CN109517524A - A kind of ancient times bone protection of resources agent - Google Patents

A kind of ancient times bone protection of resources agent Download PDF

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Publication number
CN109517524A
CN109517524A CN201811501322.9A CN201811501322A CN109517524A CN 109517524 A CN109517524 A CN 109517524A CN 201811501322 A CN201811501322 A CN 201811501322A CN 109517524 A CN109517524 A CN 109517524A
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parts
ancient times
bone
protection
resources
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张全超
吕绍武
朱泓
葛丹阳
姜蒙蒙
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Jilin University
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Jilin University
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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D189/00Coating compositions based on proteins; Coating compositions based on derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/48Stabilisers against degradation by oxygen, light or heat
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/60Additives non-macromolecular
    • C09D7/63Additives non-macromolecular organic
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The present invention provides a kind of ancient times bone protection of resources agent, belongs to ancient times bone protection of resources field.10-25 parts of adhesive, 10-25 parts of propylene glycol, 0.01-0.3 parts of antioxidase analogies, 0.01-0.05 parts of plant extracts antioxidant, 0.002-0.005 parts of preservative, 0.1-0.3 parts of lysozyme, surplus is water;Adhesive is selected from mixed type water-solubility protein.The present invention is using special adhesive and propylene glycol as substrate; select particular kind of antioxidase analogies, plant extracts antioxidant, preservative, lysozyme; it is mixed with water; pass through the cooperation of different material ingredient and its content; each mutual chemiluminescence of constituent; spraying has extraordinary film forming, invertibity, protectiveness, anti-oxidant and antibacterial ability and filling capacity after ancient times bone, it is possible to reduce film formation time and further strengthens consolidation effect;And the ancient times bone protection of resources agent is harmless to human body, has ensured the safety of operator and visitor.

Description

A kind of ancient times bone protection of resources agent
Technical field
The present invention relates to ancient times bone protection of resources field more particularly to a kind of ancient times bone protection of resources agent.
Background technique
Currently, for ancient times bone resource protective agent there are many, predominantly resinae protective agent, comprising: natural resin With zapon, the dispersion of acrylic acid colloid, acrylic emulsions product, polyvinyl acetate, polyvinyl butyral, Acrylic resin, front three resin (methyl methacrylate-butyl methacrylate-methacrylic acid copolymer), except this it Outer there are also polyethylene glycol (PEG) protective agents, but with the use of people, they the shortcomings that be also gradually exposed, it is common to lack Point is that poorly reversible, toxicity is big.
Natural resin and zapon reinforcing are poor, per se with certain color, are unfavorable for the protection of osseous remains and watch Effect does not come into operation at present;The dispersion China of acrylic acid colloid is produced not yet, utilization rate very little;Propylene Acids product emulsion is poorly reversible, is equally not frequently used;And polyvinyl acetate is not only poorly reversible, its ageing-resistant effect People's needs can not be met;Polyvinyl butyral invertibity is better than above two material, but ageing-resistant effect is poor, always It is irreversible after change, osseous remains are damaged larger;Acrylic resin will affect δ15N and δ13The numerical value of C is unfavorable for identifying the osseous remains age, Often carry out acrylic resin protection again after sampling at present;Front three resin is a kind of now widely used protective agent, it will not The identification of sample is influenced, but it is poorly reversible, and due to being dissolved using the toxic organic reagent such as toluene, chloroform, to operator And the health of visitor causes centainly to threaten, meanwhile, certain harm is also generated to environment.Other than resinous material, gather In terms of ethylene glycol (PEG) is also used for the protection of ancient times bone resource, but its easy adhering dust in high humidity environment, it does not also throw at present Enter to use.
It is poorly reversible refer to that resinae protective agent is applied to ancient times bone by way of spraying or instiling after, resinae protect The solidification of shield agent can reinforce ancient times bone, but can make between ancient times bone simultaneously and between ancient times bone and soil it is hardened at Block is difficult to remove the resinae protective agent after solidifying, and ancient times bone can not be made to return to original sclerotin sense state.Resinae is protected The poorly reversible disadvantage of shield agent limits the acquisition again for the ancient times sample bone for using resinae for safeguard measure and subsequent grinds Study carefully.
Toxicity refers to that greatly resinae protective agent frequently with toluene and chloroform is solvent.For operator's body: slightly connecing The case where touching chloroform can generate conjunctival congestion, hydroderma, and Long Term Contact can lead to embryotoxicity, teratogenesis, hepatonecrosis Or many illnesss of liver cancer etc., therefore resinae protective agent is big to operator's body toxicity.For such as the Qinghai people and Lajia site, Qinghai Ledu Liuwan Graveyard, the Inner Mongol, which breathe out the busy ruins etc. of breathing out of the people, to be had high attention rate and needs the archaeology that externally exhibit for a long time Ruins, resinae protective agent are also larger to the body harm of visitor: resinae solvent chloroform and toluene can pass through sucking Or the mode absorbed through skin enters in visitor's body, stimulating mucous membrane and anaesthetizing central nervous system leads to dizziness, has a headache, vomits It spits, weakness of limbs, the symptoms such as clouding of consciousness.
