CN102268842A - Method for deacidifying paper by using soluble tetraborate as paper deacidifying agent - Google Patents
Method for deacidifying paper by using soluble tetraborate as paper deacidifying agent Download PDFInfo
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- CN102268842A CN102268842A CN201110212874XA CN201110212874A CN102268842A CN 102268842 A CN102268842 A CN 102268842A CN 201110212874X A CN201110212874X A CN 201110212874XA CN 201110212874 A CN201110212874 A CN 201110212874A CN 102268842 A CN102268842 A CN 102268842A
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Abstract
The invention discloses a method for deacidifying paper by using soluble tetraborate as paper deacidifying agent. Tetraborate aqueous solution with different concentrations and organic solvents in different types are mixed together; paper, especially acidified and aged paper, is deacidified by adopting a plurality of modes such as immersion, spraying, atomization or supercritical treatment; the soluble tetraborate serving as the paper deacidifying agent for deacidifying the paper can control the pH value of the paper within an ideal range, and diffusion of ink marks and color change of the paper can be avoided in the deacidifying process; furthermore, all the mechanical strengths of the paper are enhanced during deacidifying; the tetraborate has a certain function of restraining microorganisms; therefore, after the paper is treated by the tetraborate solution, the durability of the paper is improved obviously.
Description
Technical field
The present invention relates to a kind of use solubility tetraborate to the acidifying paper, for example the ancient books paper carries out the method for depickling; Agent is used for the method for paper deacidification as paper deacidification to be specifically related to a kind of solubility tetraborate.
Background technology
Chinese culture, with a long history, dazzling.According to estimates: the Chinese successive dynasties literature of ancient book since " the first bone oracle inscriptions of the Shang Dynasty " have literature record reaches 80,000 kinds more than." ancient books " is the write legal document for others abbreviation of nationality of Ancient Chinese, is the main carrier and the sign of human material progress and culture, is the abundant historical and cultural heritage that the brilliant civilization history in 5,000 years of the Chinese nation stays to us.But a lot of precious ancient books because of of the remote past, chaos caused by war from funeral, extreme misery invade mutually, the moth-eaten erosion of rat eaten, also have the deterioration of environment to cause most ancient books to have in various degree breakage, demand protection urgently and rescue.According to statistics, the ancient books shop of National Library has about 1,400,000 parts of ancient books now, but because of the remote past, some precious rare book handed down from ancient times also is riddled with gaping wounds, incomplete.Duration today, it is precious further only to subtract the ancient books handed down from ancient times that does not increase.In 1,400,000 ancient books collected books, slight breakage accounts for 30%, and moderate, severe respectively are 10%, three addition nearly half, and especially the ancient books in the Republic of China period is damaged even more serious.Owing to the Republic of China's paper technology backwardness in period, paper acid content height has considerable part the Republic of China thread-bound book pH value below 3, and paper severe acidification has taken place and gone mouldy, and has lost the due mechanical strength of paper, to the stage that is on the brink of to destroy.Therefore, how protecting these precious literature of ancient book, is the urgent and difficult task of pendulum in face of ours.
The type of ancient books breakage is damaged by worms, is gone mouldy, waddingization, rat eaten, fiery cinder, paper aging, acidifying etc., and acidifying, aging be a process continuously, so, if these ancient books can not effectively be handled at present, will continue to spread, in addition irrecoverable.The acidity that the acidifying of ancient books refers to the ancient books paper strengthens the phenomenon that is occurred gradually.Be rendered as specifically that paper becomes fragile, its colour changed into yellow, obfuscation, mechanical strength reduces, serious can't stir, even be broken into paper scrap.In brlken paper, the infringement that acidifying causes ancient books accounts for sizable ratio, and will have a strong impact on the preservation life-span of ancient books.The pH value of literature of ancient book is lower than 6.2, just should carry out disacidify and handle; If be lower than 5.0, just must carry out disacidify and handle.The harm that the paper acidifying brings has caused the great attention of national governments, and in recent years, various countries carry out the depickling work of treatment of papery historical relic one after another.According to experiment, pH value of paper is at the books below 5.0, preserves the time limit and the longlyest has only 200 years.As long as paper contains acidity, even only hiding, literature of ancient book need not or be in the good preservation environment, can not suppress paper generation qualitative change.
