Composite decontamination preparation for removing hair nuclide from modified chitosan oligosaccharide

Abstract

The invention relates to a compound decontamination preparation for removing hair nuclide by using modified chitosan oligosaccharide, and belongs to the technical field of nuclide decontamination and daily chemicals. The raw materials mainly comprise AESA, K12A, CDEA, NaCl, EDTA-2Na, DTPA-5Na, DTPMPA, EDTMPS, HEDP-2Na, HEDP-4Na, modified chitosan oligosaccharide and the like. The preparation method comprises the following steps: preparing the raw materials; the modified chitosan oligosaccharide is carboxymethyl chitosan oligosaccharide, and the water solubility is improved after modification. The product disclosed by the invention is produced in batches, and the efficiency verification of actinide nuclide decontamination, cobalt and cesium decontamination and iodine decontamination proves that the decontamination efficiencies in 6-hour and 12-hour experimental groups respectively reach more than 70% and more than 60%. Skin stimulation experiments of the decontamination liquid prove that the decontamination liquid has no stimulation or damage to normal head skin of a human body. A skin sensitization test proves that the guinea pig skin sensitization reaction grade is 0. The device is mainly applied to cleaning and caring hair stained by radionuclides and hair of workers in daily contact with the radionuclides. The cleaning agent is also used for personnel emergency decontamination in the fields of nuclear power stations, nuclear industry, nuclear medicine, nuclear research, nuclear accident emergency, nuclear wars and the like.

Description

Technical Field

[0001] The invention relates to a composite disinfectant preparation for removing nuclides from hair by using modified chitosan oligosaccharide, belonging to the technical field of nuclides disinfection and daily chemicals. Background Art

[0002] Radioactive nuclides are widely used in the fields of medicine, energy, military, scientific research, etc. Radioactive gases and aerosols are widely present in places where radioactive materials are produced, used and operated. The running, bubbling, dripping and leakage of radioactive liquids cause workers to contact and operate open nuclides. Although there are no clear incidents of nuclide spillage or contamination, it is inevitable that a small amount of radioactive nuclides will remain on the workers' bodies, thus causing them to be contaminated by radioactivity.

[0003] If the human body is exposed to small doses of radionuclides for a long time, it is possible to develop radiation diseases, mainly chronic radiation sickness, such as neurological symptoms (such as headache, dizziness, unsteady gait, etc.), digestive system symptoms (such as vomiting, loss of appetite, etc.), bone marrow hematopoiesis suppression, blood cell decline, bleeding and infection, etc. Therefore, when workers leave the radioactive workplace, they should clean their bodies to avoid long-term retention of radionuclides in the body, which will cause external radiation to the human body; at the same time, as time goes by, radionuclides may enter the body through the skin, and then cause internal radiation, which is more harmful.

[0004] Although there are some disinfection products at home and abroad, their disinfection efficiency is limited; the present invention intends to develop a compound preparation with modified chitosan oligosaccharide as the core to improve the ability and efficiency of disinfection of human hair. Summary of the invention

[0005] The purpose of the present invention is to provide a broad-spectrum radionuclide hair stain cleaning agent formula with modified chitosan oligosaccharide as a core component and a preparation method thereof, which can eliminate the stain of radionuclide in human hair and reduce its harm.

[0006] A composite cleaning preparation for removing hair nuclides by using modified chitosan oligosaccharide, wherein the raw materials for preparation contain the following components: pure water, fatty alcohol polyoxyethylene ether ammonium sulfate AESA, lauryl ammonium sulfate K 12 A, coconut oil fatty acid diethanolamide CDEA or 6501, sodium chloride NaCl, disodium ethylenediaminetetraacetic acid EDTA-2Na, diethylenetriaminepentaacetic acid pentasodium DTPA-5Na, diethylenetriaminepenta-methylenephosphonic acid DTPMPA, ethylenediaminetetramethylenephosphonic acid sodium EDTMPS, disodium hydroxyethylidene diphosphonic acid HEDP-2Na, tetrasodium hydroxyethylidene diphosphonic acid HEDP-4Na, modified chitosan oligosaccharide, sodium citrate, glycerol, and isothiazolinone, namely, kason, etc. The modified chitosan oligosaccharide is a material obtained by carboxymethylating -COOH of chitosan oligosaccharide with a molecular weight <2000, i.e., carboxymethyl chitosan oligosaccharide, and the molecular structure is as follows:

[0007] In the composite cleaning preparation for removing hair nuclides by modified chitosan oligosaccharide of the present invention, the proportion of each component in 1000 parts by weight of the raw materials is: 650-750 parts of pure water, 100-150 parts of AESA, 30-70 parts of K 12 A. 25~40 parts of 6501, 25~40 parts of NaCl, 15~40 parts of glycerol, 5~10 parts of EDTA-2Na, 3~10 parts of DTPA-5Na, 1~10 parts of protease, 2~5 parts of HEDP-2Na, 2~5 parts of HEDP-4Na, 2~5 parts of DTPMA, 2~5 parts of EDTMPS, 1~5 parts of modified chitosan oligosaccharide, 1~5 parts of imidazoline, 1~5 parts of sodium citrate, 0~5 parts of flavor, 0~2 parts of aloe extract, 0~2 parts of 2.5% kason preservative, 0~2 parts of methyl paraben, 0~2 parts of OCTO, 0~1 parts of amino acid moisturizer, 0~1 parts of climbazole, 0~1 parts of peppermint oil, 0~1 parts of vitamin B2, 0~1 parts (1 drop) of pigment.

