臺灣博碩士論文加值系統

摘要
本研究中主要探討之紙質文物保護材料分為三大類，分別為塑膠類、木質材料類與保存用紙類，藉由劣化試驗方式以瞭解此三類之保護材料的耐久性以及其對紙質文物之影響，並自製鹼性紙進行酸性紙之脫酸處理，以評估脫酸處理對紙質耐久性之改善情形。研究結果如下：
1. 塑膠類之紙質保護材料經戶外曝曬劣化後，以PVC為主成分之塑膠板材及膠膜較容易變黃及脆化，而A、C壓克力板及聚酯膠膜仍能保有良好的透明性與強度，具有較佳的耐候性質與較長的使用壽命，是較適宜作為長期保存紙質文物之塑膠類材料。
2. 在本試驗選用之8種木質板材，與濾紙及道林紙堆疊300天後，皆會對紙張的外觀產生負面影響，其中以柳杉、紅檜和扁柏三種樹種最為明顯，且會令紙張形成類似褐斑之黃色區塊，只有與雲杉堆疊之紙張的色差值變化最小。紙張與木材間以隔網方式進行堆疊，紙張仍然會有黃化的現象，可知即使不直接接觸木材，木材所釋出之揮發性物質亦會使得紙張變色而影響保存性。
3. 以高濕高熱方式對國內外保存用之紙質材料進行加速劣化後，酸性紙的回色現象及紙力衰退情形皆大於鹼性紙，紙張中含有機械漿者，黃化程度更是明顯，而鹼性紙中添加的碳酸鈣，能減緩紙張的劣化程度。國內產之保存用紙的性質與國外進口無酸紙相比，仍有一段差距，且國內產之保存用紙的木質素含量過多，並不符合文物保存單位之無酸紙規格。
4. 添加少量之AKD上膠劑即可賦予紙張良好的抗水性，但添加AKD上膠劑會降低紙張強度及pH值，可藉添加陽性澱粉、陽離子保留助劑及鹼性填料的方式改善之，本試驗中以添加0.1% AKD、0.5%陽性澱粉、0.5% C-PAM及5% CaCO3條件製出之鹼性紙的性質較佳。此外，自製中鹼性紙之脫酸效果並不遜色於國內外無酸紙，且增加鹼性填料添加量及加壓重力，可有效縮短脫酸處理時間與提升酸性紙之pH值。

Summary
Three kinds of material, plastics, wood and paper, have been adopted in this study for paper-based cultural relics’ protection. The permanence and performance of these materials in the protection of aged relics are our main concerns and have been well discussed. Furthermore, some laboratory-made alkaline handsheets were used to carry out the deacidification of acidic paper in this study. The effects of deacidification on paper relics’ permanence were also evaluated.
The experimental results were summarized as follows:
1. After outdoor aging, the plastic board made mainly from PVC and film became yellow and embrittled easily. Instead, the A, C acrylic boards and polyester films still retained good strength and transparency; they also had longer service life and better weather-durability. So, they are more suitable as protective materials for paper-based cultural relics.
2. Eight wooden boards were stacked with filter paper and woodfree printing paper for three hundred days. They all induced negative effects on papers, especially Cryptomeria japonica, Chamaecyparis formosensis and Chamecyparis obtusa. The above-mentioned three wooden materials caused the papers to severe foxing. Among the eight, Picea mariana caused the least change in the color difference of papers. Furthermore, when a metal wire was put between the paper and wooden materials, however the paper still became yellow even though the paper did not have direct contact with the wooden materials.
3. After the accelerated aging with high temperature and humidity, the scale of the color reversion and reduction in strength of acidic sized paper were more serious than that of alkaline sized paper. Color reversion became a rapid and unavoidable problem for the paper containing mechanical pulp. The load of CaCO3 in alkaline paper would act as acid-neutralizer and gradually decrease degradation during the aging of paper. Local-made fine papers are still not as good as imported acid-free papers. The higher content of lignin in local-made fine papers makes them unjustified to meet the definition of acid-free paper.
4. The addition of AKD decreases the strength and lowers the pH value of paper. Strength improvement can be achieved by adding the cationic starch, cationic retention aid-flocculants, and the pH value can be lifted by loading of alkaline filler. The property of alkaline paper, with addition of 0.1% AKD, 0.5% cationic starch, 0.5% cationic retention aid-flocculants and 5% CaCO3, was found to be the best in our study. Besides, the pH value of acidic papers could be increased, by pressing treatment with laboratory-made alkaline paper, to the extent of imported acid-free papers. By increasing the amounts of alkaline filler or the pressing pressures, it could decrease the pressing time and increase the pH value of acidic paper effectively.

