CN109735277A - A kind of historical relic reparation adhesives and preparation method thereof - Google Patents
A kind of historical relic reparation adhesives and preparation method thereof Download PDFInfo
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- CN109735277A CN109735277A CN201910043310.4A CN201910043310A CN109735277A CN 109735277 A CN109735277 A CN 109735277A CN 201910043310 A CN201910043310 A CN 201910043310A CN 109735277 A CN109735277 A CN 109735277A
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Abstract
The invention discloses a kind of historical relic reparation adhesives and preparation method thereof, adhesives includes: 50~60 parts of epoxy resin-base, 20~30 parts of curing agent, 1~10 part of plasticized modifier, 0.1~0.5 part of silane coupling agent, 0.5~1 part of antibacterial agent, 0.5~1 part of Antibacterial accessory ingredient, 1~10 part of base powder.When preparing adhesives, first by epoxy resin-base heating and vacuum defoamation, deaeration epoxy resin is obtained；It again disperses antibacterial agent in acetone, and is added in deaeration epoxy resin, then successively silane coupling agent, plasticized modifier, Antibacterial accessory ingredient, mica powder and base powder are added in mixed system, stir evenly to obtain modified epoxy；Finally curing agent is added in modified epoxy before carrying out historical relic reparation, mixes thoroughly and removes bubble and obtain adhesives.Using the adhesives in the present invention, it can effectively solve the problems, such as the historical relic after historical relic is repaired adhesive effect difference and repaired vulnerable to microbial attack.
Description
Technical field
The invention belongs to historical relic recovery technique fields, and in particular to a kind of historical relic reparation adhesives and its preparation side
Method.
Background technique
Historical relic is the mankind in the remains or traces transforming the objective world with carry over during subjective world, is history
, national cultural heritage, be the materialization carrier of social civilization and national spirit.But some historical relics due to storage environment not
It is good, such as be exposed in natural environment for a long time and will inevitably generate weathering phenomenon, furthermore caused by contemporary industry development
Environmental pollution, gradually aggravate the extent of corrosion of these rare cultural relics；On the other hand, due to being gone back during excavation and protection
Even broken etc. secondary injuries of scratch, delamination, fracture inevitably will be caused to historical relic, so losing to these precious culture
The protection and repair of production are extremely huge and important.
Stone cultural artifact is exposed mostly in air, with remote, environment deterioration, the artificial destruction in age, Hen Duozhen
The appearance of your stone cultural artifact is gradually smudgy, and various guard methods occur in succession and are applied in stone artifact.Mesh
Filling of the recovery technique of preceding stone cultural artifact mainly for its surfacecti proteon and stone cultural artifact after internal aging, and material used
Material is mostly inorganic material, it is weak with stone cultural artifact surface binding force compared with organic material, poor mechanical property, and does not have substantially
Antibacterial and mouldproof effect, weatherability and ageing-resistant performance are bad.In addition, these historical relic repair materials and technique are only for certain spies
Fixed historical relic material and disease, application range is relatively narrow, and the recovery technique of the historical relic for needing to be bonded after fracturing or break up is several
Do not have, therefore is badly in need of exploring new historical relic bonding renovation technique and material to protect these historical relics.
Bamboo and wood, lacquerware class historical relic are mostly buried in underground before excavation, and impregnating for a long time in underground water leads to these bamboos
The wooden lacquerware class historical relic saturated with water, thus it is more multiple to the technical process of these satisfy the lacquerware class historical relic's protection of fishscale bamboo wood and reparations
It is miscellaneous, and the performance requirement of material requested is also more harsh.The range of full fishscale bamboo wood lacquerware class historical relic's protection and reparation is very wide, presses
Journey can be divided into live emergency protection, the protection in transportational process, cleaning, full water save, decoloration, dehydration, repair after dehydration and
Preservation and exhibition after repairing etc..It is focused primarily upon at present for bamboo and wood, lacquerware class historical relic reparation and protection art solutions
Solve the dehydration and the sizing and surfacecti proteon in later period of full fishscale bamboo wood lacquerware, the material used power compared with traditional organic material
It is lower to learn performance.In addition, for the repair materials and technology of the bamboo and wood lacquerware class historical relic for needing to be bonded after fracturing or break up
It is less.