On the other hand, existing bone protection of resources agent due to film forming it is poor, can not have while keeping hardness good Ductility, during digital preservation because oxidation or ambient humidity change exist rupture, discoloration situations such as, thus lead to bone There is secondary breakoff phenomenon during protection in bone.Also side reflection has the filling capacity of bone protection of resources agent not for this Good, consolidation effect is not able to satisfy actual needs.
Summary of the invention
The present invention provides a kind of ancient times bone protection of resources agent, to solve the above problem deposited at present.
The present invention takes the technical solution to be: based on 100 parts of protective agent weight, 10-25 parts of adhesive, and propylene glycol 10-25 Part, 0.01-0.3 parts of antioxidase analogies, 0.01-0.05 parts of plant extracts antioxidant, preservative 0.002-0.005 Part, 0.1-0.3 parts of lysozyme, surplus is water.
One embodiment of the present invention: based on 100 parts of protective agent weight, 15-20 parts of adhesive, 15-20 parts of propylene glycol, resist Enzyme mimics 0.02-0.25 parts of oxidation, it is 0.02-0.05 parts of plant extracts antioxidant, 0.002-0.004 parts of preservative, molten 0.15-0.25 parts of bacterium enzyme, surplus is water.
One embodiment of the present invention: based on 100 parts of protective agent weight, 16-18 parts of adhesive, 16-18 parts of propylene glycol, resist Enzyme mimics 0.10-0.20 parts of oxidation, 0.03-0.04 parts of plant extracts antioxidant, 0.0025-0.0035 parts of preservative, 0.18-0.22 parts of lysozyme, surplus is water.
Adhesive of the present invention is selected from mixed type water-solubility protein.
Mixed type water-solubility protein of the present invention by ox bone collagen albumen and soybean water-soluble albumen by volume 1:1~ 1:6 is mixed.
Preservative of the present invention be sorbic acid and its esters, sodium hydroxy methyl glycinate, one of imidazolidinyl urea or It is a variety of.
Preservative of the present invention is sodium sorbate.
Plant extracts antioxidant of the present invention is one of tea polyphenols, Rosmarinus officinalis extract or a variety of.
Antioxidase analogies of the present invention be Cyclodextrin Bridged containing selenium with glutathione peroxidase activity, Peptide containing selenium with glutathione peroxidase activity, one in the Selenonic protein with glutathione peroxidase activity Kind is a variety of.
Containing selenium peptide of the present invention with glutathione peroxidase activity selects Arg-Gly-Sec-Arg-Asn, One or both of Sec-Arg-Gly-Asp.
Ancient times bone protection of resources agent provided by the invention, using mixed type water-solubility protein and propylene glycol as ancient times bone The substrate of protection of resources agent, not only toxicity is very low but also with water solubility well for both substrates, and has certain glue Cooperation is used, and can quickly form one layer of uniform film, and this protective film after spraying application in ancient times bone surface at room temperature With certain hardness and elasticity, can have good ductility while keeping hardness, exist compared to other protective films To during the digital preservation of bone resource because of oxidation or due to the change of ambient humidity existing for rupture event, utilize institute of the present invention Manufactured protective film can at room temperature to bone carry out digital preservation, and be not in rupture, discoloration situations such as, realize The invertibity and protectiveness of ancient times bone protection of resources agent, effectively prevent secondary destruction of bone during protection.Together When, this substrate is due to good biocompatibility, to substances such as the antioxidant contents and lysozyme added in protective agent Bioactivity bring very big protection, it can be made to keep bioactivity for a long time, achieve the purpose that persistently anti-oxidant, antibacterial, By adding non-toxic or low-toxic antioxidant-antioxidase analogies, plant extracts antioxidant, and assign ancient times bone Bone protection of resources agent reduces during excavation, transport, displaying air oxygen to ancient times bone resource to the ability of antioxidation Oxidative damage;By adding the preservative and lysozyme of certain content, and assign ancient times bone protection of resources agent antibacterial energy Power reduces erosion of the environment bacterium to ancient times bone resource in excavation, transport, show surroundings.Obtained ancient times bone resource is protected Shield agent dynamic viscosity value η is 5-300mPa.s (measuring using NDJ-1 type rotary viscosimeter), is had after spraying ancient times bone Good film forming, invertibity, protectiveness, anti-oxidant and antibacterial ability and filling capacity, it is possible to reduce film formation time and Further strengthen consolidation effect.
It is verified by test of many times, regard mixed type water-solubility protein and propylene glycol as substrate material, it can be with by mixing The substrate component of ancient times bone protection of resources agent is formed, not only toxicity is very low but also has water-soluble well for both substrate materials Property;The ancient times bone protection of resources agent configured by certain proportion, can be in its surface shape after spraying application in ancient times bone resource At layer protecting film, to play the effect of protection ancient times bone resource.Since two kinds of substrates have water solubility well, make Gu It is rinsed with water for what the protective film that bone resource surface is formed can be convenient, and ancient times bone resource is made to return to raw bone texture State realizes the invertibity of ancient times bone protection of resources agent well.