目錄
表目次---------------------------------------------------------------------------------------- III
圖目次--------------------------------------------------------------------------------------- VI
摘要-------------------------------------------------------------------------------------------- XI
Summary--------------------------------------------------------------------------------------- XII

第一章 緒論
第一節 前言----------------------------------------------------------------------------- 1
第二節 文獻回顧----------------------------------------------------------------------- 3
第二章 文物保存用塑膠材料耐候性質之探討
第一節 前言---------------------------------------------------------------------------- 21
第二節 材料與方法------------------------------------------------------------------- 21
第三節 結果與討論------------------------------------------------------------------- 25
第四節 結語---------------------------------------------------------------------------- 42
第三章 木質典藏用材對紙質文物之影響
第一節 前言---------------------------------------------------------------------------- 43
第二節 材料與方法------------------------------------------------------------------- 43
第三節 結果與討論------------------------------------------------------------------- 47
第四節 結語---------------------------------------------------------------------------- 59
第四章 市售國內外文物保存用紙劣化之研究
第一節 前言---------------------------------------------------------------------------- 60
第二節 材料與方法------------------------------------------------------------------- 60
第三節 結果與討論------------------------------------------------------------------- 63
第四節 結語---------------------------------------------------------------------------- 77


第五章 中鹼性上膠紙應用於酸性紙脫酸處理之研究
第一節 前言---------------------------------------------------------------------------- 78
第二節 中鹼性上膠紙之製備及劣化---------------------------------------------- 78
第三節 酸性紙之壓板脫酸試驗---------------------------------------------------- 85
第四節 結語---------------------------------------------------------------------------- 90
第六章 結論---------------------------------------------------------------------------------- 91
第七章 參考文獻---------------------------------------------------------------------------- 93




























表目次
表 1-1 台灣部份博物館和美術館所使用的典藏木質材料------------------------- 15
Table 1-1 The wooden materials used for classical-collection in some museums and fine art museum in Taiwan

表3-1 試驗用之木質材料種類----------------------------------------------------------- 44
Table 3-1 Wooden materials for experimental use.

表3-2 試驗木材之醇苯抽出物與pH值--------------------------------------------------- 48
Table 3-2 Alcohol-benzene extractive and pH value of wooden materials

表3-3 試驗紙樣經堆疊前及堆疊300天後之pH值---------------------------------- 48
Table 3-3 Changes in the pH value of paper superposed on different wooden materials after 300 days of long-time aging.

表3-4 濾紙和不同木質材料堆疊300天後色差值之變化----------------------------- 49
Table 3-4 Changes in the color difference of filter paper superposed on different wooden materials after 300 days aging.

表3-4 濾紙和不同木質材料堆疊300天後色差值之變化 ( 續1 )------------------ 50
Table 3-4 Changes in the color difference of filter paper superposed on different wooden materials after 300 day aging. ( Continued 1 )

表3-4 濾紙和不同木質材料堆疊300天後色差值之變化 ( 續2 )------------------ 51
Table 3-4 Changes in the color difference of filter paper superposed on different wooden materials after 300 days aging. ( Continued 2 )

表3-5 台紙道林紙和不同木質材料堆疊300天後色差值之變化-------------------- 52
Table 3-5 Changes in the color difference of woodfree printing paper superposed on different wooden materials after 300 days aging.

表3-5 台紙道林紙和不同木質材料堆疊300天後色差值變化(續1)---------------- 53
Table 3-5 Changes in the color difference of woodfree printing paper superposed on different wooden materials after 300 days aging. ( Contiuned 1 )



表3-5 台紙道林紙和不同木質材料堆疊300天後色差值變化(續2)---------------- 54
Table 3-5 Changes in the color difference of woodfree printing paper superposed on different wooden materials after 300 days aging. ( Contiuned 2 )

表3-6 試驗紙樣和不同木質材料堆疊300天後白度之變化------------------------- 56
Table 3-6 Changes in the brightness of paper superposed on different wooden materials after 300 days aging.

