CN109577091B - Paper cultural relic reinforcing liquid - Google Patents

Paper cultural relic reinforcing liquid Download PDF

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Publication number
CN109577091B
CN109577091B CN201811498286.5A CN201811498286A CN109577091B CN 109577091 B CN109577091 B CN 109577091B CN 201811498286 A CN201811498286 A CN 201811498286A CN 109577091 B CN109577091 B CN 109577091B
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Prior art keywords
based polyurethane
ethyl acetate
hydroxyl
silicon dioxide
nano silicon
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CN109577091A (en
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金姗姗
李华
李振兴
邵帅
李建文
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Zheng Zhoubowuguan
Zhengzhou University
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Zheng Zhoubowuguan
Zhengzhou University
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    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H25/00After-treatment of paper not provided for in groups D21H17/00 - D21H23/00
    • D21H25/18After-treatment of paper not provided for in groups D21H17/00 - D21H23/00 of old paper as in books, documents, e.g. restoring
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/03Non-macromolecular organic compounds
    • D21H17/05Non-macromolecular organic compounds containing elements other than carbon and hydrogen only
    • D21H17/14Carboxylic acids; Derivatives thereof
    • DTEXTILES; PAPER
    • D21PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21HPULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H17/00Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
    • D21H17/20Macromolecular organic compounds
    • D21H17/33Synthetic macromolecular compounds
    • D21H17/46Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H17/54Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen
    • D21H17/57Polyureas; Polyurethanes

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paper (AREA)

Abstract

The invention relates to a paper cultural relic reinforcing liquid for paper cultural relic protection, which can effectively solve the problem that the strength and the flexibility of paper cannot be simultaneously increased by the existing reinforcing liquid for paper cultural relic protection, and the reinforcing liquid is calculated by the following weight percentages: 5-30% of nano silicon dioxide-based polyurethane, 5-30% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 5-30% of organosilicon-based polyurethane and 10-85% of ethyl acetate are uniformly mixed to prepare the polyurethane; the invention has scientific and reasonable formula, abundant raw materials and easy production and preparation, not only has excellent properties of common polyurethane in the aspects of paper strength, aging resistance and the like, but also has higher transparency, avoids the adverse effects brought by the traditional resin reinforcement method in the aspects of luster, texture and the like, has reversibility, can remove a protective film under the condition of no damage or slight damage, is an innovation on the protection and reinforcement liquid of paper cultural relics, and has huge economic and social benefits.