[0008] In the composite cleaning preparation for removing hair nuclides by modified chitosan oligosaccharide of the present invention, the proportion of each component in 1000 parts by weight of the raw materials is: 700 parts of pure water, 120 parts of AESA, 50 parts of K 12 A, 30 parts of 6501, 30 parts of NaCl, 20 parts of glycerol, 8 parts of EDTA-2Na, 6 parts of DTPA-5Na, 5 parts of protease, 4 parts of HEDP-2Na, 4 parts of HEDP-4Na, 4 parts of DTPMA, 4 parts of EDTMPS, 3 parts of modified chitosan oligosaccharides, 3 parts of imidazoline, 2 parts of sodium citrate, 1.5 parts of flavor, 1 part of aloe extract, 1 part of 2.5% kason preservative, 1 part of methyl paraben, 1 part of OCTO, 0.5 parts of amino acid moisturizer, 0.5 parts of climbazole, 0.3 parts of peppermint oil, 0.2 parts of vitamin B2, 0.01 parts (1 drop) of pigment.

[0009] A method for preparing the above-mentioned composite cleaning and disinfecting preparation for removing hair nuclides using modified chitosan oligosaccharides is as follows: Liquid A: Add 400 parts of pure water into a container, heat to 65°C, stop heating, add 8 parts of EDTA-2Na, stir to fully dissolve; add 120 parts of AESA, stir to fully dissolve; add 50 parts of K 12 A, stir to fully dissolve; add 30 parts of 6501, stir to fully dissolve; add 3 parts of imidazoline, stir to fully dissolve; add 20 parts of glycerol, stir to fully dissolve; Solution B: Add 200 parts of water to a container, heat to 50°C, stop heating, add 30 parts of NaCl, stir to fully dissolve; add 4 parts of HEDP-4Na, stir to fully dissolve; add 4 parts of HEDP-2Na, stir to fully dissolve; add 6 parts of DTPA-5Na, stir to fully dissolve; add 4 parts of DTPMA, stir to fully dissolve; add 4 parts of EDTMPS, stir to fully dissolve; Liquid C: Add 100 parts of water into a container, heat to 35°C, stop heating, add 3 parts of modified chitosan oligosaccharide, stir to fully dissolve; add 2 parts of sodium citrate, stir to fully dissolve; add 5 parts of protease, stir to fully dissolve; add 1 part of aloe extract, stir to fully dissolve; add 1 part of OCTO, 0.5 parts of amino acid moisturizer, 0.5 parts of climbazole, 0.3 parts of peppermint oil, 0.2 parts of vitamin B2, stir to fully dissolve; add 1.5 parts of flavor, stir to fully dissolve; add 1 part of 2.5% kasone preservative, 1 part of methylparaben, stir to fully dissolve; add 0.01 part (1 drop) of pigment, stir to fully dissolve; After the above three solutions are prepared and cooled to a temperature of 15-30℃, first slowly add liquid B into liquid A, stirring while adding, and mix thoroughly; then add liquid C, stirring while adding, and mix thoroughly. Let it stand for more than 24 hours to ensure that all bubbles are expelled, and finally form a clear, viscous, colored solution with a pleasant smell.

[0010] An application of the above-mentioned composite cleaning and disinfecting preparation in removing hair nuclides.

[0011] The present invention adopts a new material modified chitosan oligosaccharide as the core material for decontamination of radionuclides in human hair. The material is prepared by degrading chitosan to make its molecular weight less than 2000, and then modifying the chitosan oligosaccharide and carboxylating (-COOH) to obtain carboxymethyl chitosan oligosaccharide, i.e., modified chitosan oligosaccharide. Experiments have shown that the material itself has a good function of removing hair radionuclides. A composite cleaning preparation is prepared by compounding with some chelating agents, complexing agents, surfactants, auxiliary agents and other materials. The functions of each component assist and enhance each other, so that the composite cleaning preparation has a strong ability to remove radionuclides, which is more efficient and practical than previous formulas. The formula can be used for the prevention and treatment of daily radionuclides contamination on the surface of human hair, and can also be used for emergency treatment of nuclear accident contamination, and has the dual functions of nuclide cleaning and hair decontamination.

[0012] The present invention uses modified chitosan oligosaccharide as the core component and uses it in combination with a variety of complexing agents to increase the complexing ability of the entire series of nuclides and increase the decontamination ability and decontamination breadth. The active agents mainly include AESA and K 12A two anionic surfactants, 6501 a nonionic surfactant, the three have a synergistic effect, can reduce the surface tension efficiency, improve the solubility of radioactive substances and common hair stains in aqueous solution, achieve the purpose of activating nuclides and dirt, and make them easier to remove. At the same time, auxiliary ingredients such as protease, imidazoline, sodium citrate, aloe extract, OCTO, amino acid moisturizer, climbazole, peppermint oil, vitamin B2, etc. are added, which can achieve the effects of dandruff decomposition, dandruff removal, moisturizing, antipruritic, smooth, refreshing, hair care and lubricating the skin where the hair is located; pigments, kasson preservatives, methyl paraben, essences and other auxiliary ingredients are added, which can achieve the functions of changing the color of the preparation, preservation, fragrance, etc., so that users have a better visual and taste experience.