At acidifying is the principal element of ancient paper degraded, when repairing ancient books, add alkali compounds and make the pH value of paper bring up to neutrality or more than the neutrality, i.e. " depickling ", thus the acidic hydrolysis of barrier fibers element is avoided the purpose of breakage to reach the protection paper.Therefore, the deacidification agent of seeking suitable paper deacidification is very important, reduces the influence to texture of paper etc. when playing good deacidification effect as far as possible.
The deacidification agent that is usually used in paper deacidification at present has calcium hydroxide, calcium bicarbonate, calcium propionate, magnesium bicarbonate, barium hydroxide-methanol solution, magnesia, magnesium titanium bimetallic alkoxide, methoxy magnesium carbonate, ethoxyethyl group magnesium carbonate, methyl carbonic acid magnesium and ethyl carbonate magnesium etc.
Calcium containing compound disacidify sheet processed pH value obviously improves, the also corresponding increase of whiteness value, and the alkali retention increases.The raising of these physical and chemical indexs, will make preservation life-span of file prolong more than 100 years, be deposited on the pollution that calcium containing compound on the paper can slow down acidic gas in air.But the saturated solution alkalescence of calcium hydroxide, calcium bicarbonate is stronger, and the neutrality that is unsuitable for modern paper is handled.
PH value of paper can reach 9.4～10.4 behind the water soluble compound disacidify of magnesium, and the alkali residual quantity is 2.0%.Unnecessary will be adsorbed on paper surface naturally, generates MgCO
3Play cushioning effect as alkaline residues, can resist the erosion of acidic materials for a long time.But it is higher that the pH of back paper is handled in its depickling, surpasses 140g/m2 for paper weight, large format paper, photo, zinc oxide copy and the embrittlement paper is all inapplicable, and limitation is bigger.The paper aging test shows that the mechanical strength of paper decreases, and the paper brightness reversion is serious.
In the deacidification agent of non-water system, can make the writing diffusion after barium hydroxide-methanol solution depickling; Methoxy magnesium carbonate exists disacidify inhomogeneous, and problem such as writing fades, long hickie, wrinkling variable color and adhesive ooze out is so there is certain limitation; Behind the ethoxyethyl group magnesium carbonate disacidify, help to improve paper durability, can delaying aging, but fading with diffusion, phenomenons such as the different and disacidify effect of feel after some nifves, the paper process is inhomogeneous being arranged of paper variable color, white depositions, Newton's ring, writing also appearred.It is comparatively harsh that the alkoxide of magnesium then has preparation condition, shortcomings such as complex process, and books are had in various degree infringement, processed books may quicken to absorb moisture, tangible variable color is arranged, occurred yellow and translucent stain simultaneously, be not suitable as extensive deacidification agent.
Paper deacidification has carried out decades, does not see the report that uses tetraborate to carry out depickling, illustrates that those skilled in the art can not go out to use tetraborate to carry out depickling from existing deacidification agent material simple inference.Borate includes metaborate, ortho-borate and multi-borate etc.Wherein most important borate is the sodium tetraborate in the tetraborate, is commonly called as borax (Na
2B
4O
710H
2O), can be used as the glaze of disinfectant, antistaling and antiseptic agent, water softener, eyewash, soap additive, pottery and frit etc., borax also has important effect in industrial production.With sodium tetraborate the tetraborate of some similar quality is arranged, two SP are arranged in its borate
2The BO of hydridization
3Plane triangle and two SP
3The BO of hydridization
4Tetrahedron is tied by top, shared angle O atom.In the aqueous solution of tetraborate, there is following hydrolysising balance:
Because there is such hydrolysising balance, the tetraborate aqueous solution can be made the pH correcting fluid.Because the pH of the saturated tetraborate aqueous solution can effectively avoid solution alkalescence strong excessively, the residual problem not up to standard of alkali about 9.24.In addition, the SP in the borate
2The short of electricity minor structure makes tetraborate have stronger electron-withdrawing power, is easy to the polyol adduction and strengthens the ability of intermolecular force with this; Because it is the special short of electricity minor structure of boride makes its compound have multiple special nature, frequent in addition as the modifier in the industrial production, but without any relating in the application aspect paper deacidification or the enhancing.
