CN108956597B - Plasma sterilization indicator paper - Google Patents

Plasma sterilization indicator paper Download PDF

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CN108956597B
CN108956597B CN201811003745.8A CN201811003745A CN108956597B CN 108956597 B CN108956597 B CN 108956597B CN 201811003745 A CN201811003745 A CN 201811003745A CN 108956597 B CN108956597 B CN 108956597B
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parts
color
sterilization
coating
agent
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CN108956597A (en
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汤百灿
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GUANGZHOU BAOLI BANGDE HIGH POLYMER MATERIAL CO LTD
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Guangzhou Mofu Material Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N21/78Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/75Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
    • G01N21/77Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
    • G01N2021/775Indicator and selective membrane

Abstract

The utility model relates to a plasma sterilization indicates the field, discloses a plasma sterilization indicator paper, indicator paper includes the substrate layer and coats or prints the instruction coating on the substrate layer, indicate the coating including the coating that discolours, the coating that discolours includes more than one can produce the dyestuff that the colour changes under hydrogen peroxide plasma effect to and a pyridine derivative who plays the fixation effect at indicator system. The plasma sterilization indicator paper has obvious color change before and after hydrogen peroxide plasma sterilization, the color after sterilization cannot be restored to the original color, the color stability is excellent, and whether a sterilization target object is subjected to a sterilization process or not can be reliably judged; the introduction of the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of the sterilization target object is proper or not can be judged through the change of the color tone.

Description

Plasma sterilization indicator paper
Technical Field
The present invention relates to the field of plasma sterilization indication, and more particularly, to a plasma sterilization indicator paper which confirms whether a sterilization target has been subjected to a sterilization process or whether sterilization has been effectively performed, by changing a color tone when hydrogen peroxide low-temperature plasma sterilizes the sterilization target.
Background
With the rapid development of medical health and health care and the continuous improvement of medical technology, various precision instruments and equipment are gradually popularized and applied, and the equipment can not be sterilized at high temperature (mainly high-temperature high-pressure steam and high-temperature dry heat). In order to solve this problem, various low-temperature chemical sterilization methods have been developed, such as ethylene oxide low-temperature sterilization applied to hospital sterilization in the 50 th century, and ethylene oxide sterilizers are widely used by some large-city hospitals in the U.S. and china by the middle of the 90 th century. The epoxy ethane has the function of killing various microorganisms such as bacteria, spores, fungi, viruses and the like; the sterilization mechanism is combined with amino, hydroxyl, carboxyl or sulfydryl in bacterial protein molecules, enzymes and nucleic acid to damage the bacterial cells, thereby achieving the sterilization effect. However, ethylene oxide is toxic and is a suspected carcinogen, and besides extremely strict indoor air concentration control, complicated purification and emission treatment is also needed, so that the operation period is long; the other widely used method is low-temperature steam formaldehyde sterilization, the sterilization mechanism of the method is similar to that of ethylene oxide, and the method also has the defects of gas toxicity, strict concentration control and purification treatment, long sterilization operation period and the like.
In the 90 s of the 20 th century, plasma sterilization began to be a pilot test as a new low temperature sterilization technique. Plasma is generated by gas under the action of heating or strong electromagnetic field, and mainly comprises electrons, ions, atoms, molecules, active free radicals, rays and the like, namely the gas slurry is called as a material aggregation state. The existing plasma sterilization is mainly performed by exciting hydrogen peroxide (H2O2) into 'gas slurry' for sterilization, wherein the hydrogen peroxide (H2O2) is an active oxidant, and the decomposition products of the hydrogen peroxide are water and nascent oxygen. The sterilization mechanism of hydrogen peroxide plasma is mainly caused by the combined action of ultraviolet rays, high-energy particles and active free radicals, wherein active substances such as active free radicals, hydrogen peroxide radicals and hydroxyl radicals are combined with proteins and nucleic acids in bacteria to destroy the metabolism of the bacteria, so that the sterilization effect is achieved. The hydrogen peroxide low-temperature plasma sterilization system has the characteristics that: the sterilization speed is high, only about 55 minutes is needed, and the detoxification time is not needed; no toxic substance is left, and the final decomposition product is water and oxygen which are safe for the environment and medical staff. Therefore, the hydrogen peroxide low-temperature plasma sterilization system (particularly GB/T32309-2015) can be used for sterilizing medical instruments and also used in the industries and works requiring sterilization of sanitary materials, food, tableware and the like.