[0013] Although there are some disinfection products at home and abroad, the disinfection efficiency is limited. The product of the present invention has been mass-produced. The compound preparation with modified chitosan oligosaccharide as the core developed by the present invention can improve the ability and efficiency of human hair disinfection. The verification of actinide nuclide disinfection, cobalt and cesium disinfection efficiency has proved that the disinfection efficiency in the 6h and 12h experimental groups reached more than 70% and more than 60%. The results of the skin irritation test of the composite disinfection preparation showed that no abnormality occurred on the head skin of all experimenters, proving that it has no irritation or damage to the normal head skin of the human body. The skin sensitization test of the composite disinfection preparation showed that the sensitization reaction level to the guinea pig skin was 0. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 Molecular structure of modified chitosan oligosaccharide. DETAILED DESCRIPTION

[0015] The invention discloses a broad-spectrum radionuclide hair stain cleaning agent formula with new material modified chitosan oligosaccharide as a core component and a preparation method thereof, which can eliminate the stain of radionuclide on human hair and reduce its harm.

[0016] 1. Preparation of modified chitosan oligosaccharides Modified chitosan oligosaccharide refers to a material obtained by degrading chitosan to obtain chitosan oligosaccharide with a molecular weight less than 2000, and then subjecting it to carboxymethylation (-COOH), namely, carboxymethyl chitosan oligosaccharide.

[0017] Preparation of modified chitosan oligosaccharide - The method of degradation and modification of chitosan is as follows: ①Degrade chitosan to a molecular weight of <2000 The molecular weight of chitosan is usually around hundreds of thousands. Due to the effect of hydrogen bonds in its molecules, it can only be dissolved in a few dilute acid solutions, but not directly dissolved in water. It can be degraded into chitosan oligosaccharides with a molecular weight of <2000 by irradiation decomposition (a method for degrading high molecular weight chitosan by interaction of electron beam irradiation and radiation sensitizer; application (patent) number: CN201610127153.1; application date: 2016-03-07; authorization announcement number: CN105732843B) or enzymatic hydrolysis (a method and application of preparing chitosan oligosaccharides in one step by enzymatic hydrolysis using shrimp and crab shells as raw materials; application (patent) number: CN201510232838.8; application date: 2015-05-08; authorization announcement number: CN104829749B). This technology is relatively mature, and chitosan oligosaccharides with a molecular weight of <2000 after degradation can also be directly purchased, such as the related products produced by Shandong Weikang Biomedical Technology Co., Ltd.

[0018] ② Modify chitosan oligosaccharide and carboxymethylate it (-COOH) Prepare an isopropanol solution containing sodium hydroxide in a container so that the concentration of sodium hydroxide is 40%; add the chitosan oligosaccharide with a molecular weight of <2000 after degradation; slowly drop the isopropyl acetic acid solution into the container under stirring, and continue stirring and reacting for 3 hours after the addition. After the reaction is completed, add concentrated hydrochloric acid to the reaction material, adjust the pH value of the material to 6-7, filter, and wash the filter cake with anhydrous ethanol for 3 times. After drying the washed filter cake below 50°C, obtain the primary product of carboxymethyl chitosan oligosaccharide, and then purify it to obtain carboxymethyl chitosan oligosaccharide, which is the modified chitosan oligosaccharide carboxymethyl chitosan oligosaccharide, with the molecular structure as shown below: Figure 1 .

[0019] ③Characteristics of modified chitosan oligosaccharide Modified chitosan oligosaccharide (carboxymethyl chitosan oligosaccharide) is a water-soluble chitosan oligosaccharide derivative and an amphoteric polyelectrolyte. After modification, its water solubility is improved, especially its solubility in neutral and alkaline solutions is significantly enhanced, making it have film-forming, thickening, moisturizing, chelating, antibacterial, anti-infection and other properties. It has strong complexing and removal capabilities for some nuclides.

[0020] (II) Preparation of composite disinfectant preparations with modified chitosan oligosaccharides and verification experiments 1. Decontamination solution formula components (Table 1): The main ingredients of the decontamination liquid include: pure water, fatty alcohol polyoxyethylene ether ammonium sulfate (AESA), lauryl ammonium sulfate (K 12A), coconut oil fatty acid diethanolamide (CDEA or 6501), sodium chloride (NaCl), disodium ethylenediaminetetraacetic acid (EDTA-2Na), diethylenetriaminepentaacetic acid pentasodium (DTPA-5Na), diethylenetriaminepenta (methylenephosphonic acid) (DTPMPA), sodium ethylenediaminetetramethylenephosphonate (EDTMPS), disodium hydroxyethylidene diphosphonate (HEDP-2Na), tetrasodium hydroxyethylidene diphosphonate (HEDP-4Na), modified chitosan oligosaccharide, sodium citrate, glycerol (glycerol), isothiazolinone (kason).

[0021] The proportion of each component is adjustable, and the rest is made up with pure water.