Summary of the invention
Agent is used for the method for paper deacidification as paper deacidification to the invention provides a kind of solubility tetraborate.
Technical scheme of the present invention is, be meant when 20 ℃ of the room temperatures that as the solubility tetraborate of paper deacidification agent solubility is greater than the tetraborate of 0.002g/ml in the solvent, described solubility tetraborate is the mixture of a kind of solubility tetraborate or several solubility tetraborates, and the solubility tetraborate can randomly mix use with other deacidification agents; The aqueous solution of paper deacidification agent mixes for 100:0～10:90 by volume with dissimilar organic solvents, above-mentioned paper deacidification agent aqueous solution mass concentration scope 0.005%～saturated, paper deacidification agent consumption is 0.001～10 times of paper quality, and deacidification agent solution and paper contact time are 0.2～5h.
Aforesaid method, used organic solvent are one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the glycerine.
Aforesaid method, the mode of utilizing this deacidification agent to implement depickling comprises all depickling behaviors that this solubility deacidification agent is contacted with paper such as immersion, sprinkling, atomizing or supercritical fluid depickling.
Aforesaid method, handled paper can be Modern Paper and ancient paper, and treating capacity can be single-sheet stationery or multipage paper or books.
Aforesaid method, the preferred mass concentration scope of above-mentioned paper deacidification agent is 0.14～3.52%, paper deacidification agent solution volume value is 0.005～10 times of paper quality preferably, deacidification agent solution and paper contact time be 0.6～2.5h preferably, used organic solvent is ethanol preferably, and water and ethanol volume ratio be 90:10～30:70 preferably
Aforesaid method is characterized in that above-mentioned several solubility tetraborate is lithium tetraborate, sodium tetraborate, dipotassium tetraborate or calcium tetraborate.
The present invention utilizes the solubility tetraborate in the aqueous solution hydrolysis can take place, and as the characteristic of pH buffer, with its saturated aqueous solution and dissimilar organic solvents according to certain volume than after mixing, the acidic materials in the paper are neutralized.In the process of depickling, tetraborate solution not only can effectively be controlled at pH value of paper desirable scope, and promptly neutral to 8.5, the residual situation of its alkali is also good; In the senile experiment, sheet processed has been slowed down the further acidifying of paper, and the Long-term Storage of paper has been played protective effect.
The present invention has utilized the sub-property of the typical short of electricity of tetraborate, promptly have the stronger ability of accepting electronics and self-polymerization easily takes place, form complex, with ability such as polyol adduction.With process that paper contacts in, can combine with the hydroxyl of cellulosic molecule, improve the active force between cellulosic molecule, improved strength of paper to a certain extent.
The method of utilizing the solubility tetraborate to modern book or ancient books depickling provided by the invention, do not cause the bigger variation of texture of paper colourity, tetraborate be difficult for paper in easily some coloured group of oxidation react, so significant change does not take place in paper color.
The solubility tetraborate that the present invention adopts also has certain biocidal property, can suppress microbial growth, to a certain extent paper has been played protective effect.
Though the embodiment of the invention has only been enumerated several in the tetraborate, but the tetraborate that can be used for paper deacidification is not only to only limit to this several tetraborates, those skilled in the art can use all solubility tetraborates to carry out paper deacidification according to the principle of the invention.
Carry out paper deacidification though the present invention only chooses the most cheap newspaper, this technology is not only to only limit to newspaper is carried out depickling.Newspaper and books all are to be a kind of mode that carrier carries out the Word message record with the paper, and the bound volume and the books of newspaper just vary in size.
The present invention realizes by following scheme:
Getting the mass concentration scope mixes according to certain volume proportion with dissimilar organic solvent at the tetraborate aqueous solution of 0.005%～saturated concentration (being preferably 0.14～3.52%), proportioning is that 100:0～10:90(is preferably 90:10～30:70), adopt and soak, spray, depickling modes such as atomizing or supercritical fluid, be preferably 0.6～2.5h) through 0.2～5h(, according to the deacidification agent solution usage is 0.001～10 times (being preferably 0.005～10) of paper quality, act on acidated ancient books paper, with in and paper in acidic materials, the pH value behind the paper deacidification is 7.1～8.5.Paper after the depickling dries by the fire 72h(and is equivalent to 25 years under field conditions (factors) in 105 ℃), carry out the artificial ageing simulated experiment, detect the maintenance situation of its pH and intensity.