Verified, mixed type water-solubility protein is made of two kinds of components of ox bone collagen albumen and soybean water-soluble albumen, Adhesiving effect is good, and is easy to wash off, and invertibity effect is good.
For ancient times bone resource during excavation, transport, displaying, oxidation can generate biggish damage to it.In order to Avoid oxidation destruction caused by ancient times bone resource.It is verified through test of many times, bone protection of resources agent in ancient times is matched Non-toxic or low-toxic antioxidant composition is added in side: antioxidase analogies, plant extract antioxidant can assign ancient times bone Bone protection of resources agent greatly reduces ancient times bone resource during excavation, transport, displaying to the ability of antioxidation Oxidative damage.Antioxidase analogies select the Cyclodextrin Bridged containing selenium with glutathione peroxidase activity, contain selenium Peptide is any one or more of.Selenium is the essential trace elements of the human body, is counted as always being important antioxidant for a long time, While selenium or important antioxidase: the constituent of glutathione peroxidase can guarantee glutathione peroxidase Scavenger of ROS and play oxidation resistant effect, can effectively prevent biomolecule occur oxidation reaction.Cyclodextrin Bridged containing selenium is small Mouse takes orally LD50=3.6g/kg (low toxicity), and peptide containing selenium is the peptide molecule containing selenium, and Mouse oral LD50=2.8-4.1g/kg is (low Poison).The molecules such as Cyclodextrin Bridged containing selenium, peptide containing selenium have activity (the referred to as antioxidase simulation of glutathione peroxidase Object), not only there is antioxidant activity, but also possess the stability for being better than native enzyme, is more suitable for being added to ancient times bone resource In protective agent.Plant extract antioxidant selects tea polyphenols, Rosmarinus officinalis extract any one or more of.Tea polyphenols are tealeaves In main active material, be with compared with strong anti-oxidation nontoxic natural, early in the nineteen ninety-five Commission of Light Industry Just it is applied to field of food industry as antioxidant, is now the food additives of Ministry of Public Health's approval, is widely used in eating During product are fresh-keeping.Rosmarinus officinalis extract is that have the natural for protecting biomolecule to resist oxidation, in the extract Playing oxidation resistant ingredient is mainly rosmanol, Rosmarinic acid, ursolic acid, carnosol etc., and Rosmarinus officinalis extract is wide It is general to be applied to air freshener, perfume, perfumed soap, in toner, and be used in beverage, skin care oil, hair restorer.It is above-mentioned anti- Oxidation component is applied to not only prevent ancient times bone resource by oxidative damage in the protection of resources agent of ancient times bone, can be with Protect operator's safety.
Due to ancient times bone Resource exploitation, the limitation of transport and show surroundings condition, relevant environment can not be truly realized It is sterile, therefore have various environmental microorganisms and corrode ancient times bone resources, so as to cause ancient times bone resource character variation or It loses, this is great loss to non-renewable ancient times bone resource.It is verified through test of many times, in ancient times bone protection of resources Non-toxic or low-toxic antiseptic ingredient: preservative and lysozyme is added in the formula of agent, to assign ancient times bone protection of resources agent Anti-corrosion ability reduces environment bacterium of the ancient times bone resource in excavation, transport, show surroundings and corrodes.Compound preservative selects tool There is the activity for inhibiting mould, saccharomycete, aerobic bacteria, has been widely used for food, beverage, pickles, tobacco, medicine, makeup The preservative in product field.Lysozyme is a kind of protein nontoxic, without side-effects, has natural antibacterial activity, to gram Hay bacillus, micrococcus radiodurans in positive bacteria have decomposition, to Escherichia coli, proteus vulgaris and vibrio parahemolyticus Equal Gram-negative bacterias also have certain dissolution, are widely used to the anti-of aquatic products, meat products, cake, milk powder and beverage In corruption.Above-mentioned antiseptic ingredient is not required to heat during sterilization and anticorrosion, therefore can be applied to the protection of ancient times bone resource, and Ancient times bone resource will not be damaged.
In the present invention, this three big kinds of components of substrate component, antioxidant composition, antiseptic ingredient are matched by a large number of experiments Than after, the mutual chemiluminescence of each constituent of obtained ancient times bone protection of resources agent has after spraying ancient times bone Extraordinary film forming, invertibity, protectiveness, anti-oxidant and antibacterial ability and filling capacity, it is possible to reduce film formation time with And further strengthen consolidation effect.Wherein, adhesive is selected from the nutritional ingredient of mankind's diet, people's oral, non-toxic.
State food pharmaceuticals administration general bureau in 2015 approval " cosmetics safety technical specification " in, sorbic acid and The maximum allowable use concentration of its esters preservative is 0.6%, and the maximum allowable use concentration of sodium hydroxy methyl glycinate is 0.5%, miaow The maximum allowable use concentration of oxazolidinyl urea is 0.6%.The selected preservative metering of the present invention is below above-mentioned technical specification, table Bright safety is higher.