[0022] Table 1 Components and contents of three formulas of hair nuclide compound decontamination preparations

[0023] 2. Formula ingredients and raw materials (Table 2): Functions of other main components: Disodium hydroxyethylidene diphosphonate, abbreviated as HEDP-2Na, chemical formula: C2H6Na2O7P2, molar mass 250, white solid crystalline particles, soluble in water, belongs to the organic phosphonate class of scale inhibitors and corrosion inhibitors, can form stable complexes with a variety of metal ions, and can dissolve oxides. Pentasodium diethylenetriamine pentaacetate, abbreviated as DTPA-5Na, chemical formula: C 14 H 23 N3Na5O 10 , molar mass 508.3, easily soluble in water, an organic compound that can quickly form water-soluble complexes or stable chelates with radioactive metal ions, and has a wide range of complexing properties. Disodium ethylenediaminetetraacetate, abbreviation: EDTA-2NA, chemical formula: C 10 H 14 N2Na2O8▪2H2O, molar mass 372.24, easily soluble in water, solubility 0.3mol / L, 11.1g can be dissolved in every 100ml of water. It is an organic compound with multidentate ligands, containing carboxyl and amino groups, with extensive complexing properties, and can form stable chelates with radioactive metal ions. Diethylenetriaminepenta(methylenephosphonic acid), abbreviation: DTPMPA, chemical formula: C9H 28 O 15 N3P5, molar mass 573.2, acidic, good anti-scaling and corrosion inhibition effect. Fatty alcohol polyoxyethylene ether ammonium sulfate, abbreviated as AESA, easily soluble in water, anionic surfactant, with excellent cleaning, emulsification and foaming properties. Lauryl ammonium sulfate, abbreviated as K 12 A, easily soluble in water, anionic surfactant, with excellent cleaning and foaming properties. Coconut oil fatty acid diethanolamide, also known as CDEA, 6501, chemical formula: C 11 H 23CO (CH2CH2OH) 2, molar mass 287.16, easily soluble in water, non-ionic surfactant, with excellent foaming, foam stabilization, and penetrating cleaning properties. Glycerol, also known as glycerol, chemical formula: C3H8O3, molar mass 92, miscible with water and ethanol, neutral aqueous solution, a colorless, odorless, sweet, clear thick liquid. Isothiazolinone, also known as Kasson, chemical formula: C8H9ClN2O2S2, molar mass: 264.75, by breaking protein bonds, it has a strong inhibitory and killing effect on common bacteria, fungi, algae, etc. (The above ingredients are all international standards, purchased on the market) The hair cleaning preparation uses modified chitosan oligosaccharide as the core ingredient and is used in combination with a variety of complexing agents to increase the complexing ability of the entire series of nuclides, thereby increasing the decontamination ability and decontamination breadth. The active agents mainly include AESA and K 12 A two anionic surfactants, 6501 a nonionic surfactant, the three have a synergistic effect, can reduce the surface tension efficiency, improve the solubility of radioactive substances and common hair stains in aqueous solution, achieve the purpose of activating nuclides and dirt, and make them easier to remove. At the same time, protease, imidazoline, sodium citrate, aloe extract, OCTO, amino acid moisturizer, climbazole, peppermint oil, vitamin B2 and other auxiliary ingredients are added, which can achieve the effects of dandruff decomposition, dandruff removal, moisturizing, antipruritic, smooth, refreshing, hair care and lubricating the skin where the hair is located; pigments, kasson preservatives, methyl paraben, essences and other auxiliary ingredients are added (the above auxiliary ingredients are all purchased on the market), which can achieve the functions of changing the color of the preparation, preservation, fragrance enhancement, etc., so that users have a better visual and taste experience.

[0024] Table 2 Specifications of hair radionuclide decontamination reagents purchased from manufacturers

[0025] 3. Preparation of disinfectant solution The composition ratio of 1000 parts is: 700 parts pure water, 120 parts AESA, 50 parts K 12 A. 30 parts of 6501, 30 parts of NaCl, 20 parts of glycerol, 8 parts of EDTA-2Na, 6 parts of DTPA-5Na, 5 parts of protease, 4 parts of HEDP-2Na, 4 parts of HEDP-4Na, 4 parts of DTPMA, 4 parts of EDTMPS, 3 parts of modified chitosan oligosaccharide, 3 parts of imidazoline, 2 parts of sodium citrate, 1.5 parts of flavor, 1 part of aloe extract, 1 part of 2.5% kasone preservative, 1 part of methyl paraben, 1 part of OCTO, 0.5 parts of amino acid moisturizer, 0.5 parts of climbazole, 0.3 parts of peppermint oil, 0.2 parts of vitamin B2, 0.01 parts (1 drop) of pigment. "For example, prepare the disinfectant: Liquid A: Add 400 parts of pure water into a container, heat to 65°C, stop heating, add 8 parts of EDTA-2Na, stir to fully dissolve; add 120 parts of AESA, stir to fully dissolve; add 50 parts of K 12 A, stir to fully dissolve; add 30 parts of 6501, stir to fully dissolve; add 3 parts of imidazoline, stir to fully dissolve; add 20 parts of glycerol, stir to fully dissolve; Solution B: Add 200 parts of water to a container, heat to 50°C, stop heating, add 30 parts of NaCl, stir to fully dissolve; add 4 parts of HEDP-4Na, stir to fully dissolve; add 4 parts of HEDP-2Na, stir to fully dissolve; add 6 parts of DTPA-5Na, stir to fully dissolve; add 4 parts of DTPMA, stir to fully dissolve; add 4 parts of EDTMPS, stir to fully dissolve; Liquid C: Add 100 parts of water into a container, heat to 35°C, stop heating, add 3 parts of modified chitosan oligosaccharide, stir to fully dissolve; add 2 parts of sodium citrate, stir to fully dissolve; add 5 parts of protease, stir to fully dissolve; add 1 part of aloe extract, stir to fully dissolve; add 1 part of OCTO, 0.5 parts of amino acid moisturizer, 0.5 parts of climbazole, 0.3 parts of peppermint oil, 0.2 parts of vitamin B2, stir to fully dissolve; add 1.5 parts of flavor, stir to fully dissolve; add 1 part of 2.5% kasone preservative, 1 part of methylparaben, stir to fully dissolve; add 0.01 part (1 drop) of pigment, stir to fully dissolve.

