CN100372898C - Colorful protecting agent for efflorescent and faded colored drawing cultural relic - Google Patents
Colorful protecting agent for efflorescent and faded colored drawing cultural relic Download PDFInfo
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- CN100372898C CN100372898C CNB2006101044233A CN200610104423A CN100372898C CN 100372898 C CN100372898 C CN 100372898C CN B2006101044233 A CNB2006101044233 A CN B2006101044233A CN 200610104423 A CN200610104423 A CN 200610104423A CN 100372898 C CN100372898 C CN 100372898C
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Abstract
The invention discloses a color protective of weathered fading coloured drawing on the ancient cultural relics, which comprises the following parts: 0.30-0.72% di(1,2,2,6,6-pentamethylphenol-4-piperidine base)-sebacate, 0.14-0.28% phosphorous acid tri(nonyl phenol) ester, 0.06-0.15% phosphorous acid benzene diisophthalate, 0.42-0.90% vinylidene fluoride-trifluorochloroethylene copolymer, 0.30-0.80% methyl methacrylate-styrene copolymer, 42. 00-46. 00% acetone, 10.00-12. 00% acetic ester, 10.00-12. 00% butyl acetate, 10.00-12. 00% amyl acetate, 10.00-10.00% methyl-ethyl ketone and 10.00-12. 00% cellosolve.
Description
Technical field
The invention belongs to the material technology field, be specifically related to manifest the weathering paint-coated colour developing protective material of ancient records and relics that fades.
Background technology
Serious weathering is faded behind ancient wall, historical relic colored drawing, architectural painting process centuries even the more than one thousand years, disappearance phenomenon ubiquity totally, to reduce on bright clear all kinds of colored drawing potteries, color figurines, mural painting, wooden casket, stone carving, inscription on the memorial tablet within a tomb, the architectural painting generation is arranged all from spring and autumn, it is former valuable that national treasure level, national grade historical relic are lost, and brings puzzlement for historical archaeology research.Fade because of serious weathering as unique discovery, precious Qin Dynasty imperial palace mural painting, team of four horses, the most of picture in car territory are on the verge of to disappear.Colored drawing Terracotta warrior army of large-scale Western Han Dynastry battle array that China of Xianyang museum collection, exhibition finds first, the seventies is beautiful in colour, life-like when being unearthed, nowadays most color dimnesses, an ash grey brain.The 60 to 70's of last century Qian Mausoleum of Tang Dynasty Yongtai princess, Zhanghuai prince, admirable virtue crown prince's tomb are excavated be unearthed a large amount of exquisite mural paintings and colored drawing pottery, after several years, smudgy, be beyond recognition, finish the archaeology report for these three great archaeology projects and bring serious puzzlement, fail so far to finish.Temple, the Tang Qing mountain Buddhism mural painting of Lintong District museum collection, color and figure still exist when being unearthed, and after the several years, are beyond recognition because of fading.Several width of cloth mural paintings in six palaces, Palace Museum west become grey fully, and no artistry can be sayed.The Han dynasty ancient painted pottery that is unearthed is excavated by Xuzhou City, Jiangsu Province archaeological team, and a few days just seriously fades, and can't copy its pattern.The at present unearthed emperor's tomb-Tombs of Emperors of the Southern Tang Dynasty Two Mausoleums of Southern Tang with a highest standard in China the south of the lower reaches of the Yangtze River is plotted in the exquisite colored drawing completely dissolve on the stone matter building slab.Big area Song dynasty colored drawing on the tower of Huqiu, name tower Suzhou, the south of the River has become grey.The architectural painting great majority in the loyal mansion of a prince, Taiping Heavenly Kingdom Suzhou in period are smudgy.Fade because of the historical relic weathering and to cause the example that to engage in archaeological studies with historical research too numerous to enumerate.Famous archaeologist, Museum of Life-size Terra-cotta Horse and Armored Warriors Excavated from Sites Near the Tomb of Qin Shi Huang fame curator Mr. Yuan Zhongyi point out: " the historical relic image colour developing protection original appearance that weathering is faded is a problem the most difficult of long-term puzzlement archaeology, departments in charge of cultural and historical relics.People see that helplessly many ancient tombs go out soil colored drawing image, and weathering is faded gradually, and is smudgy, disappear totally, and feel pained.It is long-awaited eldest child's difficult problem that the ancient wall that current archaeology and departments in charge of cultural and historical relics fade to weathering, historical relic colored drawing, architectural painting manifest primary colors.
Summary of the invention
Technical problem to be solved by this invention is the ancient wall, historical relic colored drawing, the architectural painting that fade for weathering, provides a kind of and can make it manifest original appearance, and keep stablizing, having reversibility, handlability, preparation method's weathering simple, easy handling the paint-coated colour developing protective material of ancient records and relics that fades.