At present, material involved in historical relic vertex-gluing graph aspect is damaged mainly to be bonded by natural material blending
And filling capacity, but obtained bonding agent and historical relic ontology binding force be not high, and curing time is longer to cause vertex-gluing graph to be imitated
Rate is not high；Erosion of the historical relic after reparation by microorganism simultaneously, it is difficult to keep repairing effect for a long time.
Summary of the invention
For the above-mentioned prior art, the present invention provides a kind of historical relic reparation adhesives and preparation method thereof, to solve
Historical relic repairs the problem of historical relic after adhesive effect difference and reparation is vulnerable to microbial attack.
In order to achieve the above object, the technical scheme adopted by the invention is that: a kind of historical relic reparation adhesives is provided
It comprises the following components in parts by weight: 50~60 parts of epoxy resin-base, 20~30 parts of curing agent, 1~10 part of plasticized modifier, silicon
0.1~0.5 part of alkane coupling agent, 0.5~1 part of antibacterial agent, 0.5~1 part of Antibacterial accessory ingredient, 1~10 part of base powder；Antibacterial agent is to carry
Silver-colored four needle zinc oxide, Antibacterial accessory ingredient are diatomite, chitosan, titanium dioxide, n,N-Dimethylformamide or 2- mercapto benzo miaow
Azoles, the material of base powder are identical as the material of historical relic to be repaired.
Based on the above technical solution, adhesives of the invention can also do following improvement.
Further, adhesives comprises the following components in parts by weight: 55 parts of epoxy resin-base, 25 parts of curing agent, and toughening
5 parts of modifying agent, 0.4 part of silane coupling agent, 0.8 part of antibacterial agent, 0.8 part of Antibacterial accessory ingredient, 1.3 parts of base powder.
Further, epoxy resin-base is E44 epoxy resin.
Further, curing agent is 650 polyamide and/or 651 polyamide.
Further, plasticized modifier is the liquid natural rubber that viscosity average molecular weigh is 4000~20000.
Further, plasticized modifier is made by the following method: natural rubber being cut into the fritter that partial size is 1~2cm, so
The toluene or carbon tetrachloride of 2~3 times of amounts are added afterwards, 2~4h is swollen under the conditions of 35~45 DEG C, then adds into the system after swelling
Enter potassium permanganate, and the pH of regulation system is 4~6, obtains plasticized modifier after reacting 2~6h；The potassium permanganate and day being added
0.5~1:1 of mass ratio of right rubber.
Further, the partial size of base powder is 300 mesh.
It further, further include 1~10 part of mica powder.
In the present invention bonding agent preparation method the following steps are included:
(1) epoxy resin-base is put into reaction vessel, and is heated to 100~130 DEG C, then 2~3h of vacuum defoamation,
Obtain deaeration epoxy resin；
(2) silver-colored four needle zinc oxide will be carried to be scattered in acetone, antimicrobial is obtained, then under agitation by antibacterial agent
Solution is added in deaeration epoxy resin, then remaining component in addition to curing agent is added in mixed system, is stirred evenly
Obtain modified epoxy；
(3) the historical relic preceding 5~10min of reparation is being carried out, curing agent is added in modified epoxy, mixes thoroughly and removes gas
Steep to obtain adhesives.
The silver-colored four needle zinc oxide of load used when adhesives are prepared to be made by following steps:
S1: the sour nitre zinc solution for being 0.1~0.6mol/L with deionized water configuration concentration, concentration are 0.6~1.5mol/L
Ammonia spirit and concentration be 0.5mol/L silver nitrate solution, and silver nitrate solution is slowly added dropwise into ammonia spirit, shape
At precursor solution, the volume ratio of the silver nitrate solution and ammonia spirit that are added is 5:1；
S2: being added dropwise silver nitrate solution into precursor solution under agitation, and m (Ag): m (Zn) in control system=
0.01~0.05,20h then is reacted under the conditions of 90~120 DEG C, obtains product solution；
S3: filtering product solution is successively washed sediment, alcohol is washed and is dried, and must carry silver-colored four needle zinc oxide
Antibacterial agent.