Important in the application of these sterilization methods are: whether the equipment to be sterilized is subjected to the sterilization process is judged, and whether the sterilization effect on the equipment is proper is checked. On the other hand, indicator compositions that change color tone during sterilization have become a means of determining whether sterilization has been performed or a means of inspecting whether the sterilization effect is appropriate.
Various indicator compositions exist for indicating the presence of hydrogen peroxide based on the principle of acid-base titration. Acid-base indicators each having a different pKa value and thus a different acid-base indicating color, such as: methyl violet, picric acid, methyl green, malachite green, cresol red, methyl violet, thymol blue, methyl violet, alizarin yellow R, dimethyl yellow, bromophenol blue, congo red, alizarin red, bromocresol green, methyl red, bromophenol red, bromocresol purple, bromothymol blue, neutral red, phenol red, cresol red, phenolphthalein, thymolphthalein, alizarin red S, alizarin yellow R, dandan yellow, and the like. The applicable acid-base indicator is matched with iodide, metal salt, transition metal salt and the like, and the applicable aqueous polymer solution is matched with hydrogen sulfide, sodium hypochlorite and the like to be soaked in the filter test paper; the hydrogen peroxide forms plasma under the action of high-frequency electromagnetic field in the sterilizer, and active factors such as free radical HO, perhydroxyl free radical HO2, excited H2O2, active oxygen atom O, active hydrogen atom H and the like in the plasma react with the active factors to generate color change, so that the prepared test paper can detect the hydrogen peroxide. Also, some products in the form of printing ink are applied to a hydrogen peroxide low-temperature plasma sterilization system based on the chemical action, but the finished indicator product is unstable before and after use, such as the product is influenced by external air moisture and acid and alkali substances of contact products, the indicator changes are not obvious after being stored for a long time, or the indicator fades during the recording period after being processed by the sterilization system, and the like, which all affect the daily management of a hospital supply center.
Disclosure of Invention
In order to solve the technical problems, the patent adopts the following technical scheme:
the plasma sterilization indicator paper comprises a substrate layer and an indicator coating coated or printed on the substrate layer, wherein the indicator coating comprises a color-changing coating, the color-changing coating comprises more than one dye capable of generating color transformation under the action of hydrogen peroxide plasma, and a pyridine derivative playing a role in color fixation in an indicator system.
The hydrogen peroxide plasma sterilization indicator is substantially the same as the dye used in the ethylene oxide gas sterilization indicator. However, because the sterilization mechanisms of the ethylene oxide gas and the dye are different, the ethylene oxide gas kills the thalli through alkylation, and the hydrogen peroxide plasma kills the thalli through stronger (radio frequency ion) oxidation, so the dye discoloration mechanisms of the ethylene oxide gas and the dye are different, and the ethylene oxide gas and the dye can be stably generated or degenerated into another color after the reaction; however, even if hydrogen peroxide having a strong oxidizing action reacts with a dye after the hydrogen peroxide plasma is generated in the sterilizer, the indicator may not change color, or may change color but may be unstable or may not change color after being left for a long time. Therefore, the pyridine derivative is introduced into the color-changing coating layer to be used as a fading inhibitor of the color-changed dye generated in the hydrogen peroxide plasma sterilization treatment, so that the color change is generated more stably.
Further, the pyridine derivative is one or more of pyridone, pyrithione or a pyrithione salt.
The pyridine derivative and the dye generate other colors under the fading or matching action under the action of hydrogen peroxide with strong oxidation effect, and the action of the pyridine derivative is very critical and important, influences and controls the color development speed and the color development stability, and plays a role in controlling the color development speed and the color fixation stably.
