JPH0119706B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an ethylene oxide sterilization marking ink. Conventionally, medical instruments and the like have been sterilized by boiling or high-pressure steam, but recently a method has been used in which the object to be sterilized is placed in a sealed container and ethylene oxide is passed through the container. ing. When sterilizing using these sterilization methods, in order to identify whether sterilization has been completed or not, the object to be sterilized is marked with ink that changes color when sterilization conditions are reached, and the color change of the mark I am now aware of this. A dye represented by the general formula AN=N-B as an ink composition for sterilization labeling using ethylene oxide [A is a pyridine ring, quinoline ring, isoquinoline ring, triazole ring, or tetrazole ring containing a nitrogen atom to which no alkyl group is added] a heterocyclic compound residue selected from the group of rings, indazole rings and thiadiazole rings, which residues may or may not have non-refutable substituents; B represents a conventional coupling moiety; metal salts of aromatic acids,
An ink composition for marking sterilization with ethylene oxide, which contains an organic liquid whose volatile ratio is always less than 1, has been proposed (Japanese Patent Application Laid-Open No. 56-95053), and its effectiveness has been recognized. The ink composition of this prior art changes color depending on three factors: ethylene oxide concentration, sterilization temperature, and sterilization time, but cannot capture the influence of humidity during sterilization. Therefore, the optimum relative humidity for sterilization (30
When sterilizing under conditions other than 80%), for example, under 0% relative humidity, it may not be sterilized despite the discoloration. In addition to the above three factors, the ink composition of the present invention changes color due to the addition of a humidity factor. Therefore, under optimal relative humidity conditions (30-80%), it exhibits discoloration similar to that of the prior art, but below relative humidity of 30%, discoloration gradually slows down, and the resistance of bacteria to ethylene oxide under low humidity increases. It has become possible to match the humidity conditions during sterilization and to detect that the humidity conditions during sterilization are not optimal. The dispersible dye used in the present invention is represented by the following general formula. A-N=N-B [wherein A is a pyridine ring, quinoline ring, isoquinoline ring, triazole ring, tetrazole ring, indazole ring, thiazole ring, benzothiazole ring and thiadiazole ring containing a nitrogen atom to which no alkyl group is attached] A heterocyclic compound residue selected from the group of rings - the residue may or may not have a non-dissociable substituent, B represents a usual coupling component] Dye included in the above general formula Since there are a wide variety of dyes, it is possible to freely select a dye that changes color and is suitable for the intensity of the sterilization conditions and the color development before and after treatment with ethylene oxide gas. Examples of the heterocyclic compound residues used in this invention include the following.

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[Formula] Here, R and R' are a methyl group, an ethyl group, a methoxy group, an ethoxy group, a halogen group, a cyano group,
Nitro group, hydroxyl group, amino group, dimethylamino group, diethylamino group, diethanolamino group, carboxyl group, phenyl group, phenoxy group, benzyl group, sulfonic acid group, anilino group,
An example is an acetamide group, and a wide variety of common coupling components that can be used in the synthesis of dyes include the following. Aminobenzene, dimethylaminobenzene, diethanolaminobenzene, 1-amino-2-methylbenzene, 1-amino-3-methylbenzene, 1-amyl-2,5-dimethylbenzene, 1
-amino-2-methoxy-5-methylbenzene,
1,3-diaminobenzene, 1,3-diamino-
4-methylbenzene, 1-3-diamino-4-chlorobenzene, 1,3-diamino-4-nitrobenzene, 2,4-diaminobenzenesulfonic acid,