It is to make composition with following weight percentages to solve the problems of the technologies described above the technical scheme that adopted:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.30～0.75%
Tricresyl phosphite (nonyl phenyl) ester 0.06～0.15%
Phosphorous acid benzene di-isooctyl 0.06～0.15%
Vinylidene-chlorotrifluoroethylene 0.51～1.00%
Copolymer of methyl methacrylatestyrene 0.27～0.95%
Acetone 40.00～50.00%
Ethyl acetate 8.00～12.00%
Butylacetate 8.00～12.00%
Pentyl acetate 8.00～12.00%
Methylethylketone 9.00～12.00%
Ethylene glycol ethyl ether 8.00～12.00%
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
The raw material for preparing preferred weight per distribution ratio of the present invention is:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.30～0.72%6
Tricresyl phosphite (nonyl phenyl) ester 0.08～0.12%
Phosphorous acid benzene di-isooctyl 0.08～0.12%
Vinylidene-chlorotrifluoroethylene 0.60～0.90%6
Copolymer of methyl methacrylatestyrene 0.30～0.80%6
Acetone 42.00～46.00%
Ethyl acetate 10.00～12.00%
Butylacetate 10.00～12.00%
Pentyl acetate 10.00～12.00%
Methylethylketone 10.00～12.00%
Ethylene glycol ethyl ether 10.00～12.00%
The raw material for preparing optimum weight per distribution ratio of the present invention is:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.50%
Tricresyl phosphite (nonyl phenyl) ester 0.10%
Phosphorous acid benzene di-isooctyl 0.10%
Vinylidene-chlorotrifluoroethylene 0.75%
Copolymer of methyl methacrylatestyrene 0.55%
Acetone 44.00%
Ethyl acetate 11.00%
Butylacetate 1.00%
Pentyl acetate 11.00%
Methylethylketone 10.00%
Ethylene glycol ethyl ether 11.00%.
Each component in the said ratio is sell goods on the market, wherein two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebate produced by auxiliary reagent factory, Beijing, tricresyl phosphite (nonyl phenyl) ester is produced by U.S. Weston company, phosphorous acid benzene di-isooctyl is that Japan three smooth companies produce, and vinylidene-chlorotrifluoroethylene is produced by Sichuan morning twilight chemical research institute, and copolymer of methyl methacrylatestyrene is produced by Shanghai Pen Making Chemical Factory.
Preparation method of the present invention is as follows:
1, preparation mixed solvent
Acetone in the proportioning of the present invention, ethyl acetate, butylacetate, pentyl acetate, methylethylketone, ethylene glycol ethyl ether are hybridly prepared into mixed solvent.
2, preparation vinylidene-chlorotrifluoroethylene solution
According to a conventional method with vinylidene-chlorotrifluoroethylene powder dissolution in mixed solvent, be heated to 80～85 ℃ with electric mantle, stir, refluxed 90 minutes with stirrer, make concentration and be vinylidene-chlorotrifluoroethylene solution of 2%, dilute with mixed solvent by proportioning during use.
3, preparation copolymer of methyl methacrylatestyrene solution
Place three-necked round bottom flask to add mixed solvent copolymer of methyl methacrylatestyrene according to a conventional method, be heated to 80～85 ℃, refluxed 60 minutes, be mixed with concentration and be 2% copolymer of methyl methacrylatestyrene solution.
4, preparation the present invention protective material that develops the color
With the vinylidene-chlorotrifluoroethylene solution of above-mentioned steps 2 preparations, the copolymer of methyl methacrylatestyrene solution and two (1 of step 3 preparation; 2; 2; 6; 6-pentamethyl--4-piperidyl)-sebate, tricresyl phosphite (nonyl phenyl) ester, phosphorous acid benzene di-isooctyl mix preparation cost invention colour developing protective material with remaining mixed solvent.
As follows with the present invention's protective material that develops the color to the fade operating procedure step of historical relic colored drawing colour developing protection of weathering:
Remove totally to the fade dirty dirt, soil rust etc. on historical relic colored drawing surface of weathering, dip in the protective material that develops the color, apply gently on the weathering historical relic colored drawing surface of fading with tweezers gripping absorbent cotton.
Adopt the present invention can make the serious weathering ancient wall that fades; the historical relic colored drawing; architectural painting manifests original appearance; preparation method of the present invention is simple; easy handling; it is stable that the original appearance that shows keeps; has reversibility; the property handled again; to historical relic " minimum interference "; adopt the present invention to the weathering ancient wall that fades; the historical relic colored drawing; after the architectural painting colour developing protection; adopt the spectral radiant emittance meter through Xian Inst. of Optics and Precision Mechanics, Chinese Academy of Sciences and Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources; scanning electronic microscope; photoelectron spectrograph; x-ray diffractometer has carried out before the colour developing protection and the protection back comparison and detection that develops the color, and detected result shows spectral signature and the material composition that does not change original pigment after colour developing is protected.Approval is listd through State Cultural Relics Bureau; the contriver adopts the present invention's serious weathering such as eaves colour painting in palace, Qin ruins mural painting, Eastern Han Dynasty's colored drawing Terracotta warrior, temple, Tang Qing mountain mural painting, Tomb of Zhao Family Wei highest-ranking imperial concubine tomb mural painting, Qian Mausoleum of Tang Dynasty Yongtai princess, Zhanghuai prince tomb mural painting and colored drawing pottery figurine, Tang's Famen Temple colored drawing stone carving, permanently happy door gate tower, bright Xi'an colour developing of fading, disappears on totally ancient wall, historical relic colored drawing, the architectural painting to protect clear its original appearance that shown.The present invention can use on ancient wall that weathering is faded, historical relic colored drawing, architectural painting.