Further, the pyrithione salt is one or more of copper pyrithione, zinc pyrithione, sodium pyrithione, magnesium pyrithione, cadmium pyrithione, zirconium pyrithione, and the like.
The vat dyes and sulfur vat dyes can obviously change color under the action of [ O ], [ H ] ion free radicals, and based on the dyes described in the patent, at least one of the vat dyes and sulfur vat dyes is preferably selected, the dyes can be reduced in alkaline solution to form soluble cryptochrome sodium salts, most of the cryptochrome sodium salts are lighter in color or colorless (the parts are just opposite), and the cryptochrome sodium salts can change the original color under the oxidation action of air or other oxidants. If some indigo vat dye leuco bodies are colorless, but are dark blue after being oxidized and reduced; for example, the leuco body of the anthraquinone vat dye is light yellow after being oxidized and reduced to red. Although other dyes have color conversion, the color difference is not higher than that of vat dyes and sulfur vat dyes; obvious front and back color difference can well play a role in indicating.
The pyridine derivative is preferably a pyridine derivative having an ionizing group. The vat dye and the sulfur vat dye are not dissolved in an aqueous system, although the leuco dye can be dissolved in the aqueous system, a non-aqueous solution can be generated along with the reduction of the pH value of the system, and the introduced copper pyrithione, sodium pyrithione and zinc pyrithione with ionized groups can stabilize the system and play a role in improving the plasma sensitivity.
The vat dye comprises at least one of anthraquinone vat dyes and indigoid vat dyes.
The anthraquinone vat dye is a vat dye synthesized by anthraquinone or derivatives thereof and a dye with an anthraquinone structure. Most of the leuco acid sodium salts of the dyes are darker than unreduced color, and only a few leuco acid sodium salts are similar to unreduced color, which is caused by that the anthraquinone without conjugated double bonds generates coherent conjugated double bonds after being reduced into the leuco acid sodium salts. The chemical reaction principle is as follows:
Figure GDA0003312211010000031
the chemical reaction principle of the indigoid vat dye is as follows:
Figure GDA0003312211010000032
the vat dye comprises at least one of vat yellow WG, vat orange 6RTK, vat yellow FFRK, vat blue RS, RSN, vat blue BC, vat blue GCDN, vat blue 3G, 5G, vat green BB, vat yellow G, vat gold orange, vat deep blue OB, vat deep blue RB, vat black BB, vat green B, FFB, red purple R, bright purple 3B, bright purple RR, purple red RRK, vat yellow GC, brilliant green FFB, indigo No. 1, vat blue 2B, vat red 5B, pink R, vat brown RRD, red purple RH, RRN, pink FFB, scarlet B, vat purple BBF, vat scarlet R, vat black B, golden yellow GK, vat bright orange GK, bright blue 4G.
The sulfur vat dyes include sulfur yellow 2G, sulfur brilliant blue CLB, sulfur blue RN, BN, BRN, sulfur new blue BBF, sulfur dark blue 3R, RL, sulfur red brown 3B, sulfur black BN, sulfur vat blue R, sulfur vat black CLN, sulfur yellow brown, sulfur red brown, etc.
The color-changing coating also comprises a waterborne polymer resin binder, wherein the waterborne polymer resin binder comprises one or more of cellulose derivatives, waterborne polybutadiene resin, waterborne epoxy resin, waterborne alkyd resin, waterborne polyester resin, waterborne polyurethane resin and waterborne acrylate emulsion. The cellulose derivative comprises at least one of hydroxymethyl cellulose (CMC), Methylcellulose (MC), hydroxyethyl cellulose (HEC), hydroxyethyl methylcellulose (HEMC), hydroxypropyl cellulose (HPC), and hydroxypropyl methylcellulose (HPMC).
In the invention, one or two different types of waterborne polyurethane emulsion and another or two different types of waterborne acrylate emulsion are preferably compounded for application.
The substrate layer is a non-hygroscopic material, preferably any synthetic paper material of PVC, PP and PET.