The beneficial effects of the present invention are:
1. historical relic maintenance cost can be substantially reduced as matrix using E44 epoxy resin in the present invention；Curing agent is using poly-
Amides curing agent, polyamide-based curing agent are normal temperature cure agent, and solidification temperature range is wide, and solidification speed can be adjusted by dosage
Degree, gained bonding agent good toughness and adhesive strength are high；For plasticized modifier using liquefaction natural rubber, molecular weight control is easy,
Can obtain viscosity average molecular weigh by control reaction temperature, reaction time and regulation system pH value is 4000~20000 and band
There is the liquefaction natural rubber of carboxyl and carbonyl, obtained liquefaction natural rubber has good dispersibility in the epoxy,
Mutually separation is generated in solidification process and forms island structure, and the toughness of epoxy resin greatly improves；Antibacterial agent is needle-shaped using silver four is carried
Zinc oxide, carries silver-colored four-needle-like zinc oxide and Antibacterial accessory ingredient acts synergistically, and can avoid microorganism in the bonding plane of protection historical relic reparation
Upper attachment is bred, meanwhile, zinc oxide has the effect of shielding ultraviolet irradiation, and the ageing-resistant performance of epoxy resin can be improved；It is bonded material
Base powder and epoxy resin in material keep good dispersibility, this compatability is good with historical relic, while can also increase text
Object body color similitude.
2. the preparation for carrying silver-colored four-needle-like zinc oxide and size regulation used are easy in the present invention, can be by adjusting hydro-thermal reaction
It is middle be added ammonium hydroxide concentration come control it is single carry Ag-ZnO diameter and draw ratio, pass through control be added silver nitrate concentration
Mention the antibiotic rate of high silver supported four-needle-like zinc oxide.
3. the mica powder in adhesives has good shielding ultraviolet rays and reflects the optical characteristics of ultraviolet light, can be improved
The weatherability of material enhances the protective effect to restoring relics.
Specific embodiment
One, raw material
Epoxy resin: as the matrix of adhesives in the present invention, E44 epoxy resin is preferentially used；
Polyamide: using as curing agent, preferentially uses 650 polyamide or 651 polyamide；
Liquid natural rubber: using as plasticized modifier, and liquid natural rubber is made by the following method: by natural rubber
Glue is cut into the fritter that partial size is 1~2cm, the toluene or carbon tetrachloride of 2~3 times of amounts (quality multiple) is then added, in 35~45
It is swollen 2~4h under the conditions of DEG C, then potassium permanganate is added into the system after swelling, and the pH of regulation system is 4~6, reaction 2~
Plasticized modifier is obtained after 6h；0.5~1:1 of mass ratio of the potassium permanganate and natural rubber that are added；Prepared liquid day
The viscosity average molecular weigh of right rubber is 4000~20000.
Silane coupling agent: can be the models such as KH-560 for improving the interface performance of the raw materials such as epoxy resin body
Silane coupling agent；
Antibacterial agent: the antibacterial agent in the present invention is made using silver-colored four needle zinc oxide are carried by following steps:
S1: the sour nitre zinc solution for being 0.1~0.6mol/L with deionized water configuration concentration, concentration are 0.6~1.5mol/L
Ammonia spirit and concentration be 0.5mol/L silver nitrate solution, and silver nitrate solution is slowly added dropwise into ammonia spirit, shape
At precursor solution, the volume ratio of the silver nitrate solution and ammonia spirit that are added is 5:1；
S2: being added dropwise silver nitrate solution into precursor solution under agitation, and m (Ag): m (Zn) in control system=
0.01~0.05,20h then is reacted under the conditions of 90~120 DEG C, obtains product solution；
S3: filtering product solution is successively washed sediment, alcohol is washed and is dried, and must carry silver-colored four needle zinc oxide
Antibacterial agent；
Antibacterial accessory ingredient: working with antibacterial agent one, improves the antibacterial ability of antibacterial agent；Antibacterial accessory ingredient is diatomite, shell is poly-
One of sugar, titanium dioxide, N,N-dimethylformamide and 2 mercapto benzimidazole；
Base powder: the material of base powder is identical as the material of historical relic to be repaired, for example to repair stone cultural artifact, then base
Bottom powder is mountain flour, and Yao Xiufu bamboo matter historical relic, then base powder is bamboo powder；The partial size of base powder is 300 mesh.
Two, adhesives is prepared
1. epoxy resin-base is put into reaction vessel, and 100~130 DEG C are heated to, then 2~3h of vacuum defoamation,
Obtain deaeration epoxy resin；
2. silver-colored four needle zinc oxide will be carried to be scattered in acetone, antimicrobial is obtained, then under agitation by antibacterial agent
Solution is added in deaeration epoxy resin, then successively by silane coupling agent, plasticized modifier, Antibacterial accessory ingredient, mica powder and substrate
Powder is added in mixed system, stirs evenly to obtain modified epoxy；
3. repairing preceding 5~10min carrying out historical relic, curing agent is added to modified epoxy and is stirred evenly, is obtained viscous
Connect material.