Ancient times bone protection of resources agent provided by the invention is selected specific using special adhesive and propylene glycol as substrate Antioxidant (antioxidase analogies, plant extracts antioxidant), the lysozyme of type, mix with water, by not The cooperation of commaterial ingredient and its content, each mutual chemiluminescence of constituent, spray after ancient times bone have it is very good Film forming, invertibity, protectiveness, anti-oxidant and antibacterial ability and filling capacity, it is possible to reduce film formation time and into one Step reinforces consolidation effect.And each component of ancient times bone protection of resources agent provided by the invention is non-toxic or low-toxic substance, Its additive amount refers to state food or cosmetic standard, and bone protection of resources agent obtained is harmless to human body, has ensured behaviour Make the safety of personnel and visitor.
Specific embodiment
Embodiment 1
Based on 100 parts of protective agent weight, 10 parts of adhesive, 10 parts of propylene glycol, 0.01 part of antioxidase analogies, plant is mentioned 0.01 part of object antioxidant is taken, 0.002 part of preservative, lysozyme 0.1, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:1 mixing by volume At;
The preservative is sodium sorbate;
The plant extracts antioxidant is tea polyphenols;
The antioxidase analogies are the Cyclodextrin Bridged containing selenium with glutathione peroxidase activity;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 2
Based on 100 parts of protective agent weight, 25 parts of adhesive, 25 parts of propylene glycol, 0.3 part of antioxidase analogies, plant is mentioned 0.05 part of object antioxidant is taken, 0.005 part of preservative, 0.3 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:6 mixing by volume At;
The preservative is sodium hydroxy methyl glycinate;
The plant extracts antioxidant is Rosmarinus officinalis extract;
The antioxidase analogies are the Selenonic protein with glutathione peroxidase activity;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 3
Based on 100 parts of protective agent weight, 17.5 parts of adhesive, 17.5 parts of propylene glycol, 0.15 part of antioxidase analogies, 0.03 part of plant extracts antioxidant, 0.003 part of preservative, 0.2 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:3 mixing by volume At;
The preservative is imidazolidinyl urea;
The plant extracts antioxidant is Rosmarinus officinalis extract;
The antioxidase analogies are the peptide containing selenium with glutathione peroxidase activity;
The peptide containing selenium with glutathione peroxidase activity selects Arg-Gly-Sec-Arg-Asn and Sec- Arg-Gly-Asp;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 4
Based on 100 parts of protective agent weight, 15 parts of adhesive, 15 parts of propylene glycol, 0.02 part of antioxidase analogies, plant is mentioned 0.02 part of object antioxidant is taken, 0.002 part of preservative, 0.15 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:2 mixing by volume At.
The preservative is sodium sorbate and sodium hydroxy methyl glycinate;
The plant extracts antioxidant is tea polyphenols and Rosmarinus officinalis extract;
The antioxidase analogies are Cyclodextrin Bridged containing selenium with glutathione peroxidase activity, with paddy The peptide containing selenium and the Selenonic protein with glutathione peroxidase activity of the sweet peptide peroxidase activity of Guang;
The peptide containing selenium with glutathione peroxidase activity selects Arg-Gly-Sec-Arg-Asn;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 5
Based on 100 parts of protective agent weight, 20 parts of adhesive, 20 parts of propylene glycol, 0.25 part of antioxidase analogies, plant is mentioned 0.05 part of object antioxidant is taken, 0.004 part of preservative, 0.25 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:4 mixing by volume At;
The preservative is sodium hydroxy methyl glycinate and imidazolidinyl urea;
The plant extracts antioxidant is tea polyphenols;
The antioxidase analogies are Cyclodextrin Bridged containing selenium with glutathione peroxidase activity, with paddy The peptide containing selenium and the Selenonic protein with glutathione peroxidase activity of the sweet peptide peroxidase activity of Guang;
The peptide containing selenium with glutathione peroxidase activity selects Sec-Arg-Gly-Asp;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 6
Based on 100 parts of protective agent weight, 16 parts of adhesive, 16 parts of propylene glycol, 0.10 part of antioxidase analogies, plant is mentioned 0.03 part of object antioxidant is taken, 0.0025 part of preservative, 0.18 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:5 mixing by volume At;
The preservative is sodium sorbate, sodium hydroxy methyl glycinate and imidazolidinyl urea;
The plant extracts antioxidant is Rosmarinus officinalis extract;
The antioxidase analogies are the peptide containing selenium with glutathione peroxidase activity;
The peptide containing selenium with glutathione peroxidase activity selects Arg-Gly-Sec-Arg-Asn and Sec- Arg-Gly-Asp;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Embodiment 7
Based on 100 parts of protective agent weight, 18 parts of adhesive, 18 parts of propylene glycol, 0.20 part of antioxidase analogies, plant is mentioned 0.04 part of object antioxidant is taken, 0.0035 part of preservative, 0.22 part of lysozyme, surplus is water;
Described adhesive is selected from mixed type water-solubility protein;
The mixed type water-solubility protein is by ox bone collagen albumen and the soybean water-soluble albumen system of 1:3 mixing by volume At;
The preservative is sorbic acid;
The plant extracts antioxidant is tea polyphenols;
The antioxidase analogies is the Cyclodextrin Bridgeds containing selenium with glutathione peroxidase activity and have The peptide containing selenium of glutathione peroxidase activity;
The peptide containing selenium with glutathione peroxidase activity selects Arg-Gly-Sec-Arg-Asn and Sec- Arg-Gly-Asp;
Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Its invertibity is measured respectively below by ancient times bone protection of resources agent made from experimental example 1~4, protectiveness, is resisted Oxidisability, antibiotic property and film forming.