Aromatic amines such as 4,6-diamino-1,3-benzenedisulfonic acid. Phenols such as phenol, P-cresol, resorcinol, 1,3,5-benzenetriol, salicylic acid, and 3-methylsalicylic acid. α-naphthol, β-naphthol, 1,5-naphthalene diol, 1-hydroxy-3-naphthalenesulfonic acid, 1-hydroxy-4-naphthalenesulfonic acid, 1-hydroxy-5-naphthalenesulfonic acid, 1-hydroxy-3 , 6-naphthalenedisulfonic acid, 2-hydroxy-6,8-naphthalenedisulfonic acid, 1,8-dihydroxy-4
- Naphthols such as naphthalenesulfonic acid and 1,8-dihydroxy-3,6-naphthalenedisulfonic acid. 1-amino-2-hydroxybenzene, 1-amino-2-hydroxy-5-methylbenzene, 1
-Aminophenols such as amino-2,5-dihydroxybenzene. 1-aminonaphthalene, 8-amino-3-naphthalenesulfonic acid, 8-amino-2-naphthalenesulfonic acid, 1-anilide-7-naphthalenesulfonic acid, 2-aminonaphthalene, 2-amino-
3,6-naphthalenedisulfonic acid, 2-amino-
Aminonaphthols such as 3-naphthalenecarboxylic acid. 1-hydroxy-6-amino-3-naphthalenesulfonic acid, 1-amino-8-hydroxy-4-
Naphthalenesulfonic acid, 1-amino-8-hydroxy-2,4-naphthalenesulfonic acid, 1-amino-5-hydroxy-7-naphthalenesulfonic acid, 1-amino-2-ethoxy-6-naphthalenesulfonic acid, 3- Aminonaphthols such as hydroxy-2-naphthanilide. 5-oxo-3-methyl-1-phenyl-2-
Pyrazoline, 5-oxo-phenyl-2-pyrazoline-3-carboxylic acid, 1-(4-sulfophenyl)-5-oxo-1-methyl-2-pyrazoline, 5-imino-3-methyl-1-phenyl-2
- Compounds that can be enolized and have reactive methylene groups such as pyrazoline. Among the dispersible dyes having the above structure, CI Dispersed Red 58, 88,
111 and 206, CI Disperse Violet
43 and CI Daspurs Blue 102. In addition to the above-mentioned dispersible dyes, some ordinary water-soluble dyes may be added for color adjustment. Water-soluble polymers used in the present invention include polyvinyl alcohol, polyvinylpyrrolidone, synthetic resins such as water-soluble acrylic acid resin, hydroxyethyl cellulose, hydroxypropyl methyl cellulose, methyl cellulose, cellulose sodium glycolate, carboxymethyl cellulose, etc. Natural or modified starches such as cellulose derivatives, horse starch, dextrin, pullulan, and water-soluble thickening agents such as gum arabic and water-soluble gelatin can be mentioned. The organic acids used in the present invention include aliphatic dicarboxylic acids such as oxalic acid, malonic acid, and maleic acid, sulfonic acids such as butanesulfonic acid, butanedisulfonic acid, and benzenesulfonic acid, benzoic acid, phthalic acid, phenol, Examples include aromatic acids such as salicylic acid and sulfosalicylic acid. In particular, when polybasic acids of the acid salt type, such as sodium sulfosalicylate and zinc salicylate, in which one or more of the acid groups of the polybasic acid is in the form of a free acid and the other one or more are in the form of a salt, are used as printing inks. It can be used effectively because it does not sublimate from the inside of the printed surface and the storage stability of printed matter is good. The solvent used in the present invention is mainly water, but an appropriate amount of a water-soluble solvent such as a polyhydric alcohol such as ethylene glycol, glycerin, ethylene glycol monoethyl ether, or ethylene glycol monomethyl ester may be used in place of water to improve the drying speed. It can adjust the viscosity or permeability into the painted surface, and also makes the coloring of the dye beautiful. Further, some additives used in ordinary water-based ink compositions, such as surfactants, preservatives, rustproofing agents, and fragrances, can be used. To produce the ink of the present invention, the dye of formula (1) is added in an amount of 0.05 to 3.0% by weight (hereinafter referred to as % by weight) based on the ink composition.
is simply expressed as %), preferably 0.1 to 2%, organic acid 0.1 to 10%, preferably 1 to 6%, water-soluble polymer resin 1 to 35%, preferably 2 to 20%, water 30 to 90%.
%, preferably 40 to 85%, of a water-soluble organic solvent and/or additives as required, and sufficiently dissolved or dispersed. Next, examples will be shown to further clarify the present invention. Example 1 18.0 parts of polyvinyl alcohol (manufactured by Kuraray, Popal 105) was added to 74.6 parts of water and stirred at 95°C to completely dissolve. Then
Cool to 60-70° and use CI Dispersed Red 58 (Mitsui Toatsu Chemical Co., Ltd.).