Description of drawings
Fig. 1 develops the color with the present invention to protect the curve of spectrum of scarlet after 10 years on Eastern Han Dynasty's ancient painted pottery.
Fig. 2 does not develop the color with the present invention to protect the wine-colored curve of spectrum on Eastern Han Dynasty's ancient painted pottery.
Fig. 3 develops the color with the present invention to protect the curve of spectrum of deep yellow after 10 years.
Fig. 4 does not develop the color with the present invention to protect the curve of spectrum of deep yellow.
Fig. 5 develops the color with the present invention to protect the curve of spectrum of incomplete colored drawing pottery scarlet after 10 years.
Fig. 6 does not develop the color with the present invention to protect the wine-colored curve of spectrum of incomplete colored drawing pottery.
Fig. 7 develops the color with the present invention to protect the photoelectron spectrum figure of colored drawing pottery in spring and autumn after 10 years.
Fig. 8 does not develop the color with the present invention to protect the photoelectron spectrum figure of colored drawing pottery in spring and autumn.
Fig. 9 develops the color with the present invention to protect the photoelectron spectrum figure of grey a word used in person's names mausoleum ancient architecture colour painting relic after 5 years.
Figure 10 does not develop the color with the present invention to protect the photoelectron spectrum figure of grey a word used in person's names mausoleum ancient architecture colour painting relic.
Figure 11 develops the color with the present invention to protect the energy spectrogram of Qian Mausoleum of Tang Dynasty Tomb of Princess Yongtai colored drawing after 6 years.
Figure 12 does not develop the color with the present invention to protect the paint-coated energy of Qian Mausoleum of Tang Dynasty Tomb of Princess Yongtai spectrogram.
Figure 13 develops the color with the present invention to protect the X diffraction oscillogram of colored drawing pottery in spring and autumn after 10 years.
Figure 14 does not develop the color with the present invention to protect the X diffraction oscillogram of colored drawing pottery in spring and autumn.
Figure 15 develops the color with the present invention to protect the X diffraction oscillogram of eaves colour painting relic after 8 years in the permanently happy door in Xi'an.
Figure 16 does not develop the color with the present invention to protect the X diffraction oscillogram of eaves colour painting relic in the permanently happy door in Xi'an.
Figure 17 develops the color with the present invention to protect the X diffraction oscillogram of grey a word used in person's names mausoleum ancient architecture colour painting relic after 5 years.
Figure 18 does not develop the color with the present invention to protect the X diffraction oscillogram of grey a word used in person's names mausoleum ancient architecture colour painting relic.
Embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail, but the invention is not restricted to these embodiment.
Product 100kg of the present invention is an example with production, and used raw material and weight proportion thereof are:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebate 0.50kg
Tricresyl phosphite (nonyl phenyl) ester 0.10kg
Phosphorous acid benzene di-isooctyl 0.10kg
Vinylidene-chlorotrifluoroethylene 0.75kg
Copolymer of methyl methacrylatestyrene 0.55kg
Acetone 44.00kg
Ethyl acetate 11.00kg
Butylacetate 11.00kg
Pentyl acetate 11.00kg
Methylethylketone 10.00kg
Ethylene glycol ethyl ether 11.00kg.
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
Its compound method is as follows:
The present invention of present embodiment proportioning preparation protective material that develops the color is applicable to that pig blood, tung oil, lime, incense ashes, hemp cut etc. recover for the paint-coated colour developing of building of ground battle.
Preparation method of the present invention is as follows:
1, preparation mixed solvent
Acetone in the proportioning of the present invention, ethyl acetate, butylacetate, pentyl acetate, methylethylketone, ethylene glycol ethyl ether are hybridly prepared into mixed solvent.
2, preparation vinylidene-chlorotrifluoroethylene solution
According to a conventional method with vinylidene-chlorotrifluoroethylene powder dissolution in mixed solvent, be heated to 80～85 ℃ with electric mantle, stir, refluxed 90 minutes with stirrer, make concentration and be vinylidene-chlorotrifluoroethylene solution of 2%, dilute with mixed solvent by proportioning during use.
3, preparation copolymer of methyl methacrylatestyrene solution
Place three-necked round bottom flask to add mixed solvent copolymer of methyl methacrylatestyrene according to a conventional method, be heated to 80～85 ℃, refluxed 60 minutes, be mixed with concentration and be 2% copolymer of methyl methacrylatestyrene solution.