[0026] After the above three solutions are prepared and cooled to a temperature (15~30℃), first slowly add liquid B into liquid A, stirring while adding, and mix thoroughly; then add liquid C, stirring while adding, and mix thoroughly. Let it stand for more than 24 hours to ensure that all bubbles are discharged, and finally form a clear, viscous, colored solution with a pleasant smell.

[0027] Note: The stirring speed and stirring time vary according to the equipment, with the full dissolution of the solvent as the indicator; full dissolution means that the solvent is completely dissolved in the aqueous solution, without precipitation, flocculation, agglomeration, and clear and transparent; the order of solvent addition should be strictly followed, otherwise there may be an intermediate reaction, affecting the final product decontamination efficiency and finished product effect; AESA dissolves slowly, so it must be fully stirred to ensure complete dissolution. If necessary, a homogenizer (emulsifier) ​​can be used for dissolution; multiple reagents should not be added at the same time and then stirred to avoid reactions. After liquid A, liquid B, and liquid C are heated to the specified temperature, heating should be stopped. The solution temperature can be used to accelerate dissolution and disinfection at the same time; after all the solvents that need to be added are dissolved, the solution temperature is basically close to room temperature or slightly higher than room temperature, and then the solution can be added. The pH of the preparation can be adjusted by sodium citrate, and the viscosity is mainly adjusted by NaCl.

[0028] 4. Verification of Decontamination Solution Efficiency (Table 3) 1) Actinide nuclide decontamination method: The contaminated nuclides in this experiment are mixed solutions of uranium and thorium, and the medium is 0.5Mol / L HNO3 solution. A certain weight of the contaminated solution is applied to the surface of the rabbit skin, and then decontaminated with actinide nuclide surface contamination decontamination solution after 0h, 6h, and 12h.

[0029] Detection method: Use ICP-MS instrument to detect the content of uranium and thorium in the contaminated liquid and the decontaminated liquid respectively, measure and read, and revise the errors in the experiment.

[0030] ①Material preparation: rabbit skin with fur, uranium standard solution, thorium standard solution, shaker, disinfection box, 50ml solution tube, disinfection reagent, ICP-MS, label paper, pen, tweezers, waste bucket, cotton swab, pipette, pipette tip, high-precision electronic balance, 0.5M HNO3 solution, etc.; ②Cut the rabbit skin with fur (without scalding) into appropriate size and put it into the disinfection box, label it and number it; set up 3 parallel control samples for each group, set up three experimental groups at 0h, 6h and 12h, and set up a control group for each experimental group without the rabbit skin with fur; ③ Prepare actinide nuclide poisoning solution: Mix 0.1ml / 1g of uranium and thorium, add 0.5M HNO3 to dilute to 10PPM, and use it as the poisoning stock solution.

[0031] ④ Take 1ml / 1g actinide nuclide solution (uranium and thorium), inject it onto the surface of the rabbit skin with a pipette and spread it evenly; for each control group, wait until the disinfection treatment is carried out, and then directly inject it onto the disinfection reagent in the disinfection box; ⑤ The 0h group started treatment 5-10 minutes after exposure, the 6h group started treatment 6 hours after exposure, and the 12h group started treatment 12 hours after exposure; ⑥ Apply 20 ml of radionuclide decontamination shampoo to the surface of the rabbit skin (the control group is directly applied to the disinfection box); put the disinfection box on the shaker, set it to 200 rpm, and disinfect for 10 minutes; collect the disinfection liquid after disinfection.

[0032] ⑦ Repeat step ⑥ 2 times according to the disinfection situation; collect a total of 60ml / 60g of disinfection solution and mix well; ⑧Take 1ml / 1g of solution ⑦, dilute it to 40ml / 40g with 0.5M HNO3 solution, and shake it evenly on a shaker; ⑨ Take 1ml / 1g of solution ⑧, dilute it to 40ml / 40g with 0.5M HNO3 solution, and shake it evenly on a shaker; ⑩ Place solution 9 on the ICP-MS for measurement, read the total number of uranium and thorium nuclides respectively, and record them; the reading of the control group is the nuclide contamination amount, and the reading of the experimental group is the decontamination amount. The decontamination efficiency = decontamination liquid / contamination liquid × 100%; enter the data into the database and use the formula to calculate the decontamination efficiency.

[0033] 2) Cobalt and cesium decontamination experimental method: The contaminating radionuclides in this experiment are cobalt and cesium mixed solutions, and the medium is aqueous solution. Take 0.5ml of the contaminating solution and apply it to the surface of the rabbit skin. Use the radionuclides decontamination shampoo preparation to decontaminate after 0h, 6h, and 12h.

[0034] Detection method: Use a gamma spectrometer to detect the radioactive content of cobalt and cesium in the wooly rabbit skin after poisoning and disinfection, measure and read, and correct the errors in the experiment.