The indicator coating also includes a colorimetric coating for comparison.
The color of the colorimetric coating is the final color of the color-changing coating, and whether the sterilization condition meets the requirement or not and whether the sterilization effect on the sterilization target object is proper or not can be quickly judged through the comparison between the color-changing coating and the colorimetric coating.
This patent compares with prior art has following beneficial effect: the plasma sterilization indicator paper has obvious color change before and after hydrogen peroxide plasma sterilization, the color after sterilization cannot be restored to the original color, the color stability is excellent, and whether a sterilization target object is subjected to a sterilization process or not can be reliably judged; the introduction of the pyridine derivative can control the color change speed of the dye in hydrogen peroxide plasma, so that whether the sterilization condition of the sterilization target object is proper or not can be judged through the change of the color tone.
Detailed Description
This patent is described in further detail below with reference to specific examples.
The plasma sterilization indicator paper comprises a substrate layer and an indicator coating layer coated or printed on the substrate layer, wherein the indicator coating layer comprises a color-changing coating layer and a colorimetric coating layer; the color-changing coating comprises more than one dye capable of generating color transformation under the action of hydrogen peroxide plasma, and a pyridine derivative playing a role in fixing color in an indicator system; the color of the colorimetric coating is the final color of the color-changing coating.
Example 1
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 5 parts of reactive red B and 0.5 part of OB dye blue;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 2 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 2
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: active blue BF4R 2.4.4 parts, disperse pink R3L 2.0.0 parts;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion;
auxiliary agent: 3.0 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 3
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 1.0 part of active violet 5R and 0.5 part of vat yellow G;
pyridine derivatives: 1 part of zinc pyrithione and 1 part of barium pyrithione;
aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion;
auxiliary agent: 3.0 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 12.5 parts.
Example 4
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 0.4 part of vat black B, 1.0 part of active violet 5R, 0.1 part of disperse blue RRL and 0.2 part of vat yellow G;
pyridine derivatives: 1 part of sodium pyrithione and 1 part of copper pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 5.0 parts of nano titanium dioxide, 0.2 part of rheological agent, 0.8 part of film forming agent, 0.2 part of defoaming agent and 10 parts of thickening agent;
solvent: 10.1 parts of deionized water/alcohol.
Example 5
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 3.5 parts of vat blue RS;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 4.0 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 6
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 4.4 parts of vat yellow WG;
pyridine derivatives: 2 parts of sodium pyrithione;
aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion;
auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 7
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 2.0 parts of reduced indigo and 0.5 part of disperse pink;
pyridine derivatives: 1.5 parts of sodium pyrithione;
aqueous polymer resin binder: 35 parts of polyurethane emulsion and 35 parts of acrylic emulsion;
auxiliary agent: 2 parts of nano titanium dioxide, 0.2 part of rheological agent, 1.0 part of film forming agent, 0.3 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 12.5 parts.
Example 8
In this embodiment, the color-changing coating comprises the following components in parts by weight:
dye: 3.5 parts of reducing orange RF;
pyridine derivatives: 1.5 parts of sodium pyrithione and 0.5 part of cadmium pyrithione;
aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion;
auxiliary agent: 4 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent;
solvent: deionized water/alcohol 19.2 parts.
Example 9
This example differs from example 5 in that the aqueous polymer resin binder comprises 60 parts of aqueous polybutadiene resin, otherwise the example 5.
Example 10
This example is different from example 6 in that the waterborne polymer resin binder comprises 60 parts of waterborne epoxy resin, and the rest is the same as example 6.
Comparative example 1
This comparative example differs from example 1 in that the color-changing coating does not include a pyridine derivative, and is otherwise the same as example 1.
Comparative example 2
This comparative example differs from example 6 in that the color-changing coating layer does not include a pyridine derivative, and is otherwise the same as example 6.
The test method comprises the following steps:
1. the mixture of the components of each of the above examples and comparative examples was manually coated on a polypropylene-based synthetic paper (Yupo FGS-250, manufactured by Yupo corporation) substrate layer with a 0.45m/m ring-and-rod type wet film coater to form a color-changing coating layer, and after drying, indicator paper was obtained, and the initial color of each indicator paper was recorded in Table 1.