Experimental example 1
Based on 100 parts by weight, 15 parts of mixed type water-solubility protein, wherein ox bone collagen albumen and soybean water-soluble proteosome Product than be 1:1,15 parts of propylene glycol, 0.02 part of Se-contained cyclodextrin, 0.05 part of tea polyphenols, 0.003 part of sodium sorbate, lysozyme 0.1 Part, surplus is water;Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Experimental example 2
Based on 100 parts by weight, 20 parts of mixed type water-solubility protein, wherein ox bone collagen albumen and soybean water-soluble proteosome Product than be 1:6,20 parts of propylene glycol, 0.02 part of Se-contained cyclodextrin, 0.05 part of tea polyphenols, 0.003 part of sodium hydroxy methyl glycinate, bacteriolyze 0.1 part of enzyme, surplus is water;Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Experimental example 3
Based on 100 parts by weight, 20 parts of mixed type water-solubility protein, wherein ox bone collagen albumen and soybean water-soluble proteosome Product is 15 parts of propylene glycol, 0.02 part of peptide containing selenium, 0.01 part of Rosmarinus officinalis extract, 0.005 part of sodium hydroxy methyl glycinate, molten than being 1:3 0.2 part of bacterium enzyme, surplus is water;Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
Experimental example 4
Based on 100 parts by weight, 15 parts of mixed type water-solubility protein, wherein ox bone collagen albumen and soybean water-soluble proteosome Product than be 1:5,15 parts of propylene glycol, 0.02 part of Selenonic protein, 0.05 part of tea polyphenols, 0.002 part of sodium hydroxy methyl glycinate, bacteriolyze 0.1 part of enzyme, surplus is water;Each component content is mixed into the spray up to the protection of resources agent of ancient times bone.
One, invertibity measures
1, ancient times bone protection of resources agent made from experimental example 1~4 is measured into its invertibity by way of fluorescent marker
(1), adhesive is subjected to fluorescent marker using albumen-fluorescent labeling reagent box;
(2), it is configured to ancient times bone protection of resources agent provided by the invention in proportion and is sprayed on ancient times bone, sprays With a thickness of 100 ± 10 μm;
(3), fluorescence is carried out in checking the fluorescence coverage condition on bone on box UV, visible light Transflective instrument after dry It takes a picture and Image-Pro Plus software is applied to carry out fluorescent quantitation, which is m;
(4), same bone flowing water is sufficiently washed 5 minutes later, after dry, be fixed on same position and lay equal stress on Operation in multiple (3), the data definition of acquisition are n;
(5), fluorescence reduced rate X=(m-n)/m × 100%.
2, ancient times bone protection of resources agent made from experimental example is measured into its invertibity by way of iodine water
(1), it is configured to ancient times bone protection of resources agent provided by the invention in proportion and is sprayed on ancient times bone, sprays With a thickness of 100 ± 10 μm;
(2), iodinized water is taken pictures, and carries out quantification of m to its color;
(3), same bone flowing water is sufficiently washed 10 minutes later, after dry, is fixed on same position simultaneously Operation in (2) is repeated, the data definition of acquisition is n;
(4) blue reduced rate X=(m-n)/m × 100%.
Obtain that the results are shown in Table 1.
Table 1 ancient times bone protection of resources agent invertibity measurement result
As it can be seen from table 1 when the ancient times bone protection of resources agent of experimental example preparation of the present invention is with specific soluble protein, X value range is: 96.99%≤X≤99.61% illustrates that the protective agent can be very easily washed with water;And it ought repeat again Washing operation simultaneously finds that all experimentss group X=100% illustrates that all protective agents are washed off, shows that its is superior after being measured Invertibity.
Two, protectiveness and inoxidizability measurement
(1) bone surface draws lines to measure bone hardness with portable hardometer after setting-out as demarcation indicatia in ancient times For a;
It (2) is that boundary uniformly sprays ancient times bone prepared by experimental example of the present invention to a side surface of above-mentioned ancient times bone to draw lines Bone protection of resources agent, the side for spraying ancient times bone protection of resources agent are known as protection end, and the other end is known as non-protected end, after dry The bone hardness for measuring protection end is b, and randomly selects 8 thickness selected with mircrometer gauge measurement the formed protective film of protective agent, Protective agent is calculated to bone hardness increase rate Φ=(b-a)/a × 100% simultaneously;Wherein, it sprays points for 3 times, is successively sprayed, Protective film is sprayed with a thickness of 45-55 μm for the first time, is sprayed protective film for the second time with a thickness of 75-95 μm, is sprayed protective film for the third time With a thickness of 115-135 μm;
(3) after the ancient times bone after spraying 3 times being placed in room temperature, is kept out of the direct sun displaying 6 months and 12 months, point Not Ce Ding the bone hardness c of the protection end and bone hardness d at non-protected end, calculate the bone hardness reduced rate Y=(b- of protection end C)/b × 100%, bone hardness reduced rate Z=(a-d)/a × 100% at non-protected end.The results are shown in Table 2.