[0035] ①Material preparation: rabbit skin with fur, transition metal nuclide solution, shaker, disinfection box, disinfection reagent, high-purity germanium gamma spectrometer, label paper, pen, non-woven fabric, tweezers, waste bucket, cotton swab, pipette, pipette tip, etc.; ② Cut the rabbit skin (without scalding) into appropriate size and put it into the disinfection box, label it and number it; set 3 parallel control samples for each group, set 0h, 6h and 12h three groups; then put it on the high-purity germanium gamma spectrometer for measurement, the measurement time is 200s, read the background total count and count rate of cesium, cobalt and manganese respectively, and record them (multiple experiments show that the background total count and count rate are 0); ③ Take 1 ml of transition metal nuclide solution, inject it onto the surface of the rabbit skin with a pipette and spread it evenly; ④ Place the rabbit skin disinfection box with the nuclide applied on the high-purity germanium gamma spectrometer for measurement. The measurement time is 200s. Read the total count and count rate of cesium, cobalt, and manganese contamination nuclides and record them; ⑤ The 0h group started treatment 5-10 minutes after exposure, the 6h group started treatment 6 hours after exposure, and the 12h group started treatment 12 hours after exposure; ⑥ Apply an appropriate amount of radionuclide decontamination shampoo to the surface of the rabbit skin and spread it with a cotton swab; place the disinfection box on the shaker, set it to 200 rpm, and disinfect for 10 minutes; pour out the disinfection solution after disinfection.

[0036] ⑦ Repeat step ⑥ once according to the disinfection results; if the disinfection effect is not good, repeat step ⑥ once more; disinfection can be repeated up to 3 times; ⑧ Wipe the decontaminated rabbit skin with non-woven cloth and put it into a clean decontamination box, then place it on a high-purity germanium gamma spectrometer for measurement. The measurement time is 200s. Read the total counts and count rates of cesium, cobalt, and manganese after decontamination and record them; ⑨Enter the data into the database and use the formula to calculate the decontamination efficiency. Decontamination efficiency = (1-after decontamination / after contamination) × 100%.

[0037] 3) Iodine decontamination experimental method: The toxic radionuclide in this experiment is iodine solution, and the medium is aqueous solution. Take 1ml of the toxic solution and apply it to the surface of the rabbit skin. Use the radionuclide decontamination shampoo preparation to decontaminate after 0h, 6h, and 12h.

[0038] Detection method: Use a low-energy gamma spectrometer to detect the radioactive content of iodine in the wooly rabbit skin after poisoning and disinfection, measure and read, and revise the errors in the experiment.

[0039] ①Material preparation: rabbit skin with fur, iodine radionuclide solution, shaker, disinfection box, disinfection reagent, high-purity germanium gamma spectrometer, label paper, pen, non-woven fabric, tweezers, waste bucket, cotton swab, pipette, pipette tip, etc.; ② Cut the rabbit skin (without scalding) into appropriate size and put it into the disinfection box, label it and number it; set 3 parallel control samples for each group, set 0h, 6h and 12h three groups; then put it on the low-energy high-purity germanium gamma spectrometer for measurement, the measurement time is 200s, read the total background count and count rate of iodine, and record them (multiple experiments show that the total background count and count rate are both 0); ③ Take 1 ml of iodine radionuclide solution, inject it onto the surface of the rabbit skin with a pipette and spread it evenly; ④ Place the rabbit skin disinfection box with the nuclide applied on the high-purity germanium gamma spectrometer for measurement. The measurement time is 200s. Read the total count and count rate of the iodine-contaminated nuclides and record them. ⑤ The 0h group started decontamination 5-10 minutes after exposure, the 6h group started decontamination 6 hours after exposure, and the 12h group started decontamination 12 hours after exposure; ⑥ Apply an appropriate amount of radionuclide decontamination shampoo to the surface of the rabbit skin and spread it with a cotton swab; place the disinfection box on the shaker, set it to 200 rpm, and disinfect for 10 minutes; pour out the disinfection solution after disinfection.

[0040] ⑦ Repeat step ⑥ once according to the disinfection results; if the disinfection effect is not good, repeat step ⑥ once more; disinfection can be repeated up to 3 times; ⑧ Wipe the decontaminated rabbit skin with non-woven fabric and put it into a clean decontamination box, then place it on a high-purity germanium gamma spectrometer for measurement. The measurement time is 200 seconds. Read the total count and count rate of iodine after decontamination and record them. ⑨Enter the data into the database and use the formula to calculate the decontamination efficiency. Decontamination efficiency = (1-after decontamination / after contamination) × 100%.

[0041] Table 3 Hair nuclide decontamination efficiency of composite decontamination preparations (three formulations)

[0042] The radionuclide decontamination efficiency of the three formula composite decontamination preparations is shown in Table 3. The test results show that the decontamination efficiency of actinide nuclides, cobalt and cesium has been verified, and the decontamination efficiency in the 6h and 12h experimental groups has reached more than 70% and more than 60% respectively.

[0043] 5. Results of the skin irritation test of disinfectant The prepared radionuclide decontamination shampoo was subjected to an animal irritation experiment. Three adult male white rabbits (experimental white rabbits purchased in the market) were selected, and the same rabbit was used for left and right control. The control side was smeared with physiological saline, and the experimental side was smeared with the prepared radionuclide decontamination shampoo. The shampoo was applied to the rabbit's ears, eyes, exposed skin, skin wounds and other parts respectively. The changes in the smeared parts of the white rabbits before smearing, 0h, 1h, 4h, 12h, 24h, 48h, 72h and 120h after smearing were qualitatively judged and quantitatively scored. The scoring items include whether the skin and ears are red, swollen, inflamed, etc.; whether the eyes are red, swollen, congested, etc.; whether the wounds are red, swollen, inflamed, and healing is delayed. The experimental results show that the prepared radionuclide decontamination shampoo did not cause irritation reactions in the ears, eyes, exposed skin, and skin wounds of the white rabbits.