Description

Paper cultural relic reinforcing liquid
Technical Field
The invention relates to a chemical product, in particular to a paper cultural relic reinforcing liquid for protecting paper cultural relics.
Background
The paper cultural relics are precious historical data and important cultural heritage of ancient art in China, the precious paper cultural relics recording the human cultural relics are continuously damaged, the phenomenon of self-destruction of a large number of books is found in examination of libraries in American national congress and libraries in French national library, China has history of five thousand years civilization, the precious paper historical relics are as large as those in the smoky sea and as inexhaustible enumeration, but with the passing of years, the damage phenomena of yellowing, mildew, pulverization, brittle fracture, rotting, breakage, smudginess and the like are caused by the influence of various factors, so that the development of the paper cultural relic protection work and the research on the reinforcing and protecting materials and the process of the paper cultural relics are very important and urgent tasks. However, since paper is both elastic and plastic, paper having a high tensile strength tends to be more easily broken than paper having a low tensile strength when printed. This indicates that the tensile strength cannot accurately indicate the ability of the paper to resist tensile failure, and the ability of the paper to resist failure is not only expressed by strength, but also expressed by toughness, i.e. has a certain relationship between stress and strain, so that the development of a reinforcing liquid for synchronously enhancing the strength and the flexibility of the paper is a technical problem which needs to be solved.
Disclosure of Invention
In view of the above situation, in order to overcome the defects of the prior art, the invention aims to provide a paper cultural relic reinforcing liquid for paper cultural relic protection, which can effectively solve the problem that the strength and flexibility of paper cannot be simultaneously increased by the conventional reinforcing liquid for paper cultural relic protection.
The technical scheme of the invention is that a paper cultural relic reinforcing liquid for protecting the paper cultural relics is prepared from the following components in percentage by weight: 5-30% of nano silicon dioxide-based polyurethane, 5-30% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 5-30% of organosilicon-based polyurethane and 10-85% of ethyl acetate are uniformly mixed to prepare the polyurethane;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
The paper cultural relic protection material prepared by the invention has reversibility, can remove the protection film under the condition of no damage or slight damage, is an innovation on the protection and solidification liquid of the paper cultural relic, and has great economic and social benefits.
Detailed Description
The following detailed description of specific embodiments of the invention is provided in connection with specific use cases and examples.
Example 1: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 70% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
Example 2: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate are uniformly mixed to prepare the polyurethane; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 3: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 4: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 15% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate are uniformly mixed to prepare the polyurethane; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 5: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: the nano silicon dioxide-based polyurethane is prepared by uniformly mixing 15% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 6: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 15% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 55% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
Example 7: a paper cultural relic reinforcing liquid comprises the following components in percentage by weight: 20% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate are uniformly mixed to prepare the polyurethane adhesive; the preparation methods of the nano-silica-based polyurethane, the hydroxyl-terminated epoxycyclohexane-epichlorohydrin-based polyurethane and the organosilicon-based polyurethane are the same as in example 1.
When the paper is used specifically, the cut paper (210mm multiplied by 297mm) is soaked in the reinforcing liquid provided by the invention (or the reinforcing liquid provided by the invention is sprayed on the paper) for 2-15min, and then the paper is taken out and dried naturally.
The results of the performance indexes of the paper treated by the reinforcing liquid prepared by the methods of examples 1, 2, 3, 4, 5, 6 and 7 of the invention are shown in Table 1:
table 1:
Figure BDA0001897464720000041
the tensile strength test of the paper in the table is determined according to national standard GB/T12914-2008; the folding endurance of the paper is determined according to national standard GB/T457-2008; the tearing degree of the paper is measured according to the national standard GB/455-2002 of China; the glossiness of the paper is measured according to the national standard GB/T8941-2013; the whiteness of the paper is measured according to the national standard GB/T7974-2002 of China.
Aging test: the comparison of the performance indexes of the paper treated by the reinforcing liquid of the invention and the blank paper before and after aging is shown in Table 2:
table 2:
Figure BDA0001897464720000051
the aging experiments in the above table were determined according to national standard GB/T464-2008.
Compared with the prior art, the invention has the following beneficial technical effects:
1. the nano silicon dioxide-based polyurethane has the effects of absorbing and shielding ultraviolet rays of 200-400 nm and simultaneously has the effects of enhancing and toughening, so that the mechanical property can be enhanced and the ultraviolet resistance of the cultural relics can be improved by over 50% by adding the nano silicon dioxide-based polyurethane into a reinforcing liquid.
2. The polyurethane prepared by synthesizing the epoxy cyclohexane-epoxy chloropropane copolyether polyurethane has small molecular weight, good permeability and colorless and transparent appearance, and can improve the mechanical property of paper and keep good glossiness by more than 40 percent when being applied to the reinforcement protection of paper cultural relics;
3. the organosilicon-based polyurethane contains Si-O bonds with high bond energy (422.2kJ/m O l) on organosilicon, and the unimolecular volume of the organosiloxane is large, and the cohesive energy density is low, so that the organosiloxane is introduced to the main chain or the side chain of the polyurethane molecule, and the tolerance performance of the product can be improved. The invention combines the advantages of polysiloxane and polyurethane to obtain the paper reinforcing material with excellent performance, and particularly, the folding resistance of the paper is obviously improved, and the folding resistance times can be improved by more than 2 times.
4. The invention has scientific and reasonable formula, rich raw materials, easy production and preparation and good use effect. The paper has the advantages of enhancing the tensile strength of the paper, keeping the flexibility of the paper, having higher transparency, avoiding the defect that the traditional reinforcing material can only enhance the single performance of the paper, prolonging the preservation life of the paper cultural relics by more than 3 times, having strong ageing resistance and improving the ornamental and research values of the paper cultural relics. The paper cultural relic protection material prepared by the invention has reversibility, can remove the protection film under the condition of no damage or slight damage, is an innovation on paper cultural relic protection, and has great economic and social benefits.