Three, historical relic reparation
1. the cultural artifact surface bonded will be needed to clean, mark and preprosthetic processing；
2. the adhesives prepared is coated on the historical relic plane of disruption, bonded according to mark before；
3. the historical relic bonded is shaped with special stand, displacement is observed and corrects, vertex-gluing graph is complete after about 2h
Historical relic, which then finalizes the design almost, to be no longer subjected to displacement, and can be fully cured after 6~12h；
4. removing setting fixture after being fully cured, coated and mountain flour similar in historical relic color after bonding trace with doctor blade
And exchange views, it completes to repair.
Below with reference to embodiment, specific embodiments of the present invention will be described in detail.
Embodiment one
A kind of repairing stone relics adhesives, comprising: E44 epoxy resin-base 6kg, 651 kymene kg, liquid
Natural rubber (Mv=10000) 0.5kg, KH-560 type coupling agent 0.04kg carry four needle zinc oxide 0.08kg of silver, titanium dioxide
0.08kg, mica powder 0.3kg, the mountain flour 0.5kg of 300 mesh.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 6kg, is put into reaction vessel, and is heated to 120 DEG C, then vacuum defoamation 3h,
Obtain deaeration epoxy resin；
(2) the silver-colored four needle zinc oxide of load of 0.08kg are weighed and are scattered in acetone, antimicrobial are obtained, then in stirring bar
Antimicrobial is added in deaeration epoxy resin under part, then successively by the KH-560 type coupling agent of 0.04kg, the liquid of 0.5kg
State natural rubber, the titanium dioxide of 0.08kg, the mica powder of 0.3kg and 0.5kg mountain flour be added in mixed system, stir evenly
Obtain modified epoxy；
(3) preprosthetic 5min is being carried out to stone cultural artifact, the polyamide 6 51 of 3kg is being added in modified epoxy,
It mixes thoroughly and removes bubble and obtain adhesives.
Embodiment two
A kind of bamboo matter historical relic reparation adhesives, comprising: E44 epoxy resin-base 5kg, 650 polyamide 2kg, liquid
Natural rubber (Mv=20000) 0.3kg, KH-560 type coupling agent 0.05kg carry four needle zinc oxide 0.1kg of silver, diatomite
0.1kg, mica powder 0.95kg, the bamboo powder 0.7kg of 300 mesh.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 5kg, is put into reaction vessel, and is heated to 100 DEG C, then vacuum defoamation 2h,
Obtain deaeration epoxy resin；
(2) the silver-colored four needle zinc oxide of load of 0.1kg are weighed and are scattered in acetone, antimicrobial are obtained, then in stirring bar
Antimicrobial is added in deaeration epoxy resin under part, then successively by the KH-560 type coupling agent of 0.05kg, the liquid of 0.3kg
State natural rubber, the diatomite of 0.1kg, the mica powder of 0.95kg and 0.7kg bamboo powder be added in mixed system, stir evenly
Obtain modified epoxy；
(3) preprosthetic 5min is being carried out to stone cultural artifact, 650 polyamide of 3kg is being added in modified epoxy,
It mixes thoroughly and removes bubble and obtain adhesives.
Embodiment three
A kind of wooden cultural relic reparation adhesives, comprising: E44 epoxy resin-base 8kg, 650 kymene kg, liquid
Natural rubber (Mv=4000) 0.5kg, KH-560 type coupling agent 0.01kg carry silver-colored four needle zinc oxide 0.05kg, 2- mercapto benzene
And imidazoles 0.01kg, mica powder 0.1kg, the bamboo powder 0.33kg of 300 mesh.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 8kg, is put into reaction vessel, and is heated to 130 DEG C, then vacuum defoamation 3h,
Obtain deaeration epoxy resin；
(2) the silver-colored four needle zinc oxide of load of 0.05kg are weighed and are scattered in acetone, antimicrobial are obtained, then in stirring bar
Antimicrobial is added in deaeration epoxy resin under part, then successively by the KH-560 type coupling agent of 0.01kg, the liquid of 0.5kg
State natural rubber, the 2 mercapto benzimidazole of 0.01kg, the mica powder of 0.1kg and 0.33kg bamboo powder be added to mixed system
In, stir evenly to obtain modified epoxy；
(3) preprosthetic 10min is being carried out to stone cultural artifact, curing agent is added in modified epoxy, is mixed thoroughly simultaneously
Removing bubble obtains adhesives.