Table 2 ancient times bone protection of resources agent inoxidizability measurement result
Spray from table 2 it can be seen that carrying out 1 ancient times bone protection of resources agent: protective film is with a thickness of 45-55 μm, Φ value Range is 71%≤Φ≤82%;Carry out 2 ancient times bone protection of resources agent to spray: protective film is with a thickness of 75-95 μm, Φ value model Enclosing is 101%≤Φ≤124%;Carry out 3 ancient times bone protection of resources agent to spray: protective film is with a thickness of 115-135 μm, Φ Value range is 198%≤Φ≤216%;From the above data, it can be seen that being provided using the ancient times bone that experimental example of the present invention provides Source protection agent, which carries out single or multiple spray to ancient times bone, effectively can form protective film in bone surface and enhance bone Bone hardness.
Determine the bone hardness reduced rate for spraying latter 6 months and 12 months.6 months: Y value range be 3.0%≤Y≤ 4.6 %;Z value range is 20.3%≤Z≤25.8%.12 months: Y value range was 8.1%≤Y≤9.7%;Z value range is 40.8%≤Z≤46.9%.
From the above data, it can be seen that do not spray the ancient times bone of ancient times bone protection of resources agent in room temperature, avoid daylight After direct projection is shown 6 months and 12 months, hardness is decreased obviously, caused by this is the damage as oxidation ancient times bone.And Sprayed protectant ancient times bone described in this patent, room temperature, keep out of the direct sun displaying 6 months and 12 months after, hardness Decline is very unobvious, illustrates antioxidant contained in ancient times bone protection of resources agent (antioxidase and polyphenoils) energy It is enough effectively reduced damage of the oxidation to ancient times bone, so that precious ancient times bone resource be effectively protected.
In addition, the excavation process of archaeology is ancient times bone resource there are the mutation process of environment, with ancient times bone with bury The equilibrium system between environment is hidden by broken ring, ground environment (including temperature, humidity, illumination, fungus damage etc.) can give ancient times bone resource Bring serious damage.It can be shown in situ according to ancient times bone, shift the different by ancient times bone of the requirements such as displaying, scientific research The protection of bone resource is divided into two kinds of " in-situ conservation " and " extract protection ".
" in-situ conservation ", which refers to, does not change the unearthed position for excavating out ancient times bone, that is, the scene protection carried out;It " extracts and protects Shield " refers to the protection during removed ancient times bone in the soil buried to ancient times bone, it is after historical relic is unearthed Mobile for the first time, the quality of quality of protection directly affects later displaying and research work.
In-situ conservation work is relatively easy, need to spray ancient times bone protection of resources agent provided by the invention in being exposed to soil Thickness is allowed on the ancient times bone on surface and reaches 40-140 μm, and permeates ancient times bone protection of resources agent in the block soil, face Product, which reaches, is exposed to 1.5 times of soil surface ancient times bone area or more, and depth reaches 0.3m or more, to reach protection soil table The effect in ancient times bone below face.Extraction protection work first has to (complete, broken to extracted ancient times bone resource degree of crushing Split, be loose, poor rotten, dusting etc.) and hardness evaluated, for more complete and hardness also preferable ancient times bone can first by It is stripped out in soil, then sprays 40-140 μm of ancient times bone protection of resources agent provided by the invention on its surface, later For subsequent displaying and scientific research;The ancient times bone that degree of crushing is high or hardness is poor first need to be bonded and be reinforced, incite somebody to action this The ancient times bone protection of resources agent that invention provides makes it possible to meet ancient times bone using repeatedly drop infiltration method injection ancient times bone in situ The purpose that bone extracts, using ancient times, the adhesiveness of bone protection of resources agent bonds ancient times bone, and ancient times bone protection of resources The hardness of ancient times bone can also improve after agent is dry, be used for subsequent displaying and scientific research later.The practical preservation item of ancient times bone Part is different, and it can be time quantum with 3 months or 6 months that there is also differences for the protecting effect of ancient times bone protection of resources agent, right Ancient times bone implements the tracking evaluation of protecting effect and protectant work that fills spray.