Deacidification agent comprises all solubility tetraborates, as borax (Na
2B
4O
710H
2O), Na
2B
4O
75H
2O, Li
2B
4O
7(anhydrous), K
2B
4O
7, CaB
4O
7Deng in the tetraborate one or more; Solvent for use is but is not only one or more mixture (being preferably the mixture of water or ethanol or water and ethanol) in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol, the G ﹠ W, can be to dissolve any solvent of deacidification agent and composition thereof.
Beneficial effect of the present invention is:
1. use the deacidification agent of solubility borate solution as paper, pH value of paper can be controlled at suitable scope after the depickling, promptly between 7.1～8.5, paper is alkaline moderate after the depickling, and paper is played good deacidification effect; Because saturated tetraborate pH value of aqueous solution is less than 9.30, avoided that the pH value is too high to cause the further basic hydrolysis of cellulose.
2. use solubility tetraborate solution as deacidification agent, be difficult for paper in some chromophoric group react, after depickling was handled, obvious variation did not take place in the colourity of paper.
3. boron element has the sub-configuration of special short of electricity, can form electron-defect compound.Tetraborate belongs to typical electron-defect compound, and the stronger ability of accepting electronics is arranged, and have easy generation self-polymerization, form complex, with ability such as polyol adduction.With process that paper contacts in, can combine with the hydroxyl of cellulosic molecule, improve the active force between cellulosic molecule, improved strength of paper to a certain extent.
4. when the retention of research deacidification agent, by the artificial ageing simulated experiment, baking 72h(is equivalent to 25 years under field conditions (factors) in 105 ℃) pH value and the intensity of test paper in back after wearing out, it keeps in order.
5. tetraborate also has certain biocidal property, helps the long preservation of paper.
Specific embodiments
Further elaborate using method of the present invention below by embodiment.
New York Times newspaper in 1989 is adopted in experiment, and its various performance parameters such as following table are listed:
| pH | Tensile strength (KN/m) | Percentage elongation (%) | Tearability mN) | Folding strength (inferior) |
| 3.23 | 1.72 | 0.87 | 122.0 | 5 |
Embodiment 1
The about 130g of New York Times newspaper that got 1989 packs in the suitably big or small container, under 25 ℃ of room temperatures, be that the mixed of 80:20 is even according to volume ratio with sodium tetraborate saturated aqueous solution and ethanol, get the alcohol solution of 850ml, immersion treatment 40min, in and paper in acidic materials.Paper pH is 8.46 after the depickling; Tensile strength is 1.82, than having improved 5.8% before the depickling; Percentage elongation is 1.39, than having improved 59.8% before the depickling; Tearability is 146.8, than having improved 20.3% before the depickling; Folding strength is 7, than having improved 40% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Before and after the paper deacidification, the aged properties parameter comparison is as shown in the table:
| ? | pH | Tensile strength | Percentage elongation % | Tearability mN | Folding strength |
| After the depickling | 8.46 | 1.82 | 1.39 | 146.8 | 7 |
| After aging | 8.02 | 1.71 | 1.11 | 135.2 | 4 |
Embodiment 2
Get the about 207g of New York Times newspaper in 1989, in the container of the suitable size of packing into, under 25 ℃ of room temperatures, be that the mixed of 80:20 is even according to volume ratio with tetraborate (sodium tetraborate, dipotassium tetraborate, calcium tetraborate etc.) saturated aqueous solution and ethanol, get the alcohol solution of 1200ml, immersion treatment 40min, in and paper in acidic materials.Take off the listed deacidification agent of table, mix with ethanol, adopt identical condition, the paper of same amount is handled as reference according to identical solvent volume proportioning.More as can be seen, use borate to carry out depickling from the depickling result, its deacidification effect obviously is better than the deacidification agent of the listed other types of following table.Intensity keeps good behind 105 ℃ of aging 72 lab scales.