4, preparation the present invention protective material that develops the color
With the vinylidene-chlorotrifluoroethylene solution of above-mentioned steps 2 preparations, the copolymer of methyl methacrylatestyrene solution and two (1 of step 3 preparation; 2; 2; 6; 6-pentamethyl--4-piperidyl)-sebate, tricresyl phosphite (nonyl phenyl) ester, phosphorous acid benzene di-isooctyl mix preparation cost invention colour developing protective material with remaining mixed solvent.
Product 100kg of the present invention is an example with production, and used raw material and weight proportion thereof are:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebate 0.30kg
Tricresyl phosphite (nonyl phenyl) ester 0.06kg
Phosphorous acid benzene di-isooctyl 0.06kg
Vinylidene-chlorotrifluoroethylene 0.51kg
Copolymer of methyl methacrylatestyrene 0.27kg
Acetone 50.00kg
Ethyl acetate 8.80kg
Butylacetate 8.00kg
Pentyl acetate 8.00kg
Methylethylketone 12.00kg
Ethylene glycol ethyl ether 12.00kg.
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
Its preparation method is identical with embodiment 1.
The present invention of present embodiment proportioning preparation protective material that develops the color is applicable to colored drawing stone carving, wooden casket, woodcarving colored drawing and directly is plotted in the paint-coated colour developing protection of building on the timber compoment.
Product 100kg of the present invention is an example with production, and used raw material and weight proportion thereof are:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebate 0.75kg
Tricresyl phosphite (nonyl phenyl) ester 0.15kg
Phosphorous acid benzene di-isooctyl 0.15kg
Vinylidene-chlorotrifluoroethylene 1.00kg
Copolymer of methyl methacrylatestyrene 0.95kg
Acetone 40.00kg
Ethyl acetate 12.00kg
Butylacetate 12.00kg
Pentyl acetate 12.00kg
Methylethylketone 9.00kg
Ethylene glycol ethyl ether 12.00kg.
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
Its preparation method is identical with embodiment 1.
The present invention of present embodiment proportioning preparation protective material that develops the color, mural painting, pottery figurine, the brick quality of be applicable to the colored drawing pottery, hold with soil and lime held the colour developing of mural painting and brick matter inscription on the memorial tablet within a tomb and protected with serving as.
Product 100kg of the present invention is an example with production, and used raw material and weight proportion thereof are:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebate 0.75kg
Tricresyl phosphite (nonyl phenyl) ester 0.15kg
Phosphorous acid benzene di-isooctyl 0.15kg
Vinylidene-chlorotrifluoroethylene 1.00kg
Copolymer of methyl methacrylatestyrene 0.95kg
Acetone 48.00kg
Ethyl acetate 8.00kg
Butylacetate 12.00kg
Pentyl acetate 12.00kg
Methylethylketone 9.00kg
Ethylene glycol ethyl ether 8.00kg.
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
Its preparation method is identical with embodiment 1.
The present invention of present embodiment proportioning preparation protective material that develops the color, mural painting, pottery figurine, the brick quality of be applicable to the colored drawing pottery, hold with soil and lime held the colour developing of mural painting and brick matter inscription on the memorial tablet within a tomb and protected with serving as.
In order to determine best proportioning of the present invention and practicality of the present invention, the contriver has carried out a large amount of research trial (name is called ancient wall, historical relic colored drawing, the architectural painting that weathering fades and manifests strengthening agent during test), and various test situation are as follows:
1, adopts the present invention's protection historical relic original color changing conditions in time in natural preservation process that develops the color
Portable minute optical density(OD) instrument of testing tool: SP62 is by produced in USA.
(1) analog sample
1996; make analog sample with mass colour, ultramarine, Zhu's fat, gamboge, bright red, ochre, malachite green, azurite, 9 kinds of pigment of cinnabar and size mixture; with UV-light promote the oxidation, efflorescence it is faded; employing the present invention develops the color after the protection; producing the round-the-clock ageing device of 1200CPS with Germany is that 40 ℃, relative humidity are in 75% the environment aging 72 hours in temperature; make it stable, measure 5 same color development protection and the aberration at colour developing protection position with portable minute optical density(OD) instrument of SP62 in June, 1996～2006 year June.Test result sees Table 1.
Table 1 is tested the aberration result with the present invention to analog sample colour developing protection back
By table 1 as seen, in 10 years, carry out the aberration of 5 test simulation samples, the aberration kept stable of mass colour, ultramarine, Zhu's fat, gamboge, bright red, ochre, malachite green, azurite, 9 kinds of pigment of cinnabar.
(2) ancient wall
The protection that develops the color of mural painting, temple, Tang Qing mountain brick matter mural painting, Tang Zhaoling Wei highest-ranking imperial concubine tomb mural painting is held in the Qin Xianyang palace of adopting the present invention that weathering is faded calcareously, uses portable minute optical density(OD) instrument of SP62 to test aberration 5 times to colour developing protection position and color of the same race with near the protection of the not colour developing unicursal position.
Test result sees Table 2, table 3, table 4.