[0044] Taking the rabbit naked skin stimulation experiment as an example, the specific rules of qualitative judgment and quantitative scoring are explained: Method for applying radionuclide decontamination shampoo preparation on the experimental side skin: One day before the test, shave 10cm×15cm area of ​​rabbit hair on the two parts to be applied, used as test and observation parts, add 0.5ml of radionuclide decontamination shampoo preparation to the two parts to be applied, cover each part to be applied with 2.5cm×2.5cm gauze, and then fix it with adhesive tape to form a patch. Remove the patch after 4 hours, wash with warm water and wipe dry.

[0045] Method for applying normal saline to the skin on the control side: Apply 0.5 ml of normal saline to the area to be applied on the control side. The operation method is the same as the method for applying the radionuclide decontamination shampoo preparation on the experimental side.

[0046] Observe the skin reaction under full-spectrum lighting at 0h, 1h, 4h, 12h, 24h, 48h, 72h and 120h after removing the patch, and describe and score the skin erythema and edema reactions at each contact site at each specified time according to the scoring system given in Table 4.

[0047] Table 4 Skin reaction scoring system

[0048] After scoring at 72h, add up all the erythema and edema scores caused by the test sample of each animal at 24h, 48h and 72h, and then divide the sum of all scores by 6 (two test side / control side application sites, 3 time points) to calculate the primary irritation score of the test material of a certain animal. Add up all the primary irritation scores of each animal and divide them by the total number of animals (3 rabbits) to obtain the primary irritation index of the test sample. According to the irritation reaction type corresponding to the irritation index given in Table 5, report the corresponding reaction type.

[0049] Table 5 Types of stimulation responses corresponding to primary or cumulative stimulation index in rabbits

[0050] The test results show that during the 72-day observation period, the prepared radionuclide decontamination shampoo preparation did not show any irritation reactions such as erythema and edema at the application site on the reaction test side / control side, and the irritation reaction to the rabbit skin was 0 points. The primary irritation index of the test sample was 0, and the reaction type was extremely mild irritation. That is, the irritation reaction type of the prepared radionuclide decontamination shampoo preparation to the rabbit skin was extremely mild irritation.

[0051] At the same time, the prepared radionuclide decontamination shampoo was also subjected to a human skin irritation experiment. More than 10 people were selected to apply the radionuclide decontamination shampoo on the hair surface, wash it, rinse it with water after 1 minute, and observe the changes in the hair and head skin. The experimental results showed that there was no abnormality in the head skin of all the experimenters, proving that it has no irritation or damage to the normal head skin of the human body.

[0052] 6. Skin sensitization test of radionuclide-stained hair preparations The prepared radionuclide decontamination shampoo was subjected to an animal skin sensitization test, and guinea pigs (purchased from the laboratory guinea pig market) were selected as the test animals. Both international and national standards recommend the use of albino guinea pigs to contact the test material or its extract to induce and stimulate the evaluation of skin sensitization reactions.

[0053] Experimental group setting: 15 guinea pigs were selected, of which 10 were for the experimental sample group and 5 were for the negative control group.

[0054] Preparation of test samples: Take 5 ml of the prepared radionuclide decontamination shampoo preparation, which is the test sample.

[0055] Induction: drip the test sample onto a 2.5×2.5cm sheet of filter paper, fix it on the induction site of the corresponding group of guinea pigs, cover it with gauze and fix it with adhesive tape, remove the bandage and apply the patch after 6 hours, wash it with warm water and wipe it dry. Repeat this step for 3 consecutive days in a week, and operate in the same way for 3 weeks. The control group animals were operated in the same way with 0.9% sodium chloride injection.

[0056] Provocation: Depilate the guinea pig's back 13 days after the last induction patch. 24 hours later, drip 0.9% sodium chloride injection or 0.5 ml of the test sample onto a 2.5×2.5 cm sheet of filter paper, fix it to the provocation site of the guinea pig in the corresponding group, cover it with gauze and fix it with adhesive tape. Remove the bandage and apply the patch 6 hours later, wash it with warm water and wipe it dry.

[0057] Observation indicators: 24h and 48h after stimulation, the stimulation site was scored according to the Magnusson and Kligman grading standard given in Table 6.

[0058] Table 6 Magnusson and Kligman grading standard table

[0059] Sensitization is indicated when the grade in the control group animals is less than 1 and the grade in the test group animals is greater than or equal to 1. If the grade in the control group animals is greater than or equal to 1, sensitization is considered when the reaction of the test group animals exceeds the most severe reaction in the control animals.

[0060] The test results showed that the prepared radionuclide decontamination shampoo and 0.9% sodium chloride injection had a 0-level sensitization reaction to the guinea pig skin; the sensitization rate of the guinea pig skin in the test sample group and the negative control group was 0, and there was no obvious change in the skin.

[0061] 7. Test results of other indicators of disinfectant The decontamination liquid has no stratification, no obvious suspended matter or precipitation, no mechanical impurities, transparent liquid, and no odor. The stability test results show that after being stored at 40°C for 24 hours and returning to room temperature, there is no stratification, no precipitation, no odor or discoloration, and no turbidity; after being stored at -5°C for 24 hours and returning to room temperature, there is no stratification, no precipitation, no discoloration, and no turbidity. The total effective content of active ingredients is greater than 7%, the pH is neutral, the formaldehyde content is far less than 500mg / kg, and toxic and harmful substances such as methanol, mercury, lead, arsenic, cadmium and dioxane are not detected. The total colony count is less than 10CFU / g, and the mold and yeast are less than 10CFU / g. Heat-resistant Escherichia coli, Staphylococcus aureus and Pseudomonas aeruginosa are not detected.