Claims (8)

1. A paper cultural relic reinforcing liquid is characterized in that: the reinforcing liquid is prepared from the following components in percentage by weight: 5-30% of nano silicon dioxide-based polyurethane, 5-30% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 5-30% of organosilicon-based polyurethane and 10-85% of ethyl acetate are uniformly mixed to prepare the polyurethane;
the nano silicon dioxide-based polyurethane comprises the following components in parts by weight: 40g of hexamethylene diisocyanate trimer, 0.5g of nano silicon dioxide, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the nano silicon dioxide is placed in a vacuum drying oven and dried for 10-24h, and moisture is removed to obtain dried nano silicon dioxide; adding hexamethylene diisocyanate trimer into ethyl acetate to obtain mixed solution; adding dried nano silicon dioxide into the mixed solution, adding dibutyltin dilaurate, heating to 70 ℃, reacting, measuring the content of isocyanate group (-NCO) every other hour, stopping the reaction when the content of the isocyanate group (-NCO) is not changed any more, and removing ethyl acetate by reduced pressure distillation to obtain nano silicon dioxide-based polyurethane;
the hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane is prepared from the following components in parts by weight: 5g of hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, 40g of hexamethylene diisocyanate tripolymer, 0.1g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane copolyether, the hexamethylene diisocyanate tripolymer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, and when the weight content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, so that hydroxyl-terminated epoxy cyclohexane-epoxy chloropropane polyurethane is obtained;
the organic silicon-based polyurethane comprises the following components in parts by weight: 30g of hydroxyl-terminated polydimethylsiloxane, 40g of hexamethylene diisocyanate trimer, 0.2g of dibutyltin dilaurate and 30g of ethyl acetate, wherein the hydroxyl-terminated polydimethylsiloxane, the hexamethylene diisocyanate trimer and the dibutyltin dilaurate are added into the ethyl acetate, the mixture is heated to 70 ℃ for reaction, the content of isocyanate group (-NCO) is measured every other hour, when the content of the isocyanate group (-NCO) is not changed any more, the reaction is terminated, and the ethyl acetate is removed through reduced pressure distillation, so that the organosilicon-based polyurethane is obtained.
2. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 10% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 70% of ethyl acetate.
3. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: comprises the following components in percentage by weight: 10% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate.
4. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 10% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
5. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 15% of organosilicon-based polyurethane and 60% of ethyl acetate.
6. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 15% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
7. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 15% of nano silicon dioxide-based polyurethane, 20% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 10% of organosilicon-based polyurethane and 55% of ethyl acetate.
8. The paper cultural relic-strengthening liquid as claimed in claim 1, which is characterized in that: the weight percentages are as follows: 20% of nano silicon dioxide-based polyurethane, 10% of hydroxyl-terminated epoxy cyclohexane-epichlorohydrin-based polyurethane, 20% of organosilicon-based polyurethane and 50% of ethyl acetate.
CN201811498286.5A 2018-12-08 2018-12-08 Paper cultural relic reinforcing liquid Expired - Fee Related CN109577091B (en)

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CN111424464B (en) * 2020-03-19 2022-06-24 郑州大学 Preparation method and application of modified chitosan/silicon composite reinforcement liquid for paper protection
CN111270554B (en) * 2020-03-19 2021-12-07 郑州大学 Amphipathic cationic chitosan-phosphate starch composite strengthening liquid for paper protection
CN113774708B (en) * 2021-07-16 2023-09-19 浙江理工大学 Preparation and application methods of paper cultural relic protection liquid
CN115110340B (en) * 2022-04-24 2023-04-28 郑州大学 Multifunctional protective liquid for paper
CN116556107A (en) * 2023-03-29 2023-08-08 郑州大学 Protective liquid for protecting paper cultural relics

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WO1999020706A2 (en) * 1997-10-17 1999-04-29 Graphische Sammlung Albertina Teilrechtsfähig Gemäss Forschungsorganisationsgesetz 1981 (Fog) I.D.N.1989 Compress and its use for unsticking
CN103224408A (en) * 2013-04-22 2013-07-31 中国科学院上海硅酸盐研究所 Reinforcement material for preservation of cultural relics, and preparation method and application thereof
CN108221482B (en) * 2018-01-29 2020-07-10 郑州博物馆 Reinforcing liquid for protecting paper cultural relics
CN108440736B (en) * 2018-03-27 2020-09-25 郑州博物馆 Transparent polyurethane reinforced liquid for protecting paper cultural relics

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