Table 2 is tested the aberration result with the present invention to the colour developing of the mass colour on the mural painting relic of Qin Xianyang palace protection
| Time | In April, 1996 | In June, 1996 | In June, 1998 | In July, 2000 | In June, 2002 | In May, 2006 |
| Aberration | 16.05 | 13.87 | 13.31 | 13.17 | 13.29 | 13.24 |
Table 3 is tested the aberration result with the present invention to the light blue colour developing protection on the Tang Zhaoling Wei highest-ranking imperial concubine tomb mural painting
| Time | In April, 1996 | In June, 1996 | In June, 1998 | In July, 2000 | In June, 2002 | In May, 2006 |
| Aberration | 17.30 | 11.47 | 10.50 | 10.20 | 10.23 | 10.13 |
Table 4 is tested the aberration result with the present invention to the colour developing of the redness on the brick matter mural painting of temple, Tang Qing mountain protection
| Time | In April, 1996 | In June, 1996 | In June, 1998 | In July, 2000 | In June, 2002 | In May, 2006 |
| Aberration | 15.24 | 10.27 | 9.20 | 9.23 | 9.10 | 9.19 |
By table 2, table 3, table 4 as seen, in 10 years, carry out the aberration of 5 test historical relic colored drawing relics, the aberration of mass colour, light blue, red 3 kinds of colors, with the present invention's historical relic relic that the protection weathering fades that develops the color, after 2 years, the aberration kept stable.
2, the present invention is to the test of handling property again of analog sample
(1) analog sample
1996; the analog sample that the contriver makes with mass colour, ultramarine, Zhu's fat, gamboge, bright red, ochre, malachite green, azurite, 9 kinds of pigment size mixture of cinnabar; with UV-light promote the oxidation, efflorescence it is faded; with the present invention's protection that develops the color; in relative humidity is 75%; temperature is accelerated deterioration 72 hours in 40 ℃ the xenon source environment, makes it stable.After keeping 10 years, with the present invention's protection that develops the color, embodied the property handled again of the present invention again.
(2) ancient wall
Protection develops the color for palace, the Qin ruins mural painting relic that employing the present invention is faded to weathering, the position that the serious weathering in mural painting two places of Tang Zhaoling Wei highest-ranking imperial concubine tomb is faded; after stable maintenance 10 years; with the present invention's protection that develops the color, embodied the property handled again of the present invention again.
3, efflorescence degree test of the present invention
With the present invention develop the color protection with lime with being battle simulate the mural painting sample, according to the measuring method of the colored paint coating efflorescence degree of stipulating among the GB/T14826-93, measure its efflorescence degree after 10 years.
Measurement result sees Table 5.
Table 5 the present invention is to the efflorescence type test result of mural painting
| Sample of colour | Mass colour | Gamboge | Malachite green | Azurite | Zhu's fat | Peony | Ochre | Kermes | Cyanine | Cinnabar | Bright red |
| The position of being untreated, colour developing |
0 1 | 0 1 | 0 2 | 0 3 | 0 3 | 0 3 | 0 3 | 0 3 | 0 3 | 0 3 | 0 4 |
As shown in Table 5, through 10 years tracking and testings, colour developing protection back pigment efflorescence do not occur and plays first, obscission, and efflorescence has not in various degree appearred in colour developing protection position.
4, tracking and testing reversibility (clearance)
1996 with the present invention to the colored drawing pottery, hold the mural painting protection that develops the color calcareously.The present invention is soluble in acetone, uses acetone solution, with layer watchman's clapper paper or rice paper absorption.In in April, 1996, in April, 2006 with the colored drawing pottery of weighting method after to the colour developing protection, hold mural painting calcareously and test and calculate clearance respectively.
Colour developing protection back was tested and was calculated with weighting method in April, 1996, and colored drawing pottery clearance is 70～80%, and the clearance of holding mural painting calcareously is 70～80%.
In April, 2006 to before 10 years with the present invention to the colored drawing pottery, hold mural painting with the weighting method test and calculate calcareously, the clearance of colored drawing pottery is 70～80%, Zhang clearance is 70～80% calcareously.
Through twice test, clearance of the present invention reaches more than 70% in 10 years, can recover the preceding situation of colour developing protection from macroscopic view.
5, the colour developing protective material for preparing with the embodiment of the invention 3 develops the color to 2 of Eastern Han Dynasty's colored drawing pottery pots and protects the spectrum comparison and detection of front and back with a kind of color
Censorship article: 2 of Eastern Han Dynasty's colored drawing pottery pots.
Test item: surface mass spectrum noon is answered curve.
Detecting instrument: the spectral radiant emittance meter, model FSP350-1050P, by produced in USA, china institute of metrology is demarcated; Reflection source: solar simulator, model XTM-2000.
Instrument performance: solar simulator is a standard light source, and homogeneity is greater than 98%; The spectral measurement ranges of spectral radiant emittance meter is 340-1060nm, and spectral resolution is 3nm.