Comparative example one
A kind of bamboo matter historical relic reparation adhesives, comprising: E44 epoxy resin-base 5kg, 650 polyamide 2kg, liquid
Natural rubber (Mv=20000) 0.3kg, KH-560 type coupling agent 0.05kg, diatomite 0.1kg, mica powder 0.95kg, 300 mesh
Bamboo powder 0.7kg.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 5kg, is put into reaction vessel, and is heated to 100 DEG C, then vacuum defoamation 2h,
Obtain deaeration epoxy resin；
(2) by KH-560 type coupling agent, the liquid natural rubber of 0.3kg, the diatomite of 0.1kg, the 0.95kg of 0.05kg
Mica powder and the bamboo powder of 0.7kg be added in deaeration epoxy resin, stir evenly to obtain modified epoxy；
(3) preprosthetic 5min is being carried out to stone cultural artifact, 650 polyamide of 3kg is being added in modified epoxy,
It mixes thoroughly and removes bubble and obtain adhesives.
Comparative example two
A kind of bamboo matter historical relic reparation adhesives, comprising: E44 epoxy resin-base 5kg, 650 polyamide 2kg, liquid
Natural rubber (Mv=20000) 0.3kg, KH-560 type coupling agent 0.05kg carry four needle zinc oxide 0.1kg of silver, mica powder
0.95kg, the bamboo powder 0.7kg of 300 mesh.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 5kg, is put into reaction vessel, and is heated to 100 DEG C, then vacuum defoamation 2h,
Obtain deaeration epoxy resin；
(2) the silver-colored four needle zinc oxide of load of 0.1kg are weighed and are scattered in acetone, antimicrobial are obtained, then in stirring bar
Antimicrobial is added in deaeration epoxy resin under part, then successively by the KH-560 type coupling agent of 0.05kg, the liquid of 0.3kg
The bamboo powder of state natural rubber, the mica powder of 0.95kg and 0.7kg is added in mixed system, stirs evenly to obtain modified epoxy tree
Rouge；
(3) preprosthetic 5min is being carried out to stone cultural artifact, 650 polyamide of 3kg is being added in modified epoxy,
It mixes thoroughly and removes bubble and obtain adhesives.
Comparative example three
A kind of bamboo matter historical relic reparation adhesives, comprising: E44 epoxy resin-base 5kg, 650 polyamide 2kg, liquid
Nitrile rubber 0.3kg, KH-560 type coupling agent 0.05kg carries silver-colored four needles zinc oxide 0.1kg, diatomite 0.1kg, mica powder
0.95kg, the bamboo powder 0.7kg of 300 mesh.
Above-mentioned adhesives the preparation method comprises the following steps:
(1) the E44 epoxy resin for weighing 5kg, is put into reaction vessel, and is heated to 100 DEG C, then vacuum defoamation 2h,
Obtain deaeration epoxy resin；
(2) the silver-colored four needle zinc oxide of load of 0.1kg are weighed and are scattered in acetone, antimicrobial are obtained, then in stirring bar
Antimicrobial is added in deaeration epoxy resin under part, then successively by the KH-560 type coupling agent of 0.05kg, the liquid of 0.3kg
Body nitrile rubber, the diatomite of 0.1kg, the mica powder of 0.95kg and 0.7kg bamboo powder be added in mixed system, stir evenly
Obtain modified epoxy；
(3) preprosthetic 5min is being carried out to stone cultural artifact, 650 polyamide of 3kg is being added in modified epoxy,
It mixes thoroughly and removes bubble and obtain adhesives.
Comparative example four
A kind of antibacterial solid agent, including following components:
50 parts of chitosan oligosaccharide, 100 parts of catechin, cetomacrogol 1000 part, 850 parts of water, 150 parts of ethyl alcohol.
Wherein the molecular weight of polyethylene glycol is 2000 in polyglycol solution, and the average molecular weight of chitosan oligosaccharide is 2000, is taken off
Acetyl degree is 94.2%, and the Epigallo-catechin gallate (EGCG) EGCG content of catechin is 63.2%, and epicatechin is not eaten
Sub- acid esters ECG content is 14.6%, and epicatechin EC content is 8.5%.