表3-6 試驗紙樣和不同木質材料堆疊300天後白度之變化(續)-------------------- 57
Table 3-6 Changes in the brightness of paper superposed on different wooden materials after 300 days aging. ( Continued )

表3-7 堆疊300天後之試驗紙張於85℃，90% RH條件加速劣化後之白度變化---------------------------------------------------------------------------------------------------- 58
Table 3-7 Changes in the brightness of paper superposed on different wooden materials after 300 days aged at 85℃ and 90% RH.

表3-7 堆疊300天之試驗紙張於85℃，90% RH條件加速劣化後之白度變化 (續)----------------------------------------------------------------------------------------------- 59
Table 3-7 Changes in the brightness of paper superposed on different wooden materials after 300 days aged at 85℃ and 90% RH. ( Continued )

表4-1 市售國內外紙袋信封之基本性質------------------------------------------------- 63
Table 4-1 The basic properties of domestic and imported envelopes.

表4-2市售國內外紙袋信封之耐摺強度經時變化-------------------------------------- 66
Table 4-2 The changes in the folding endurance of domestic and imported envelopes after 300 hours aging.

表4-3 市售國內外紙板之基本性質------------------------------------------------------- 68
Table 4-3 The basic properties of domestic and imported paper boards.

表4-4 市售國內外紙張之基本性質------------------------------------------------------- 72
Table 4-4 The basic properties of domestic and imported paper.

表4-5 市售國內外紙張耐摺強度經劣化後之變化------------------------------------- 75
Table 4-5 The changes in the folding endurance of domestic and imported papers after 300 hours aging.
表5-1 實驗室手抄紙之基本性質-------------------------------------------------------- 81
Table 5-1 The basic properties of handsheets.

表5-2 實驗室手抄紙與國內外市售紙張經加速劣化後之耐摺強度變化情形---- 83
Table 5-2 The changes in the folding endurance of handsheets of domestic and imported papers after accelerated aging at 85℃and 90%RH.

表5-3 E廠道林紙經不同中鹼性紙脫酸後之pH值變化----------------------------- 87
Table 5-3 The changes in the pH value of E woodfree printing paper superposed on different alkaline paper after 30 days.

表5-4 不同重力及鹼性填料添加量對酸性紙脫酸效果之影響---------------------- 90
Table 5-4 Effect of pressure and alkaline filler dosage on the deacidification of acidic paper and over 90%RH.
























圖目次
圖1-1 纖維素化學結構---------------------------------------------------------------------- 4
Fig.1-1 Chemical structure of cellulose

圖1-2 半纖維素的主要基本單醣成分---------------------------------------------------- 5
Fig. 1-2 Chemical structure and major component of Hemicellulose

圖1-3 木質素的基本構造------------------------------------------------------------------- 6
Fig. 1-3 Basic structure of lignin

圖1-4 木質素模式化合物之典型發色團------------------------------------------------- 6
Fig. 1-4 Classic chromophore of lignin model compounds

圖 1-5 木質素之光化學反應--------------------------------------------------------------- 7
Fig. 1-5 Photoreaction of lignin

圖1-6 木質素內β-O-4結構的殘基之光化學反應--------------------------------------- 8
Fig. 1-6 Photoreaction of β-O-4 residues of lignin

圖1-7 以各種藥品調整pH值後抄紙對紙張抗張強度之影響--------------------- 10
Fig. 1-7 Effects of pH on tensile strength of paper

圖 1-8 AKD之結構及其與纖維的反應------------------------------------------------ 11
Fig. 1-8 Structure of alkyl ketene dimmer and its possible reaction products.

圖 1-9 纖維素的酸加水分解------------------------------------------------------------- 12
Fig. 1-9 Acid-catalyzed hydrolysis of cellulose

圖 1-10 各種塑膠材料之基本結構------------------------------------------------------ 18
Fig 1-10 Basic structure of plastic materials

圖 1-11 各種塑膠材料之劣化情形------------------------------------------------------- 19
Fig. 1-11 The changes of plastic materials after six months aging

圖2-1 彎曲強度之測定方式-------------------------------------------------------------- 24
Fig. 2-1 The model of bending test

圖2-2 抗拉伸試驗之試片規格----------------------------------------------------------- 24
Fig. 2-2 Specification of tensile test specimens.

