CN102775841B - Composite microemulsion cleaning agent for cleaning aged trimethyl resin - Google Patents
Composite microemulsion cleaning agent for cleaning aged trimethyl resin Download PDFInfo
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- CN102775841B CN102775841B CN201210297957.8A CN201210297957A CN102775841B CN 102775841 B CN102775841 B CN 102775841B CN 201210297957 A CN201210297957 A CN 201210297957A CN 102775841 B CN102775841 B CN 102775841B
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- 239000004530 micro-emulsion Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000011347 resin Substances 0.000 title claims description 38
- 229920005989 resin Polymers 0.000 title claims description 38
- 238000004140 cleaning Methods 0.000 title claims description 36
- 239000012459 cleaning agent Substances 0.000 title abstract 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims abstract description 18
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims abstract description 12
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007788 liquid Substances 0.000 claims description 33
- 238000010422 painting Methods 0.000 claims description 32
- 230000032683 aging Effects 0.000 claims description 12
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- 239000004141 Sodium laurylsulphate Substances 0.000 claims description 9
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 9
- 238000000034 method Methods 0.000 abstract description 12
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- 239000000203 mixture Substances 0.000 abstract description 7
- 231100000053 low toxicity Toxicity 0.000 abstract description 3
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- ODLMAHJVESYWTB-UHFFFAOYSA-N ethylmethylbenzene Natural products CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 abstract 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 abstract 1
- 239000002904 solvent Substances 0.000 description 18
- 239000013543 active substance Substances 0.000 description 11
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- 230000000694 effects Effects 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 7
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- 239000000049 pigment Substances 0.000 description 6
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- 238000005516 engineering process Methods 0.000 description 4
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 description 4
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 description 4
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- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
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- FIMVMYXUGWSJKE-UHFFFAOYSA-N 1,4-xylene Chemical compound CC1=CC=C(C)C=C1.CC1=CC=C(C)C=C1 FIMVMYXUGWSJKE-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a composite microemulsion cleaning agent which is an oil-in-water type composite microemulsion and comprises the following components: 3-4g/100ml of lauryl sodium sulfate, 6-8% of n-amyl alcohol in volume ratio, 1-7% of propylene carbonate in volume ratio and 1.5-11% of oil phase in volume ratio, wherein the oil phase comprises ethyl acetate or methylbenzene, dimethylbenzene, ethyl acetate and butyl ester in volume ratio of 39:11:11:39, or a mixture of n-butyl acetate, ethyl acetate and methylbenzene in volume ratio of 55:40:5. The invention also discloses a method for preparating the composite microemulsion cleaning agent. The composite microemulsion cleaning agent provided by the invention has the advantages of stable system, small collective, high trend, large interface, larger oil-water interface radius of curvature, safety, low toxicity, convenience in transportation and use and the like.
Description
Technical field
The present invention relates to a kind of composite micro-emulsion liquid clean-out system, relate to particularly a kind of composite micro-emulsion liquid clean-out system cleaning for wall painting surface covering aged resin.
Background technology
An important process in protection world cultural heritage is the protection to mural painting in tombe chamber in ancient times.Known technology is to adopt front three resin on wall painting pigment layer surface, to reinforce and closure processing at present.Front three resin is formed by methyl methacrylate, butyl methacrylate and methacrylic acid copolymerization, belongs to the polymer resin of acrylic acid or the like.After going through for many years, because resin is aging, produce the phenomenons such as dazzle, variable color, be full of cracks, cause mural painting picture frame layer color burn, crisp alkali, warp, the disease phenomenon such as cracking.In addition, in the 70-90 age in last century, front three resin was once widely used in the protection of other type historical relic, as bronze work, ancient painted pottery, bamboo wood lacquerware, rock cave statue etc.
Because ancient wall has porosity large (holding calcareously porosity is 37%), the features such as wetting ability and ventilation property.Sprayed after acrylic resin, can strengthen the hydrophobicity of wall painting surface on the one hand, reduce capillary water absorption and water vapor permeation effect, along with environmental change causes dissolving and the crystallization repeated action of soluble salt, the mechanical stress of generation can make the picture frame layer of mural painting come off fast between 5-30.On the other hand, the continuous aging sex change of organic resin meeting, produces the feature that variable color and solvability reduce, and even makes some materials lose solubility.Closure material aging, has changed chemistry and the optical property of wall painting pigment layer, can make wall painting surface smudgy, and this phenomenon just once appearred in the Ajanta mural painting of India.