Detect unit: Xian Inst. of Optics and Precision Mechanics, Chinese Academy of Sciences light spectrum image-forming research department.
Detection method: the working method by instrument detects.
Adopt the colour developing protective material of the embodiment of the invention 3 preparations; fade the paint-coated operating procedure step of historical relic to the protection that develops the color of half colored drawings of 2 of Eastern Han Dynasty's colored drawing pottery pots by the protection that develops the color with the present invention; deposit censorship in 10 years after the colour developing protection, with the spectral radiant emittance meter by the working method of instrument in 2 of Eastern Han Dynasty's colored drawing pottery pots the spectral response curves red, two kinds of colors of Huang after colour developing protection and the colour developing protection carried out comparison and detection.
Detected result: see Fig. 1～Fig. 6.
Detect conclusion: in repeatability red, yellow two kinds of colors on Eastern Han Dynasty's colored drawing pottery pot under the sampling condition repeatedly; adopt the present invention to develop the color and protect part consistent with the spectral pattern before the colour developing protection; red, the yellow two kinds of color development protection back that shows two positions is preceding consistent with the colour developing protection, the reduction of artifact color is not changed the spectral response curve of material.
6, use the colour developing protective material of the embodiment of the invention 3 preparations to Qian Mausoleum of Tang Dynasty Yongtai princess's colored drawing pottery figurine surface pigment and sizing material colour developing protection front and back comparison and detection
Censorship article: Qian Mausoleum of Tang Dynasty Yongtai princess's colored drawing pottery figurine.
Retrievable item order: configuration of surface analysis.
Sample model: solid sheet.
Detecting instrument: scanning electronic microscope, model JSM5800.
Detect unit: Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources.
Detection method: the technological method by Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources detects.
Testing environment: temperature is 26 ℃; Humidity is 68%.
Figure 11, Figure 12 are seen in the energy spectrum analysis of scanning electronic microscope.
Detect conclusion: under repeat condition, adopt the present invention to develop the color to contrast position trace print 06Pj348 before trace print 06Pj347 and the colour developing protection of princess's colored drawing pottery figurine surface, Qian Mausoleum of Tang Dynasty Yongtai pigment and sizing material of protection and carry out sem energy spectrum analysis.Analytical results shows: both inorganic integral parts of test sample are identical.
7, detecting surface mass with photoelectron spectrograph forms
With the colour developing protective material of the embodiment of the invention 3 preparation to Cang Jiemiao building wall colour painting and spring and autumn ancient painted pottery pigment with the colour developing protective material of sizing material mixolimnion relic and embodiment 2 preparations to permanently happy door colour painting relic colour developing protection front and back comparison and detection.
The censorship article: grey a word used in person's names mausoleum ancient building wall colour painting, spring and autumn ancient painted pottery pigment and sizing material mixolimnion relic.
Sample model: solid sheet.
Test item: surface mass is formed.
Detecting instrument: photoelectron spectrograph, model PH11-5400.
Detect unit: Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources.
Detection method: the technological method by Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources detects.
Testing environment: temperature is 25 ℃; Humidity is 65%.
Photoelectron spectrum figure sees Fig. 7, Fig. 8, Fig. 9, Figure 10.
Detected result: under repeat condition, adopt the develop the color ancient painted pottery pigment in spring and autumn of protection of the present invention to be numbered 06Pj341 with sizing material mixings relic and to be numbered 06Pj342 with the preceding comparative sample of colour developing protection and to carry out photoelectron spectrum mensuration.The result shows: (the detection degree of depth＜10nm) composition is consistent with the test sample material surface for test sample.
Under repeat condition, adopt the develop the color grey a word used in person's names mausoleum traditional decoration of protection of the present invention to draw relic and be numbered before 06Pj343 and the colour developing protection comparative sample and be numbered 06Pj344 and carry out photoelectron spectrum and measure.The result shows: (the detection degree of depth＜10nm) composition is consistent for both material surfaces of test sample.
Detect conclusion: the inorganic composition of test sample surface both is consistent.
8, carry out structure of matter analysis with x-ray diffractometer
With the colour developing protective material of the embodiment of the invention 3 preparation to Cang Jiemiao building wall colour painting and spring and autumn ancient painted pottery pigment with the colour developing protective material of sizing material mixolimnion relic and embodiment 2 preparations to permanently happy door colour painting relic colour developing protection front and back comparison and detection.
The censorship article: grey a word used in person's names mausoleum ancient building wall colour painting, spring and autumn ancient painted pottery pigment with sizing material mixolimnion relic, permanently happy colour painting relic.
Sample model: solid sheet.
Test item: structure of matter analysis.
Detecting instrument: x-ray diffractometer, model D/MAX-2400.
Detect unit: Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources.
Detection method: the technological method (1994) by Xi'an Mineral resources supervision inspection center of Ministry of Land and Resources detects.
Testing environment: temperature is 27 ℃; Humidity is 70%.
The X-ray diffraction oscillogram is seen Figure 13, Figure 14, Figure 15, Figure 16, Figure 17, Figure 18.