Three, antibiotic property measures
Because China is currently without the archaeology protectant antibiotic property examination criteria of class, only with reference to daily chemical products standard.This is sent out The ancient times bone protection of resources agent of bright experimental example 1-4 preparation is entrusted respectively " in China Daily Chemical Industry Research Institute's analysis test The heart " and " microbiological analysis inspection center, Guangdong Province " are with " the evaluation side of QBT 2738-2012 daily chemical products antibacterial bacteriostatic effect Method " is testing standard, and the fungistatic effect method of inspection of the antibacterial type daily chemical products referring to described in 7.5 in the standard is (antibacterial It is around-France) detection ancient times bone protection of resources agent is to the antibacterial of bacterium (escherichia coli) and fungi (candida albicans bacterium) respectively " inhibition zone diameter is greater than 7mm person, and product has bacteriostasis " is pointed out in effect, the evaluation of standard 7.5.5 fungistatic effect, and the present invention is real It tests the ancient times bone protection of resources agent inhibition zone diameter that a 1-4 is provided and is all larger than 15mm, it was demonstrated that its fungistatic effect is obvious.
In addition, can speculate that it can be used to inhibit from the formula of ancient times bone protection of resources agent provided by the invention Mould.
Four, filming performance measures
The ancient times bone protection of resources agent that experimental example of the present invention provides, using mixed type water-solubility protein and propylene glycol as ancient For the substrate of bone protection of resources agent, not only toxicity is very low but also has water-soluble well for both substrates.By centainly comparing The ancient times bone protection of resources agent of example configuration can be formed on its surface layer protecting film after spraying application in ancient times bone resource, To play the effect of protection ancient times bone resource.Since two kinds of substrates have water solubility well, make ancient times bone resource table What the protective film that face is formed can be convenient is rinsed with water, and ancient times bone resource is made to return to reset condition, realizes ancient times bone The invertibity of protection of resources agent;By the non-toxic or low-toxic natural anti-oxidation enzyme (glutathione peroxidase) of addition, naturally Polyphenoils (plant extracts antioxidant), to assign ancient times bone protection of resources agent to the ability of antioxidation, drop Oxidative damage of low ancient times bone resource during excavation, transport, displaying.By 2 recipe configuration of the above experimental example 1 and experimental example 2 portions of protective agents (is defined as: protective agent 1 and protective agent 2);Another 1 part of configuration be not added with adhesive protective agent (is defined as: comparison Protective agent 1): based on 100 parts by weight, 25 parts of propylene glycol, 0.02 part of peptide containing selenium, 0.05 part of tea polyphenols, 0.005 part of sodium sorbate, 0.3 part of lysozyme, surplus is water;According further to institute in a kind of publication CN104152046A-bone protection of resources agent of ancient times State 3 kinds of comparison protective agents of protective agent recipe configuration described in experimental example 1,4,8, be respectively defined as: comparison protective agent 2, comparison are protected Protect agent 3, comparison protective agent 4.Under the conditions of room temperature such as is protected from light at the experimental situation all the same, above-mentioned 6 kinds of protective agents are poured into In the silica dish of 20mm*10mm*5mm, and start timing, shake gently silica dish check protection agent mobility status every 5min, When inversion 30s does not flow, it is judged as that protective film is formed, is simultaneously stopped timing.By comparing protective film formed the time relatively on State the superiority and inferiority of protective agent film forming.The results are shown in Table 3.
3 different formulations ancient times bone protection of resources agent film forming comparison result of table
It is formulated label Film formation time (min)
Protective agent 1 35
Protective agent 2 30
Compare protective agent 1 135
Compare protective agent 2 102
Compare protective agent 3 95
Compare protective agent 4 89
As can be seen from Table 3,1 film formation time of comparison protective agent of adhesive is not added with significantly larger than by inventive formulation institute The protective agent stated, it was demonstrated that film formation time can be effectively reduced in the present invention really.Meanwhile with published patent family (a kind of ancient times bone protection of resources agent of CN104152046A -) compares it can be found that matching by protective agent provided by the present invention Protective agent film formation time is well below published patent made of side, it was demonstrated that the present invention is better than published similar special really Benefit, protection agent prescription proposed by the present invention can greatly improve the protection job schedule for ancient times bone resource.
Five, filling capacity
To further illustrate protectant superiority provided by the present invention, by the 0.22 μm of filter membrane mistake of protective agent 1 and 2 Filter, it can be found that can pass through, it was demonstrated that above-mentioned protective agent has good mobility;And by above-mentioned protective agent 1 and 2 Bone resource surface in ancient times is smeared, and it is apparent and microcosmic using stereomicroscope and scanning electron microscope to compare reinforcing front and back Variation.Ancient times bone resource after being reinforced using Motic SMZ-168 type stereomicroscope observation can be found that protective agent 1 and 2 Ancient times bone resource can be reinforced by the bony structures of effective adhesion ancient times bone resource soft surface;It utilizes 200 type scanning electron microscope of FEI Quanta observes ancient times bone resource surface and section, it can be found that ancient times bone resource It is filled in the crack on surface;Observation is carried out to section it is also found that the hole inside ancient times bone resource has obtained one There is apparent reduction in fixed filling, hole aperture, hole aperture d before measurement is reinforced respectively1, and reinforce metapore lyriform pore diameter d2, meter Calculate hole filling effect △ d=d1-d2.The filling capacity of above-mentioned comparison protective agent 1-4 is measured in the same manner.As a result such as Shown in table 4.