At present, for the cleaning of aged resin, generally adopt conventional clean method.Rule is that wish is removed a certain resin, just adopts and dissolves this resin solvent used.For example front three resin is dissolved in acetone solvent, just adopts acetone to wipe unnecessary front three resin.This is to follow in historical relic's protection, and protecting materials should have the principle of " reversibility ".But there is many drawbacks in traditional method:
1) neat solvent dissolves the second permeation that can cause resin.Because mural painting is being completed in battle calcareously, lime material itself is loose porous, and dissolved resin can enter infiltration along with solvent continues inside layer depth again.Cause the hydrophobicity of mural painting to strengthen, ventilation property reduces, and causes the new diseases such as coat of colo(u)r warps, comes off.
2) neat solvent cleans and is difficult to control.The internal penetration of neat solvent and the speed of surface diffusion are fast, actually use and the degree of cleaning of the cleaning objects such as mural painting is difficult to control, and may cause cultural artifact surface damage because excessively cleaning.
3) resin does not have reversibility after aging.Because resin is aging crosslinked, chemical composition and molecular weight change, and therefore original solvability changes.Originally optimum solvent can not dissolve aging same resin.
4) neat solvent toxicity and inflammable and explosive property: field experiment is many in the coffin chamber environment of relatively sealing, lacks and ventilates and circulation of air.The easy volatile of organic solvent and toxicity are easy to operator's health to impact, and ground, ruins environment is damaged.In addition in transportation and use procedure, also there is potential safety hazard in solvent.
Summary of the invention
The object of the present invention is to provide a kind of for cleaning the composite micro-emulsion liquid clean-out system of the aging front three resin of mural painting, to improve the defect existing in known technology.
For achieving the above object, composite micro-emulsion liquid clean-out system provided by the invention, is oil-in-water-type (oil-in-water) composite micro-emulsion liquid, and it consists of:
Sodium lauryl sulphate 3-4g/100ml;
Pentyl alcohol volume ratio 6-8%;
Oil phase volume ratio 1.5-11%;
Propylene carbonate volume ratio 1-7%;
Surplus is water;
Oil phase is wherein:
Ethyl acetate; Or
(preferred volume ratio is 39: 11: 11 to toluene: dimethylbenzene: ethyl acetate: positive butyl ester is 3.5-4 by volume: 1: 1: 3.5-4: 39) mix; Or
N-butyl acetate: ethyl acetate: toluene is by volume for 4.5-5.5: 3-5: 0.3-1.5 (preferred volume ratio is 55: 40: 5) mixes.
The method of the above-mentioned composite micro-emulsion liquid of preparation provided by the invention clean-out system, its key step comprises:
1) sodium lauryl sulphate is dissolved in the water;
2) add Pentyl alcohol to be stirred to solution transparent;
3) add propylene carbonate and oil phase and stir, being transparent or micro-turbid stable emulsion state to solution.
In described preparation method, step 1 be placed in 40 ℃ of waters bath with thermostatic control be heated to sodium lauryl sulphate and dissolve completely after and be cooled to room temperature.
In described preparation method, step 2 is dropwise to add cosurfactant also under agitation condition. be stirred to solution transparent.
In described preparation method, step 3 is under agitation condition, slowly dropwise to add propylene carbonate and oil phase and be stirred to solution to be transparent or micro-turbid stable emulsion state.
Composite micro-emulsion liquid clean-out system of the present invention is comprised of water, oil, tensio-active agent and cosurfactant, under suitable proportion spontaneous formation transparent or translucent, low viscosity and isotropic thermodynamic stable system.Have stable system, little aggregate, high dynamically, large interface, water-oil interface radius-of-curvature large (size that is micro emulsion drop is less), safety and low toxicity, be convenient to the advantages such as transportation use.
Accompanying drawing explanation
Fig. 1 cleans check pigment dropping situations with composite micro-emulsion liquid clean-out system of the present invention.
Fig. 2 shown clean before (a) and utilize composite micro-emulsion liquid clean-out system of the present invention to clean the Photomicrograph (50 times of amplifications) of (b) afterwards.
Fig. 3 has shown that neat solvent and composite micro-emulsion liquid clean-out system of the present invention clean front and back contact angle measuring result broken line graph.