Detected result: under repeat condition, adopt the develop the color ancient painted pottery pigment in spring and autumn of protection of the present invention to be numbered 06Pj341 with sizing material mixings relic and to be numbered 06Pj342 with the preceding comparative sample of colour developing protection and to carry out X-ray diffraction mensuration.The result shows that both inorganic substance moietys of test sample are identical.Under repeat condition, adopt the develop the color ancient painted pottery pigment in spring and autumn of protection of the present invention to be numbered 06Pj343 with sizing material mixings relic and to be numbered 06Pj344 with the preceding comparative sample of colour developing protection and to carry out X-ray diffraction mensuration.The result shows that both inorganic substance moietys of test sample are identical.Under repeat condition, adopt the develop the color ancient painted pottery pigment in spring and autumn of protection of the present invention to be numbered 06Pj345 with sizing material mixings relic and to be numbered 06Pj346 with the preceding comparative sample of colour developing protection and to carry out X-ray diffraction mensuration.The result shows that both inorganic substance moietys of test sample are identical.
Detect conclusion: the equal no change of inorganics moiety after preceding and the colour developing protection is protected in all test sample colour developings.
In order to verify beneficial effect of the present invention; the contriver adopts the present invention of the embodiment of the invention 1～4 preparation to develop the color, and (name is called the ancient wall that weathering is faded to protective material when trying out; historical relic colored drawing and buildings colour painting manifest strengthening agent) list to develop the color to protect through State Cultural Relics Bureau's approval and try out; museum, Qianling Tomb Yongtai princess; the colored drawing pottery figurine that the weathering of Zhanghuai prince tomb is faded; colored drawing Western Han Dynastry Terracotta warrior that the weathering of museum, Xianyang is faded; the colored drawing mural painting that the weathering of museum, Tomb of Zhao Family Wei highest-ranking imperial concubine tomb is faded; imperial palace, Qin ruins, historical relic's protection center, Xianyang mural painting; the research of having carried out reaching 10 years on the historical relics such as museum, Famen Temple white marble colored drawing stone carving is on probation, and various service conditions are as follows:
1, to the fade colour developing protection of colored drawing pottery figurine of Qian Mausoleum of Tang Dynasty Yongtai princess, the weathering of Zhanghuai prince tomb in museum, Qianling Tomb
Use reagent: the embodiment of the invention 3 colour developing protective materials.
The historical relic of colour developing protection: Qian Mausoleum of Tang Dynasty Yongtai princess and the weathering of Zhanghuai prince tomb fade more than 42 of colored drawing pottery figurine, mural painting etc.
Colour developing guard time: in March, 2002～2005 year May.
Operating procedure step: the fade operating procedure step of historical relic colored drawing colour developing protection of weathering is carried out by the present invention's protective material that develops the color.
Result of use: the historical relic of the protection that develops the color is to be unearthed in the 60 to 70's of last century, and colored drawing is exquisite as new when being unearthed, and fades through the weathering of decades, and the colored drawing of a large amount of pottery figurines, pottery, mural painting is smudgy, is beyond recognition.Adopt the present invention to develop the color after the protective material colour developing protection, primary colors has been protected in the color colour developing of various historical relics.
2, to the fade colour developing protection of colored drawing Western Han Dynastry Terracotta warrior of the weathering in museum, Xianyang
Use reagent: the embodiment of the invention 3 colour developing protective materials.
The historical relic of colour developing protection: Western Han Dynastry's Terracotta warrior.
Colour developing guard time: 1996～in March, 2005.
Operating procedure step: the operating procedure step of the historical relic colored drawing colour developing protection of fading is carried out by the present invention's protective material that develops the color.
Result of use: Western Han Dynastry's Terracotta warrior weathering of being unearthed more than 40 year is faded, and colored drawing is smudgy, is beyond recognition.Adopt the present invention to develop the color after the protective material colour developing protection, primary colors has been protected in the color colour developing of various historical relics.To 1 Western Han Dynastry's Terracotta warrior of colour developing protection in 1996, to take pictures through the tracking observation in 10 years, the original color of colour developing protection does not change.
3, to the fade colour developing protection of colored drawing mural painting of the Tang Zhaoling Wei highest-ranking imperial concubine tomb weathering in museum, the Tomb of Zhao Family
Use reagent: the embodiment of the invention 3 colour developing protective materials.
The historical relic of colour developing protection: Tang Zhaoling Wei highest-ranking imperial concubine tomb mural painting.
Colour developing guard time: 1996～1997 years.
Operating procedure step: the operating procedure step of the historical relic colored drawing colour developing protection of fading is carried out by the present invention's protective material that develops the color.
Result of use: Wei highest-ranking imperial concubine tomb mural painting belongs to the grade one cultural relics of the state protection, through weathering for many years, the serious phenomenon of fading occurs, the protection that develops the color in 1996, and the colour developing protection is after the tracking observation in 10 years is taken pictures, and the original color of colour developing protection does not change.
