Ltd.), the viscosity is adjusted to 17 seconds with Zaan Cup # 3 (manufactured by Kikai Co., Ltd.), and gravure printing is performed on a 12 μm PET film. Next, with a two-component curable urethane adhesive A-525 / A-52 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.), a 30 μm unstretched polypropylene film having heat sealability is laminated by a dry laminating method for autoclave use. An indicator sheet was obtained. After aging at 50 ° C. for 4 days, a heat-sealable film surface of an autoclave indicator sheet, a 12 μm PET film laminated by a dry laminating method, and a 30 μm unstretched polypropylene film sheet having heat-seal properties The film surfaces having heat sealability were combined, and a sterilization bag was obtained by heat fusion.

(Comparative Example 1)
Indicator ink No. for autoclave 1 was gravure-printed on a sterilized paper of 60 g / m ² to obtain an autoclave indicator sheet. The surface of the autoclave indicator sheet which is not printed with the autoclave indicator ink, and the film surface which is heat-sealable of a 12 μm PET film laminated by a dry laminating method and a 30 μm unstretched polypropylene film having heat-seal properties. And a sterilization bag was obtained by heat fusion.

(Comparative Example 2)
Indicator ink No. for autoclave 2 was gravure-printed on 70 g / m ² of sterilized paper to obtain an autoclave indicator sheet. The surface of the autoclave indicator sheet on which the autoclave indicator ink is not printed is combined with the heat sealant coated surface of 70 g / m ² of sterilized paper (heat sealant coating type). Got.

(Comparative Example 3)
15 parts of rosin (acid number 168, softening point 88 ° C.), 1 part of basic red 37, 50 parts of propyl acetate, 14 parts of methyl ethyl ketone and 20 parts of isopropyl alcohol were mixed for 3 hours. 5 was obtained. Indicator ink No. for autoclave 5 is gravure-printed on a 12 μm PET film, and then a 30 μm unstretched polypropylene film having heat sealability with a two-component curable urethane adhesive A-525 / A-52 (Mitsui Chemical Polyurethane Co., Ltd.). Were laminated by a dry laminating method to obtain an autoclave indicator sheet. After aging at 50 ° C. for 4 days, the heat-sealing film surface of the autoclave indicator sheet was combined with 60 g / m ² of sterilized paper, and a sterilization bag was obtained by heat fusion.

(Comparative Example 4)
20 parts of polyurethane resin solution B, 1 part of basic red 37, 50 parts of propyl acetate, 9 parts of methyl ethyl ketone and 20 parts of isopropyl alcohol were mixed for 3 hours. 6 was obtained. Indicator ink No. for autoclave 6 is gravure-printed on a 12 μm PET film, and then a 30 μm unstretched polypropylene film having heat-sealing properties with a two-component curable urethane adhesive A-525 / A-52 (Mitsui Chemical Polyurethane Co., Ltd.). Were laminated by a dry laminating method to obtain an autoclave indicator sheet. After aging at 50 ° C. for 4 days, the heat-sealing film surface of the autoclave indicator sheet was combined with 60 g / m ² of sterilized paper, and a sterilization bag was obtained by heat fusion.

(Comparative Example 5)
20 parts of polyurethane resin solution A, 15 parts of esterified product of hydrogenated rosin and pentaerythritol (acid value 13, softening point 103 ° C.), 1 part of basic red 37, 50 parts of propyl acetate, 4 parts of methyl ethyl ketone, 3 parts of isopropyl alcohol 3 parts After mixing for a while, red autoclave indicator ink No. 7 was obtained. Indicator ink No. for autoclave No. 7 was gravure-printed on a 12 μm PET film, but because the color change of the discolorable dye was poor, it was impossible to prepare an autoclave indicator sheet.

  Performance evaluation was performed about the sterilization bag obtained in Examples 1-4 and Comparative Examples 1-4. The results are shown in Table 1.

[Performance evaluation of sterilization bags]
Sterilize at a water vapor temperature of 121 ° C. for 20 minutes in an autoclave, and visually check the state after the treatment for the clarity of hue change, the appearance abnormality, and the presence or absence of water resistance of the autoclave indicator ink layer of the sterilization bag. confirmed. Evaluations were evaluated as “Good” for “Excellent” and “Poor” for poor.

  As shown in Table 1, the sterilization bags of Examples 1 to 4 clearly change in hue before and after autoclaving, have water resistance, and have no abnormal appearance. The sterilization bags of Comparative Example 1 and Comparative Example 2 have bleeding and do not have water resistance. In the sterilization bag of Comparative Example 3, floating occurs between the film substrate having the autoclave indicator ink layer and the bonded substrate. In the sterilization bag of Comparative Example 4, the change in hue is unclear. In Comparative Example 5, the color development at the time of printing of the indicator ink for autoclave is poor and is not worthy of evaluation.

  The autoclave indicator sheet of the present invention can be applied to create a sterilization bag for confirming completion of sterilization treatment in the medical field.

Claims (5)

And a polyurethane resin,
A methine dye and / or a cyanine dye,
An autoclave indicator ink, wherein a rosin having an acid value of 20 or more or a hydrogenated rosin is uniformly dissolved or dispersed in an organic solvent .   2. The indicator ink for autoclave according to claim 1, wherein the polyurethane resin is synthesized from a polyol, a polyisocyanate compound and a chain extender and has a number average molecular weight of 3,000 to 150,000. A coated product, wherein the autoclave indicator ink according to claim 1 or 2 is applied to a film substrate and has an autoclave indicator ink layer. An autoclave indicator sheet, wherein one or more films are laminated on the coated product according to claim 3 . A sterilization bag comprising the autoclave indicator sheet according to claim 4 .