Fig. 4 is scanning electron microscope-energy spectrometer and the sign of fourier transformation-attenuated total reflectance attenuated total refraction spectroscopic analysis to microemulsion cleaning performance; Wherein, (a) being the SEM photo before cleaning, is (b) the SEM photo after cleaning, and is (c) that after cleaning, red area (iron oxide red pigment) surface-element distributes, and is (d) that after cleaning, red area EDX can spectrogram.
Fig. 5 is that the spectroscopic analysis of fourier transformation-attenuated total reflectance attenuated total refraction characterizes microemulsion cleaning performance; Wherein, (a) being the ATR-FTIR photo before resin-like piece cleans, is (b) the ATR-FTIR photo after cleaning.
Fig. 6 is effect comparison before and after test in place is cleaned; Wherein, be (a) before the beautiful three Room tomb mural paintings of high sentence clean, being (b), after the beautiful three Room tomb mural paintings of high sentence clean, is (c) before loyal filial piety princess tomb cleans, and is (d) after loyal filial piety princess tomb cleans.
Fig. 7 is the size distribution schematic diagram of microemulsion B in composite micro-emulsion liquid clean-out system of the present invention.
Embodiment
The composite micro-emulsion liquid clean-out system of the present invention preparation, is comprised of water, oil, tensio-active agent and cosurfactant, under suitable proportion spontaneous formation transparent or translucent, low viscosity and isotropic thermodynamic stable system.
This microemulsion is for removing the closure resin that wall painting surface is aging.In order to reduce the volatility of oil phase, emulsion is mixed with to comparatively single mutually O/W type microemulsion as far as possible.Yet not the water of any amount, oil, tensio-active agent and cosurfactant are mixed and just can make " single " microemulsion.
1) tensio-active agent: tensio-active agent is mainly distributed in oil/water interface, oil/water interfacial tension is reduced greatly, and under the existence of cosurfactant, produce mixing and absorption, form hybrid films, interfacial tension is further declined, and the static producing by self and steric hindrance repelling effect, interfacial viscosity become the stability that large and self-bodying effect has strengthened microemulsion.Clean the aging acrylic resin of mural painting, the present invention selects sodium lauryl sulphate (SDS) as tensio-active agent, because the solubleness in water is larger, is easy to clean, and is difficult for residual wall painting surface.
2) cosurfactant: general tensio-active agent is when forming micella, osmosis due to micro emulsion drop inside, be easy to form liquid crystal, add a small amount of cosurfactant (as short-chain alcohols) can reduce the osmotic pressure of drop inside, strengthened the stability of micelle, improve the mobility of internal layer, and can increase or reduce the drop size of microemulsion, and then can greatly improve the cleaning efficiency of oil phase.The present invention selects Pentyl alcohol (1-Pe-OH) as cosurfactant.
3) oil phase: oil phase plays vital effect in microemulsion cleans, and is the nucleus of clean-out system.The selection of oil phase is mainly to consider toxicity, the proportioning of oil phase to the dissolving power of resin, volatility and oil phase.The present invention has selected the optimum solvent of the common low toxicity of several acrylic resins, then is equipped with suitable ratio according to the calculating of mixed solvent solubility parameter, forms the optimum solvent of the best of resin.Ethyl acetate (EA), propylene carbonate (PC), p-Xylol (p-xylene), toluene, n-butyl acetate (n-BA), isobutyl acetate (i-BA) have been selected.
Utilize turbidimetric titration, the solubility parameter δ value of aged resin in aging front three resin and mural painting tomb is simulated by testing laboratory, is respectively 22.12 and 22.63 (J/cm
3)
1/2.With this, configured the composite micro-emulsion liquid clean-out system of the present invention's preparation.
Effect according to medicine in microemulsion, adopts classifying drugs for several as follows the present invention:
(1) tensio-active agent: sodium lauryl sulphate (SDS), Chemical Reagent Co., Ltd., Sinopharm Group's (Shanghai examination);
(2) cosurfactant: Pentyl alcohol (1-Pe-OH), analytical pure, Chemical Reagent Co., Ltd., Sinopharm Group's (Shanghai examination).