4, imperial palace, the Qin ruins mural painting colour developing at historical relic's protection center, Xianyang is protected
Use reagent: the embodiment of the invention 4 colour developing protective materials.
The historical relic of colour developing protection: imperial palace, Qin ruins mural painting.
Colour developing guard time: 1996.
Operating procedure step: the operating procedure step of the historical relic colored drawing colour developing protection of fading is carried out by the present invention's protective material that develops the color.
Result of use: imperial palace, Qin ruins mural painting was unearthed more than 30 year, serious weathering occurred and faded and dry and cracked broken phenomenon, and original pattern is beyond recognition.The protection that developed the color in 1996, clearly colour developing has protected original color not change.The back 9 years tracking observation of colour developing protection is taken pictures, and the original color of colour developing protection does not change.
5, the white marble colored drawing stone carving colour developing in museum, Famen Temple is protected
Use reagent: the embodiment of the invention 2 colour developing protective materials.
The historical relic of colour developing protection: white marble colored drawing stone carving.
Colour developing guard time: 1996.
Operating procedure step: the operating procedure step of the historical relic colored drawing colour developing protection of fading is carried out by the present invention's protective material that develops the color.
Result of use: white marble colored drawing stone carvings such as south increases king, the wide order king in west, the gold hair lion of defending the doctrine are to be unearthed in 1987, because natural cause, the serious phenomenon of fading has taken place its color.The protection that developed the color in 1996, clearly original color and figure have been protected in colour developing.The back 10 years tracking observation of colour developing protection is taken pictures, and the original color and the figure of colour developing protection do not change.
Claims (3)
1. a weathering paint-coated colour developing protective material of ancient records and relics that fades is characterized in that it is to make composition by following weight percentages:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.30～0.75%
Tricresyl phosphite (nonyl phenyl) ester 0.06～0.15%
Phosphorous acid benzene di-isooctyl 0.06～0.15%
Vinylidene-chlorotrifluoroethylene 0.51～1.00%
Copolymer of methyl methacrylatestyrene 0.27～0.95%
Acetone 40.00～50.00%
Ethyl acetate 8.00～12.00%
Butylacetate 8.00～12.00%
Pentyl acetate 8.00～12.00%
Methylethylketone 9.00～12.00%
Ethylene glycol ethyl ether 8.00～12.00%
Vinylidene-chlorotrifluoroethylene in the said ratio is that trifluorochloroethylene and vinylidene fluoride are the amorphous copolymer of forming at 4: 1 in molar ratio.
2. according to the described weathering of the claim 1 paint-coated colour developing protective material of ancient records and relics that fades, it is characterized in that wherein making composition by following weight percentages:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.30～0.72%
Tricresyl phosphite (nonyl phenyl) ester 0.08～0.12%
Phosphorous acid benzene di-isooctyl 0.08～0.12%
Vinylidene-chlorotrifluoroethylene 0.60～0.90%
Copolymer of methyl methacrylatestyrene 0.30～0.80%
Acetone 42.00～46.00%
Ethyl acetate 10.00～12.00%
Butylacetate 10.00～12.00%
Pentyl acetate 10.00～12.00%
Methylethylketone 10.00～12.00%
Ethylene glycol ethyl ether 10.00～12.00%.
3. according to the described weathering of the claim 1 paint-coated colour developing protective material of ancient records and relics that fades, it is characterized in that wherein making composition by following weight percentages:
Two (1,2,2,6,6-pentamethyl--4-piperidyl)-sebates 0.50%
Tricresyl phosphite (nonyl phenyl) ester 0.10%
Phosphorous acid benzene di-isooctyl 0.10%
Vinylidene-chlorotrifluoroethylene 0.75%
Copolymer of methyl methacrylatestyrene 0.55%
Acetone 44.00%
Ethyl acetate 11.00%
Butylacetate 11.00%
Pentyl acetate 11.00%
Methylethylketone 10.00%
Ethylene glycol ethyl ether 11.00%.
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| CNB2006101044233A CN100372898C (en) | 2006-07-31 | 2006-07-31 | Colorful protecting agent for efflorescent and faded colored drawing cultural relic |
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| CNB2006101044233A CN100372898C (en) | 2006-07-31 | 2006-07-31 | Colorful protecting agent for efflorescent and faded colored drawing cultural relic |
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| CN100372898C true CN100372898C (en) | 2008-03-05 |
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| CN103360889B (en) * | 2013-07-31 | 2015-10-28 | 陕西师范大学 | Stone matter colored drawing strengthening agent |
| CN103773152B (en) * | 2014-01-07 | 2015-03-25 | 陕西师范大学 | Cellulose acetate filmstrip protective agent |
| CN108148450B (en) * | 2017-11-07 | 2020-03-06 | 陕西师范大学 | Fading cultural relic color development repairing agent and using method thereof |
| CN110396334A (en) * | 2019-08-08 | 2019-11-01 | 咸阳师范学院 | A kind of colour developing protective agent and its application and application method |
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