Filling effect of the different ancient times bone protection of resources agent of table 4 to ancient times bone resource internal void
It is formulated label △d(nm)
Protective agent 1 13.98
Protective agent 2 17.11
Compare protective agent 1 0.61
Compare protective agent 2 4.82
Compare protective agent 3 5.71
Compare protective agent 4 7.37
As can be seen from Table 4, compared with comparing protective agent 1-4, protectant fillibility of the present invention, which is higher than, to be disclosed About 28 times of patent family;And it can be effective after adding adhesive protective agent of the invention being made to infiltrate through ancient times bone resource inside Bonded at hole, fill up ancient times bone resource internal void as caused by long-time weathering or other factors, into One step reinforces consolidation effect.
In conclusion the ancient times bone protection of resources agent that the above-mentioned experimental example of the present invention provides, with special adhesive and the third two Alcohol selects particular kind of antioxidant (antioxidase analogies, plant extracts antioxidant), lysozyme as substrate, It is mixed with water, by the cooperation of different material ingredient and its content, each mutual chemiluminescence of constituent sprays Gu For having extraordinary film forming, invertibity, protectiveness, anti-oxidant and antibacterial ability and filling capacity after bone, can subtract Lack film formation time and further strengthens consolidation effect.And each component of ancient times bone protection of resources agent provided by the invention is equal For non-toxic or low-toxic substance, additive amount refers to state food or cosmetic standard, and bone protection of resources agent obtained is to people Body is harmless, has ensured the safety of operator and visitor.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.

Claims (10)

1. a kind of ancient times bone protection of resources agent, it is characterised in that: based on 100 parts of protective agent weight, 10-25 parts of adhesive, third 10-25 parts of glycol, 0.01-0.3 parts of antioxidase analogies, 0.01-0.05 parts of plant extracts antioxidant, preservative 0.002-0.005 parts, 0.1-0.3 parts of lysozyme, surplus is water.
2. a kind of ancient times bone protection of resources agent according to claim 1, it is characterised in that: press 100 parts of protective agent weight Meter, 15-20 parts of adhesive, 15-20 parts of propylene glycol, 0.02-0.25 parts of antioxidase analogies, plant extracts antioxidant 0.02-0.05 parts, 0.002-0.004 parts of preservative, 0.15-0.25 parts of lysozyme, surplus is water.
3. a kind of ancient times bone protection of resources agent according to claim 1, it is characterised in that: press 100 parts of protective agent weight Meter, 16-18 parts of adhesive, 16-18 parts of propylene glycol, 0.10-0.20 parts of antioxidase analogies, plant extracts antioxidant 0.03-0.04 parts, 0.0025-0.0035 parts of preservative, 0.18-0.22 parts of lysozyme, surplus is water.
4. a kind of ancient times bone protection of resources agent according to claims 1 to 3, it is characterised in that: described adhesive is selected from Mixed type water-solubility protein.
5. a kind of ancient times bone protection of resources agent according to claim 4, it is characterised in that: the mixed type water solubility egg It is white that by ox bone collagen albumen and soybean water-soluble albumen, 1:1~1:6 is mixed by volume.
6. a kind of ancient times bone protection of resources agent according to claims 1 to 3, it is characterised in that: the preservative is mountain Pears acid and its esters, sodium hydroxy methyl glycinate, one of imidazolidinyl urea or a variety of.
7. a kind of ancient times bone protection of resources agent according to claim 6, it is characterised in that: the preservative is sorbic acid Sodium.
8. a kind of ancient times bone protection of resources agent according to claim 1, it is characterised in that: the plant extracts antioxygen Agent is one of tea polyphenols, Rosmarinus officinalis extract or a variety of.
9. a kind of ancient times bone protection of resources agent according to claim 1, it is characterised in that: the antioxidase analogies For with glutathione peroxidase activity Cyclodextrin Bridged containing selenium, with glutathione peroxidase activity contain selenium One of peptide, Selenonic protein with glutathione peroxidase activity are a variety of.
10. a kind of ancient times bone protection of resources agent according to claim 9, it is characterised in that: described that there is glutathione The peptide containing selenium of peroxidase activity selects Arg-Gly-Sec-Arg-Asn, one or both of Sec-Arg-Gly-Asp.
CN201811501322.9A 2018-12-07 2018-12-07 A kind of ancient times bone protection of resources agent Pending CN109517524A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289495A (en) * 2008-05-23 2008-10-22 浙江大学 Selenium-containing pentapeptide compounds and uses thereof
CN106011125A (en) * 2016-06-08 2016-10-12 吉林大学 Peroxide nanoenzyme and preparation method thereof
AU2018100753A4 (en) * 2017-12-14 2018-07-12 Jilin University Ancient bone resource protective agent

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289495A (en) * 2008-05-23 2008-10-22 浙江大学 Selenium-containing pentapeptide compounds and uses thereof
CN106011125A (en) * 2016-06-08 2016-10-12 吉林大学 Peroxide nanoenzyme and preparation method thereof
AU2018100753A4 (en) * 2017-12-14 2018-07-12 Jilin University Ancient bone resource protective agent

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