(3) oil phase: Chemical Reagent Co., Ltd., Sinopharm Group's (Shanghai examination) produces:
Ethyl acetate (Ethyl Acetate, EA, δ=18.0 (J/cm
3)
1/2analytical pure;
Propylene carbonate (Propylene Carbonate, PC, δ=27.2 (J/cm
3)
1/2analytical pure;
Dimethylbenzene (p-xylene, δ=17.9 (J/cm
3)
1/2analytical pure;
Beijing Chemical Plant produces:
Toluene (Methylbenzene, δ=18.2 (J/cm
3)
1/2, chemical pure;
N-butyl acetate (n-Butyl Acetate, n-BA, δ=17.2 (J/cm
3)
1/2, analytical pure;
Isobutyl acetate (i-Butyl Acetate, i-BA, δ=17.4 (J/cm
3)
1/2, analytical pure.
Compound method of the present invention is:
1) weigh a certain amount of water and tensio-active agent and mix, be placed in 40 ℃ of waters bath with thermostatic control and heat 15 minutes.
2) after tensio-active agent dissolves completely, be cooled to room temperature, under agitation condition, dropwise slowly add cosurfactant.
3) be stirred to solution transparent, in the ratio according to certain, slowly drip the oil phase choosing and stir energetically, be transparent or micro-turbid stable emulsion state to solution.
The composite micro-emulsion liquid clean-out system of preparation, is oil-in-water-type (oil-in-water) composite micro-emulsion liquid according to the method described above, and it consists of:
Soil sodium dialkyl sulfate 3.5g/100ml;
Pentyl alcohol volume ratio 7%;
Oil phase gets respectively 1.5,6 and 11% 3 kind by volume;
Propylene carbonate volume ratio gets respectively 1,4 and 7% 3 kind;
Surplus is water.
In the present embodiment, adopted following three kinds of oil phases, that is to say, in tensio-active agent, cosurfactant and the propylene carbonate component of identical proportioning, respectively added different oil phases respectively and be mixed with the composite micro-emulsion liquid clean-out system of three kinds of oil phases.In effect explanation described later, all refer to the effect that these composite micro-emulsion liquid clean-out systems have jointly.
1) ethyl acetate;
2) toluene: dimethylbenzene: ethyl acetate: positive butyl ester 39: 11: 11 by volume: 39 mixture;
3) n-butyl acetate: ethyl acetate: toluene is the mixture of 55: 40: 5 by volume.
Utilize dynamic light scattering (DLS) to measure (seeing Fig. 7) to the dispersion particle particle diameter of microemulsion, prove that this emulsion particle diameter is about 2~5nm, and in formula, the content of water reaches more than 73%, really can be described as oil-in-water microemulsion.
In order to assess cleaning performance, carried out the scene of laboratory simulation cleaning and mural painting in tombe chamber and cleaned.After cleaning, cleaning performance characterizes in the following way:
(1) visual inspection, takes pictures;
(2) Stereo microscope shows cleaning microcosmic effect;
(3) contact angle measurement & characterization cleans front and back hydrophobicity variation;
(4) scanning electron microscope-energy spectrometer (SEM-EDX) characterizes and cleans front and back microscopic appearance variation and clean the residual of rear surface promoting agent;
(5) attenuated total reflectance attenuated total refraction infrared spectra (ATR-FTIR) detects and cleans the residual of front and rear surfaces resin.
Composite micro-emulsion liquid clean-out system of the present invention can adopt the method covering to carry out cultural artifact surface cleaning.Conventionally use non-woven fabrics to be folded into the area needing, dip after clean-out system, stick the surface to historical relic to be cleaned, with preservative film, wrap up nonwoven surface, after-applied certain pressure.Every half an hour, check cleaning performance, and supplement a certain amount of clean-out system.Depend on the circumstances during this time, if nonwoven surface has been dissolved abundant resin, centre needs to change non-woven fabrics 1-2 time, reaches better cleaning performance.After 2-3 hour, can dissolve the resin in region completely.Finally, by deionized water clean surface spot, prevent the residual of clean-out system, complete cleaning process.
Below in conjunction with accompanying drawing, composite micro-emulsion liquid clean-out system effect of the present invention is further described.
Taking Pictures recording (incorporated by reference to Fig. 1), Fig. 1 shows the resin that adopts composite micro-emulsion liquid clean-out system of the present invention to clean mural painting simulation sample piece surface.In cleaning process, with paper handkerchief wiping sample piece, the lower any granules of pigments of band, does not illustrate that composite micro-emulsion liquid clean-out system does not have disturbance and destruction to wall painting pigment layer.
Stereo microscope is observed (incorporated by reference to Fig. 2), Fig. 2 be before cleaning (a) and clean after the Photomicrograph of 50 times of (b) amplifications, show that cleaning rear sample piece surface resin dazzle disappears, the groove between lime and granules of pigments also cleans thoroughly, and texture structure is clear to be manifested.