圖2-3 塑膠板材曝曬劣化前後之情形 ( a ) A壓克力板 ( b ) B壓克力板 ( c ) C壓克力板 ( d ) D壓克力板( e ) PC板( f ) PVC板---------------------------------------- 26
Fig. 2-3 The changes in the transparence of plastic boards before and after irradiation. ( a ) A acrylate board ( b ) B acrylate board ( c ) C acrylate board ( d ) D acrylate board ( e ) PC board ( f ) PVC board.

圖 2-4 塑膠板材於戶外曝曬後之色澤度變化---------------------------------------- 27
Fig. 2-4 The changes in the transparency of plastic boards after irradiation for 300 days.

圖 2-5 塑膠板材於戶外曝曬後之彎曲強度變化------------------------------------- 27
Fig 2-5 The changes in the bending strength of plastic boards after irradiation for 300 days.

圖2-6 A壓克力板於戶外曝曬前後之FT-IR光譜------------------------------------- 29
Fig 2-6 FT-IR spectra of A acrylate board before and after irradiation.

圖2-7 B壓克力板於戶外曝曬前後之FT-IR光譜------------------------------------- 30
Fig 2-7 FT-IR spectra of B acrylate board before and after irradiation.

圖2-8 C壓克力板於戶外曝曬前後之FT-IR光譜------------------------------------- 30
Fig 2-8 FT-IR spectra of C acrylate board before and after irradiation.

圖2-9 D壓克力板於戶外曝曬前後之FT-IR光譜------------------------------------- 31
Fig 2-9 FT-IR spectra of D acrylate board before and after irradiation.

圖2-10 PVC板於戶外曝曬前後之FT-IR光譜----------------------------------------- 31
Fig 2-10 FT-IR spectra of PVC board before and after irradiation.

圖2-11 PC板於戶外曝曬前後之FT-IR光譜------------------------------------------- 32
Fig 2-11 FT-IR spectra of PC board before and after irradiation.




圖2-12 塑膠膜曝曬劣化前後之情形 ( a ) PVC膜 ( b ) PP膜( c ) 酯膠膜 ( d ) 投影片( e ) 護貝膜 ( f ) 玻璃紙 ( g ) ESCAL 封口膜 ( h ) 文件夾塑膠套膜---------------------------------------------------------------------------------------------------- 34
Fig. 2-12 The changes in the transparence of plastic films before and after irradiation. ( a ) PVC film ( b ) PP film ( c ) Polyester film ( d ) Transparency film ( e ) Laminat- ing film ( f ) Cellophane ( g ) Archival polyester envelopes ( h ) Portfolio film.

圖2-13 塑膠膜於戶外曝曬後之光澤度變化情形------------------------------------- 35
Fig. 2-13 The changes in the transparency of plastic films after irradiation for 300 days.

圖2-14 塑膠膜於戶外曝曬後之拉伸強度變化情形---------------------------------- 35
Fig. 2-14 The changes in the tensile strength of plastic films after irradiation for 300 days.

圖2-15 PVC膜於戶外曝曬前後之FT-IR光譜----------------------------------------- 38
Fig. 2-15 FT-IR spectra of PVC film before and after irradiation.

圖2-16 PP膜於戶外曝曬前後之FT-IR光譜------------------------------------------- 38
Fig. 2-16 FT-IR spectra of PP film before and after irradiation.

圖2-17 玻璃紙於戶外曝曬前後之FT-IR光譜----------------------------------------- 39
Fig. 2-17 FT-IR spectra of cellophane film before and after irradiation.

圖2-18 聚酯膜於戶外曝曬前後之FT-IR光譜----------------------------------------- 39
Fig. 2-18 FT-IR spectra of polyester film before and after irradiation.

圖2-19 投影片於戶外曝曬前後之FT-IR光譜----------------------------------------- 40
Fig. 2-19 FT-IR spectra of Transparency film before and after irradiation.