Claims

1. A composite cleaning preparation for removing hair nuclides using modified chitosan oligosaccharides, characterized in that: The preparation raw materials contain the following components: pure water, fatty alcohol polyoxyethylene ether ammonium sulfate AESA, lauryl ammonium sulfate K12A, coconut oil fatty acid diethanolamide CDEA or 6501, sodium chloride NaCl, ethylenediaminetetraacetic acid disodium EDTA-2Na, diethylenetriaminepentaacetic acid pentasodium DTPA-5Na, diethylenetriaminepenta-methylenephosphonic acid DTPMPA, ethylenediaminetetramethylenephosphonic acid sodium EDTMPS, hydroxyethylidene diphosphonic acid disodium HEDP-2Na, hydroxyethylidene diphosphonic acid tetrasodium HEDP-4Na, modified chitosan oligosaccharide, sodium citrate, glycerol and isothiazolinone, namely, kason; the modified chitosan oligosaccharide is a material obtained by carboxymethylating -COOH of chitosan oligosaccharide with a molecular weight less than 2000, namely, carboxymethyl chitosan oligosaccharide, and the molecular structure is as follows: .

2. The composite cleaning preparation for removing hair nuclides using modified chitosan oligosaccharides according to claim 1, characterized in that: The weight proportions of the components of the raw materials are: 650-750 parts of pure water, 100-150 parts of AESA, 30-70 parts of K12A, 25-40 parts of 6501, 25-40 parts of NaCl, 15-40 parts of glycerol, 5~10 parts of EDTA-2Na, 3~10 parts of DTPA-5Na, 1~10 parts of protease, 2~5 parts of HEDP-2Na, 2~5 parts of HEDP-4Na, 2~5 parts of DTPMA, 2~5 parts of EDTMPS, 1~5 parts of modified chitosan oligosaccharide, 1~5 parts of imidazoline, 1~5 parts of sodium citrate, 0~5 parts of flavor, 0~2 parts of aloe extract, 0~2 parts of 2.5% kason preservative, 0~2 parts of methyl paraben, 0~2 parts of OCTO, 0~1 parts of amino acid moisturizer, 0~1 parts of climbazole, 0~1 parts of peppermint oil, 0~1 parts of vitamin B2, 0~1 parts of pigment.

3. A composite cleaning preparation for removing hair nuclides using modified chitosan oligosaccharides according to claim 1 or 2, characterized in that: The weight ratio of the raw material components for the preparation is: 700 parts of pure water, 120 parts of AESA, 50 parts of K12A, 30 parts of 6501, 30 parts of NaCl, 20 parts of glycerin, 8 parts of EDTA-2Na, 6 parts of DTPA-5Na, 5 parts of protease, 4 parts of HEDP-2Na, 4 parts of HEDP-4Na, 4 parts of DTPMA, 4 parts of EDTMPS, 3 parts of modified chitosan oligosaccharides, 3 parts of imidazoline, 2 parts of sodium citrate, 1.5 parts of flavor, 1 part of aloe extract, 1 part of 2.5% kasson preservative, 1 part of methyl paraben, 1 part of OCTO, 0.5 parts of amino acid moisturizer, 0.5 parts of climbazole, 0.3 parts of peppermint oil, 0.2 parts of vitamin B2, and 0.01 parts of pigment.

4. A method for preparing the composite disinfectant preparation as claimed in claim 2 or 3, comprising the following steps: Liquid A: Add 4 / 7 of the total weight of pure water into a container, heat to 65°C, stop heating, add EDTA-2Na, stir to fully dissolve; Add AESA and stir to fully dissolve; add K12A and stir to fully dissolve; add 6501 and stir to fully dissolve; add imidazoline and stir to fully dissolve; add glycerol and stir to fully dissolve; Liquid B: Add 2 / 7 of the total weight of pure water into a container, heat to 50°C, stop heating, add NaCl, stir to fully dissolve; add HEDP-4Na, stir to fully dissolve; add HEDP-2Na, stir to fully dissolve; add DTPA-5Na, stir to fully dissolve; add DTPMA, stir to fully dissolve; add EDTMPS, stir to fully dissolve; Liquid C: Add the remaining pure water into the container, heat to 35°C, stop heating, add modified chitosan oligosaccharide, stir to fully dissolve; add sodium citrate, stir to fully dissolve; add protease, stir to fully dissolve; add aloe extract, stir to fully dissolve; add OCTO, amino acid moisturizer, climbazole, peppermint oil, vitamin B2, stir to fully dissolve; add flavor, stir to fully dissolve; add 2.5% kasone preservative and methyl paraben, stir to fully dissolve; add pigment, stir to fully dissolve; After the above three solutions are prepared and cooled to a temperature of 15-30℃, first slowly add liquid B into liquid A, stirring while adding, and mix thoroughly; then add liquid C, stirring while adding, and mix thoroughly. Let it stand for more than 24 hours to ensure that all bubbles are expelled, and finally form a clear, viscous, colored solution with a pleasant smell.

5. Use of the composite cleaning and disinfecting preparation according to any one of claims 1 to 3 in removing hair nuclides.

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