Polyethylene glycol is dissolved in water and ethyl alcohol forms the solution that mass fraction is 20%；Chitosan oligosaccharide and catechin are added to
In above-mentioned solution, stirred evenly at 40 DEG C~50 DEG C；PH value is adjusted to 5.5；It is heated in 50 DEG C~70 DEG C constant temperature baths, so that poly-
The mass fraction that ethylene glycol solution is concentrated into polyethylene glycol is 50%.
Interpretation of result
The bamboo matter historical relic of soil is taken out, and the erosion bacterium on bamboo matter historical relic is identified, is found on bamboo matter historical relic comprising thin
The bacteriums such as Alternaria, phialophora richardsiae, Aspergillus terreus, penicillium chrysogenum, Penicillium patulum, Rhizoctonia solani Kuhn, Aspergillus glaucus.Then pass through reality
It tests and has investigated product obtained by embodiment two and comparative example one to comparative example four respectively to the inhibitory effect of above-mentioned bacterium, knot
Fruit is listed in table 1, the mean size of the digital representation inhibition zone in table.
Inhibition situation of 1 adhesives of table to bacterium
| Embodiment two | Comparative example one | Comparative example two | Comparative example three | Comparative example four | |
| Alternaria is mould | -- | 2 | -- | -- | -- |
| Phialophora richardsiae | -- | -- | -- | -- | -- |
| Aspergillus terreus | -- | 8 | 6 | -- | 8 |
| Penicillium chrysogenum | -- | 7 | 6 | -- | 7 |
| Penicillium patulum | -- | 4 | 2 | -- | -- |
| Rhizoctonia solani Kuhn | -- | 3 | 1 | -- | -- |
| Aspergillus glaucus | -- | -- | 1 | -- | -- |
As can be seen from the table, being bonded using the adhesives (embodiment two) in the present invention can be to the thin of interface
Bacterium is effectively inhibited, and is avoided bonding historical relic from being corroded by bacterium and be broken again, can be kept good bonding for a long time
Effect.Comparative example one lacks the silver-colored four-needle-like zinc oxide of load compared with embodiment two, in component, and it is anti-that bacteriostatic experiment shows that it does not have
Bacterium performance cannot inhibit bacterium, and adhesive effect is poor；Comparative example two lacks antibacterial compared with embodiment one, in component and helps
Agent (diatomite), antibacterial agent cannot disperse in adhesives well, have an impact to the fungistatic effect of antibacterial agent；Comparative example
Three compared with embodiment one, and only the plasticized modifier in component is changed, and will not impact to fungistatic effect；Comparison
Example is fourth is that a kind of existing antibacterial solid agent, cannot inhibit all bacteriums, antibacterial effect is poor.
In addition, having investigated curing time (h) and adhesive strength (MPa) of above-mentioned various adhesives, and pass through ultraviolet light
The ageing-resistant performance of adhesives is investigated in irradiation, and whether ageing-resistant performance is cracked embodiment with being bonded mouth.As a result it is listed in table 2.
1 adhesives adhesive property of table
| Embodiment two | Comparative example one | Comparative example two | Comparative example three | Comparative example four | |
| Curing time/h | 3 | 3 | 3.5 | 4 | 6 |
| Adhesive strength (MPa) | 3.25 | 3.11 | 3.09 | 2.17 | 1.72 |
| Whether be open/for 24 hours | It is no | Cracking | It is no | Slight cracking | Cracking |
As can be seen from the table, using adhesives prepared by the present invention carry out historical relic bonding, not only curing time compared with
It is short, and adhesive strength with higher, mouth is bonded after ultraviolet irradiation and is not also cracked, and shows the adhesives in the present invention
It is a kind of ideal historical relic repair materials with good adhesive property and ageing-resistant performance.Documents one and embodiment two
It compares, the silver-colored four-needle-like zinc oxide of load is lacked in component and glues joint broken after ultraviolet irradiation, shows to carry silver-colored four needle-shaped oxidations
Zinc can not only be antibacterial, moreover it is possible to shield ultraviolet spoke radiation, have to the ageing-resistant performance of adhesives and remarkably promote effect；Comparison
Example two lacks Antibacterial accessory ingredient (diatomite) compared with embodiment one, in component, and curing time is extended, it may be possible to because of antibacterial
Auxiliary agent is the lesser powder of partial size, can enhance the cohesive force inside adhesives, so as to shorten curing time；Comparative example three
Compared with embodiment one, the plasticized modifier in component is changed, and obtained adhesives toughness is poor, and then to viscous
Intensity is connect to impact；Comparative example is fourth is that a kind of existing antibacterial solid agent, adhesive property are significantly fallen with anti-aging property
Adhesives in the present invention afterwards.