Contact angle is measured (incorporated by reference to Fig. 3), and Fig. 3 is contact angle measuring result broken line graph before and after neat solvent and composite micro-emulsion liquid clean-out system of the present invention clean.Contact angle measuring result by Fig. 3 shows, adopting neat solvent to remove aging front three resin, there is not considerable change in contact angle, and this shows solvent dissolving resin again, resin, along with in depth battle layer of neat solvent infiltration, has strengthened again water-repellancy and the gas tightness of simulation sample piece.Although from appearance, neat solvent can be eliminated dazzle, does not improve significantly the wettability of wall painting surface, still may become the reason that causes the potential disease of mural painting.After utilizing composite micro-emulsion liquid clean-out system of the present invention to remove, the contact angle amount of decrease of sample piece is larger, reflects that composite micro-emulsion liquid clean-out system has extraordinary effect to controlling the second permeation of solvent.
Referring to Fig. 4, is scanning electron microscope-energy spectrometer and the sign of fourier transformation-attenuated total reflectance attenuated total refraction spectroscopic analysis to composite micro-emulsion liquid clean-out system cleaning performance.Fig. 4 a is the stereoscan photograph that does not clean the top three's resin.By Hitachi S-3600N scanning electronic microscope and energy spectrometer analysis, amplifying under 600 times of observations, composite micro-emulsion liquid clean-out system of the present invention can very effectively dissolve and remove and hold the aged resin (Fig. 4 b) of filling between hole.Energy spectrometer analysis result shows that (Fig. 4 c-d) do not detect the Na element in surfactant SDS, explanation is after composite micro-emulsion liquid clean-out system of the present invention is removed resin, use again washed with de-ionized water, wall painting surface does not have the residual of detectable clean-out system, can not exert an influence to mural painting.
Refer to Fig. 5, Fig. 5 is that the spectroscopic analysis of fourier transformation-attenuated total reflectance attenuated total refraction characterizes composite micro-emulsion liquid clean-out system cleaning performance.ATR-FTIR analytical technology is a kind of important method that characterizes substance surface property.Can measure the infrared spectra of specimen surface and not be subject to the interference of matrix, what reflect is the chemical information of upper layer (being less than 5 μ m), comprise the information such as surface chemical composition, surface chemical reaction and surface ag(e)ing, and can be used for identifying the situation of cleaning rear residuals.Fig. 5 a and 5b are that resin-like piece cleans forward and backward ATR-FTIR photo.Adopt Nicolet 670spectroscopy to be equipped with the ATR-FTIR spectrum that smart OMNI-sampler ATR annex has been tested sample piece cleaning front and rear surfaces.By infrared spectra, contrast, show that front three resin is through the cleaning of composite micro-emulsion liquid clean-out system of the present invention, removing thoroughly, has no residual.If acrylic resin is at 1720cm
-1stretching vibration and the 3000cm of C=O key
-1the infrared signature peak that place's c h bond stretching vibration produces all disappears (as shown in Figure 5 b).
Field test results (incorporated by reference to Fig. 6), the early stage mural painting retaining in high sentence Room tomb mural painting in beautiful periods three and the loyal filial piety princess of Bohai Sea state tomb of take is example, and Fig. 6 a is before three Room tomb mural paintings clean, and Fig. 6 b is after three Room tomb mural paintings clean.Fig. 6 c is before loyal filial piety princess tomb cleans, and Fig. 6 d is that after loyal filial piety princess tomb cleans, middle border circular areas is cleaning area.The variable color of mural painting, dazzle, the disease such as chap, warp all improve.Further illustrate the effect that oil-in-water-type of the present invention (oil-in-water) composite micro-emulsion liquid is removed weather stain resin and do not injured historical relic body, can obtain comparatively desirable cleaning performance.
Claims (1)
1. for cleaning a composite micro-emulsion liquid clean-out system for the aging front three resin of mural painting, be oil-in-water-type composite micro-emulsion liquid, it consists of:
Sodium lauryl sulphate 3-4g/100ml;
Pentyl alcohol volume ratio 6-8%;
Oil phase volume ratio 1.5-11%;
Propylene carbonate volume ratio 1-7%;
Surplus is water;
Oil phase is wherein:
N-butyl acetate: ethyl acetate: toluene is 55:40:5 by volume.
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