Miketon Fast Pink FR) 0.3 parts CI Acid Yellow 17 (Nippon Kayaku Kayacryl Yellow GC) 0.1 parts Sodium sulfosalicylate 4.0 parts Polyethylene Glycol 300 3.0 parts were added and completely dissolved to obtain an ink composition. This coating is red and turns green under ethylene oxide sterilization conditions. Example 2 Pullulan (manufactured by Hayashibara, Pullulan PF30) 15.0 parts Water 77.35 parts CI Disperse Violet 48 (Mitsui Toatsu Chemicals, Inc., Miketon Disperse Pink 3B) 0.3 Sulfosalicylic acid 3.5 parts Monoethanolamine 3.0 parts Diethylene glycol monoethyl ether
An ink composition was obtained from 0.85 parts according to Example 1. The coating film of this ink composition is purple and becomes blue when treated with ethylene oxide. Example 3 Water-soluble gelatin (manufactured by Nitta Gelatin, H grade) 100 parts Water 84.7 parts CI Dispersed Red 58 (manufactured by Mitsui Toatsu Chemical Co., Ltd.)
An ink composition was obtained according to Example 1 from 0.3 parts of Miketone Fast Pink FR), 2.0 parts of maleic acid, and 3.0 parts of dipropylene glycol. This coating is red and turns blue when treated with ethylene oxide. Example 4 Polyvinylpyrrolidone (manufactured by BASF, Rubiscoll K-17) 10.0 parts Water 82.7 parts CI Dispersed Red 58 (mentioned above) 3.0 parts Sodium sulfosalicylate 4.0 parts Polyethylene glycol 600 3.0 parts According to Example 1 Got the ink. This coating is red and turns blue when treated with ethylene oxide. Example 5 Polyacrylic acid copolymer (Nippon Pure Chemical Industries, Ltd.)
AC20L) 15.0 parts water 41.0 parts CI Dispersed 111 (manufactured by Mitsui Toatsu Chemicals,
An ink composition was obtained according to Example 1 from 0.3 parts of Miketon Polyester Red (BSF), 0.3 parts of zinc salicylate, 3.0 parts of triethylene glycol, 3.0 parts of ethanol, and 32.7 parts of ethylene glycol monoethyl ether. This coating is reddish-purple and becomes purple when treated with ethylene oxide. Example 6 Qualitative paper was dipped or silk-printed in the ink of each example, colored and dried, and the test piece was heated at 50°C.
in the presence of water vapor in a closed vessel (65% RH)
and ethylene oxide concentration 500 in the absence of
mg/l (Daiside LLS, manufactured by Daido Sanso Co., Ltd.) for 1 and 3 hours, and the discoloration of the test piece was measured using a color difference direct reading digital colorimeter ND-, manufactured by Nippon Denshoku Industries Co., Ltd.
Color difference ΔE was measured using a Lab system using Model 504AA.
The results are shown in Table 1. From this value, it is recognized that the ink composition of the present invention accelerates the color change measurement in the presence of water vapor. In addition, the above humidity is 65%, 3
It was separately confirmed by biological tests that the conditions of exposure to ethylene oxide for a period of time were sufficient to complete sterilization in normal objects to be sterilized.

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Claims (1)

[Scope of Claims] 1 Dispersible dye represented by the general formula AN=N-B [A is a pyridine ring, quinoline ring, isoquinoline ring, triazole ring, or tetrazole ring containing a nitrogen atom to which no alkyl group is attached] , an indazole ring, a thiazole ring, a benzothiazole ring, and a heterocyclic compound residue selected from the group of thiadiazole rings, which residues may or may not have non-dissociable substituents, B is a conventional Showing coupling components] An ink composition for ethylene oxide sterilization labeling that contains a water-soluble polymer, an organic acid, and water as essential components. 2. The ink composition for ethylene oxide sterilization markings according to claim 1, wherein the water-soluble resin is soluble in water and insoluble or poorly soluble in other solvents. 3. The ink composition for ethylene oxide sterilization labeling according to claim 1, wherein the organic acid is an acid salt of a polybasic acid.