Although be described in detail to a specific embodiment of the invention in conjunction with the embodiments, should not be construed as to this
The restriction of the protection scope of patent.In range described by claims, those skilled in the art are without creative work
The various modifications and deformation that can make still belong to the protection scope of this patent.
Claims (10)
1. a kind of historical relic reparation adhesives, which is characterized in that comprise the following components in parts by weight: epoxy resin-base 50~
60 parts, 20~30 parts of curing agent, 1~10 part of plasticized modifier, 0.1~0.5 part of silane coupling agent, 0.5~1 part of antibacterial agent, resist
0.5~1 part of bacterium auxiliary agent, 1~10 part of base powder；The antibacterial agent is to carry silver-colored four needle zinc oxide, and the Antibacterial accessory ingredient is diatom
Soil, chitosan, titanium dioxide, n,N-Dimethylformamide or 2 mercapto benzimidazole, the material of the base powder with it is to be repaired
The material of multiple historical relic is identical.
2. historical relic reparation adhesives according to claim 1, which is characterized in that comprise the following components in parts by weight:
60 parts of epoxy resin-base, 30 parts of curing agent, 6 parts of plasticized modifier, 0.4 part of silane coupling agent, 0.8 part of antibacterial agent, antibacterial helps
0.8 part of agent, 2 parts of base powder.
3. historical relic reparation adhesives according to claim 1 or 2, it is characterised in that: the epoxy resin-base is
E44 epoxy resin.
4. historical relic reparation adhesives according to claim 1 or 2, it is characterised in that: the curing agent is 651 polyamides
Amine and/or 650 polyamide.
5. historical relic reparation adhesives according to claim 1 or 2, it is characterised in that: the plasticized modifier is viscous
The liquid natural rubber that average molecular weight is 4000~20000.
6. historical relic reparation adhesives according to claim 5, which is characterized in that the plasticized modifier passes through following
Method is made: natural rubber is cut into the fritter that partial size is 1~2cm, the toluene or carbon tetrachloride of 2~3 times of amounts is then added, in
It is swollen 2~4h under the conditions of 35~45 DEG C, then potassium permanganate is added into the system after swelling, and the pH of regulation system is 4~6,
Plasticized modifier is obtained after reacting 2~6h；0.5~1:1 of mass ratio of the potassium permanganate and natural rubber that are added.
7. historical relic reparation adhesives according to claim 1 or 2, it is characterised in that: the partial size of the base powder
For 300 mesh.
8. historical relic reparation adhesives according to claim 1 or 2, it is characterised in that: further include 1~10 part of mica
Powder.
9. the method for preparing the adhesives as described in any one of claim 1~6, which comprises the following steps:
(1) epoxy resin-base is put into reaction vessel, and is heated to 100~130 DEG C, then 2~3h of vacuum defoamation, obtained de-
Steep epoxy resin；
(2) silver-colored four needle zinc oxide will be carried to be scattered in acetone, antimicrobial is obtained, then under agitation by antimicrobial
It is added in deaeration epoxy resin, then remaining component in addition to curing agent is added in mixed system, stir evenly to change
Property epoxy resin；
(3) preceding 5~10min is repaired carrying out historical relic, curing agent is added in modified epoxy, mix thoroughly and remove bubble and obtain
Adhesives.
10. preparation method according to claim 9, which is characterized in that the silver-colored four needle zinc oxide process of load used in step (2)
Following steps are made:
S1: the ammonia that the sour nitre zinc solution for being 0.1~0.6mol/L with deionized water configuration concentration, concentration are 0.6~1.5mol/L
Aqueous solution and concentration are the silver nitrate solution of 0.5mol/L, and silver nitrate solution is slowly added dropwise into ammonia spirit, before formation
Liquid solution is driven, the volume ratio of the silver nitrate solution and ammonia spirit that are added is 5:1；
S2: being added dropwise silver nitrate solution into precursor solution under agitation, and m (Ag): m (Zn)=0.01 in control system~
0.05,20h then is reacted under the conditions of 90~120 DEG C, obtains product solution；
S3: filtering product solution is successively washed sediment, alcohol is washed and is dried, and must carry silver-colored four needle zinc oxide antibacterials
Agent.
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