圖2-20 護貝膜於戶外曝曬前後之FT-IR光譜----------------------------------------- 40
Fig. 2-20 FT-IR spectra of Laminating film before and after irradiation.

圖2-21 ESCAL 無酸性聚酯封口膜於戶外曝曬前後之FT-IR光譜--------------- 41
Fig. 2-21 FT-IR spectra of archival polyester envelopes before and after irradiation.

圖2-22 文件夾塑膠膜於戶外曝曬前後之FT-IR光譜-------------------------------- 41
Fig. 2-22 FT-IR spectra of portfolio film before and after irradiation.
圖3-1 試驗材料之堆疊情形-------------------------------------------------------------- 44
Fig. 3-1 Schematics of wooden materials and paper sample.

圖3-2 濾紙與柳杉、紅檜和扁柏堆疊300天後所產生之褐斑--------------------- 55
Fig. 3-2 The foxing on filter paper which was superposed on Cryptomeria japonica, Chamaecyparis formosensis and Chamecyparis obtusa.

圖4-1 市售國內外紙袋信封之白度經時變化----------------------------------------- 64
Fig. 4-1 The changes in the brightness of domestic and imported envelopes after 300 hours aging.

圖4-2 市售國內外紙袋信封之耐摺強度經時變化----------------------------------- 66
Fig. 4-2 The changes in the folding endurance of domestic and imported envelopes after 300 hours aging.

圖4-3 市售國內外紙袋信封之抗張強度經時變化----------------------------------- 67
Fig. 4-3 The changes in the tensile strength of domestic and imported envelopes after 300 hours aging.

圖4-4 市售國內外紙板之白度經時變化------------------------------------------------- 69
Fig. 4-4 The changes in the brightness of domestic and imported paper boards after 300 hours aging.

圖4-4 市售國內外紙板之白度經時變化(續)-------------------------------------------- 70
Fig. 4-4 The changes in the brightness of domestic and imported paper boards after 300 hours aging. ( Continued )

圖4-5 市售國內外紙張之白度經時變化------------------------------------------------- 73
Fig. 4-5 The changes in the brightness of domestic and imported papers after 300 hours aging.

圖4-5 市售國內外紙張之白度經時變化 (續)------------------------------------------ 73
Fig. 4-5 The changes in the brightness of domestic and imported papers after 300 hours aging. ( Continued )

圖4-6 市售國內外紙張之耐摺強度經時變化------------------------------------------- 75
Fig. 4-6 The changes in the folding endurance of domestic and imported papers after 300 hours aging.
圖4-6 市售國內外紙張之耐摺強度經時變化 ( 續 )--------------------------------- 76
Fig. 4-6 The changes in the folding endurance of domestic and i papers after 300 hours aging. ( Continued )

圖4-7 市售國內外紙張之抗張強度經時變化----------------------------------------- 76
Fig. 4-7 The changes in the tensile strength of domestic and imported papers after 300 hours aging.

圖5-1 實驗室手抄紙與國內外市售紙張經加速劣化後之白度變化---------------- 82
Table5-1 The color reversion of handsheets and domestic and imported papers after accelerated aging in 85℃and 90 RH.

圖5-2 實驗室手抄紙與國內外市售紙張經加速劣化後之耐摺強度經時變化---- 84
Fig.5-2 The changes in the folding endurance of handsheets and domestic and imported papers after accelerated aging at 85℃and 90% RH.

圖5-3 實驗室手抄紙與國內外市售紙張經加速劣化後之抗張強度經時變化---- 84
Fig.5-3 The changes in the tensile strength of handsheets and domestic and imported papers after accelerated aging at 85℃and 90% RH.

圖5-4 紙張堆疊實驗圖-------------------------------------------------------------------- 86
Fig.5-4 The layout of the experimental setup.

圖5-5 壓板脫酸後對酸性紙白度之影響----------------------------------------------- 88
Fig.5-5 Effect of pressure process on the brightness of acidic paper after accelerated aging at 85℃ and 90%RH.

圖5-6 酸性紙壓板脫酸對紙質劣化之影響---------------------------------------------- 88
Fig. 5-6 Effect of pressure process on the folding endurance of acidic paper after accelerated aging at 85℃ and 90%RH.

第七章 參考文獻
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