2. The sterilization treatment (2-minute elimination treatment and short-cycle treatment) was performed with a plasma sterilizer (LK/DZK series) of the genu laken medical science and technology ltd, and the discoloration results were recorded in table 1. The 2-minute abatement treatment is a treatment in which the sterilization chamber is depressurized to about 0.5torr, high-frequency energy is applied to the sterilization chamber in this state to produce an air plasma state, the pressure is restored to a first pressure, the sterilization chamber is depressurized to about 0.4torr again, and hydrogen peroxide is injected and diffused for 2 minutes; the short cycle treatment is a treatment in which hydrogen peroxide is diffused for 6 minutes, then slightly decompressed, and then high-frequency energy is applied to produce a low-temperature plasma state of hydrogen peroxide, and then hydrogen peroxide is injected and diffused for 8 minutes to apply high-frequency energy, followed by "2-minute elimination treatment".
3. The color change was recorded in table 1 after placing each indicator paper subjected to hydrogen peroxide plasma sterilization treatment in a constant temperature and humidity chamber at 23 ℃ and 90% RH for 1 month.
TABLE 1
Figure GDA0003312211010000071
As can be seen from the test results in table 1, the above examples exhibited significant color transition before and after the plasma sterilization treatment, and the color after the transition could be stably present. From the test results of example 1 and comparative example 1, and example 6 and comparative example 1, it can be seen that the pyridine derivative plays a key role in plasma sterilization indication, in example 1, the pyridine derivative is a key factor for indicating whether the indicator undergoes color transition before and after plasma sterilization treatment, and in example 6, the pyridine derivative affects the color difference of the indicator undergoing color transition before and after plasma sterilization treatment; from the test results of example 5 and example 9, and example 6 and example 10, it can be seen that the formulation of the polyurethane emulsion and the acrylate emulsion has obvious advantages compared with other waterborne polymers, better adhesion to various non-hygroscopic substrates, better compatibility with coloring dyes/vat dyes, and no dark color after sterilization treatment.
It should be understood that the above examples of the present patent are only examples for clearly illustrating the present patent, and are not intended to limit the embodiments of the present patent. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of this patent shall be included in the protection scope of the claims of this patent.

Claims (4)

1. The plasma sterilization indicator paper is characterized by comprising a substrate layer and an indicator coating layer coated or printed on the substrate layer, wherein the indicator coating layer comprises a color-changing coating layer;
the color-changing coating comprises the following components in parts by weight: dye: 5 parts of reactive red B and 0.5 part of OB dye blue; pyridine derivatives: 2 parts of sodium pyrithione; aqueous polymer resin binder: 30 parts of polyurethane emulsion and 30 parts of acrylic emulsion; auxiliary agent: 2 parts of nano titanium dioxide, 0.5 part of rheological agent, 0.7 part of film forming agent, 0.1 part of defoaming agent and 10 parts of thickening agent; solvent: 19.2 parts of deionized water/alcohol; or
The color-changing coating comprises the following components in parts by weight: dye: 4.4 parts of vat yellow WG; pyridine derivatives: 2 parts of sodium pyrithione; aqueous polymer resin binder: 40 parts of polyurethane emulsion and 20 parts of acrylic emulsion; auxiliary agent: 3 parts of nano titanium dioxide, 0.3 part of rheological agent, 0.7 part of film forming agent, 0.4 part of defoaming agent and 10 parts of thickening agent; solvent: deionized water/alcohol 19.2 parts.
2. The plasma sterilization indicator paper according to claim 1, wherein the substrate layer is any one of synthetic paper materials of PVC, PP and PET.
3. A plasma sterilization indicator paper as defined in claim 1, wherein the indicator coating further comprises a colorimetric coating for comparison.
4. The plasma sterilization indicator paper of claim 3, wherein the color of the colorimetric coating is the final color of the color changing coating.
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