Before and after the paper deacidification, the aged properties parameter comparison is as shown in the table:
| ? | Na 2B 4O 7 | K 2B 4O 7 | CaB 4O 7 | CaCO 3 | Ca(C 2H 5COO) 2 | Ca(OH) 2 | MgCO 3 | Mg(HCO 3) 2 | Mg(OH) 2 |
| pH | 8.33 | 8.38 | 7.32 | 6.75 | 6.84 | 9.12 | 6.70 | 6.71 | 6.78 |
Embodiment 3
Get the about 110g of New York Times newspaper in 1989, in the container of the suitable size of packing into, under 25 ℃ of room temperatures, be that the mixed of 25:25:50 is even according to volume ratio with sodium tetraborate saturated aqueous solution and the dipotassium tetraborate aqueous solution and ethanol, get the alcohol solution of 950ml, immersion treatment 40min, in and paper in acidic materials.Paper pH is 8.24 after the depickling; Tensile strength is 1.99, than having improved 15.7% before the depickling; Percentage elongation is 1.21, than having improved 68.1% before the depickling; Tearability is 142.0, than having improved 16.4% before the depickling; Folding strength is 8, than having improved 60% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 4
Get the about 211g of New York Times newspaper in 1989, pack in the atomising device of 2L, under 25 ℃ of room temperatures, be that the mixed of 40:20:40 is even according to volume ratio with dipotassium tetraborate saturated aqueous solution and calcium tetraborate saturated aqueous solution and ethanol, get the alcohol solution of 1500ml, from atomizer, squeeze into mixed solution, handle 1.5h, in and the acidic materials in the paper.Paper pH is 8.19 after the depickling; Tensile strength is 2.24, than having improved 30.2% before the depickling; Percentage elongation is 1.24, than having improved 41.7% before the depickling; Tearability is 145.5, than having improved 19.3% before the depickling; Folding strength is 8, than having improved 60% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 5
Get the about 240g of New York Times newspaper in 1989, pack in the atomising device of 2L, under 25 ℃ of room temperatures, be that the mixed of 65:35 is even according to volume ratio with calcium tetraborate saturated aqueous solution and ethanol, get the alcohol solution of 1800ml, from atomizer, squeeze into mixed solution, handle 1.5h, in and the acidic materials in the paper.Paper pH is 7.59 after the depickling; Tensile strength is 2.23, than having improved 29.7% before the depickling; Percentage elongation is 1.33, than having improved 52.9% before the depickling; Tearability is 192.8, than having improved 58.0% before the depickling; Folding strength is 14, than having improved 180% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 6
Get the about 187g of New York Times newspaper in 1989, in the container of the suitable size of packing into, under 25 ℃ of room temperatures, be that the mixed of 30:30:40 is even according to volume ratio with lithium tetraborate saturated aqueous solution and sodium tetraborate saturated aqueous solution and ethanol, get the 1000ml watering can of packing into, paper spray is handled 1h, in and the acidic materials in the paper.Paper pH is 8.47 after the depickling; Tensile strength is 1.95, than having improved 13.4% before the depickling; Percentage elongation is 1.32, than having improved 51.7% before the depickling; Tearability is 152.0, than having improved 24.6% before the depickling; Folding strength is 8, than having improved 40% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 7
Get the about 301g of New York Times newspaper in 1989, in the container of the suitable size of packing into, under 25 ℃ of room temperatures, be that the mixed of 75:25 is even according to volume ratio with sodium tetraborate saturated aqueous solution and ethanol, get the 2400ml watering can of packing into, paper spray is handled 1h, in and the acidic materials in the paper.Paper pH is 8.19 after the depickling; Tensile strength is 2.02, than having improved 17.4% before the depickling; Percentage elongation is 1.38, than having improved 58.6% before the depickling; Tearability is 146.0, than having improved 19.7% before the depickling; Folding strength is 8, than having improved 60% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 8
Get the about 169g of New York Times newspaper in 1989, the 2L supercritical CO 2 of packing into is handled in the still, at 16MPa, under 38 ℃ the condition, squeeze into entrainer sodium tetraborate saturated aqueous solution, the calcium tetraborate aqueous solution-ethanol (45:40:15) from auxiliary pump, 1000ml solution is handled 2.5h altogether, and the flow of CO2 fluid is 0.002t/h.Paper pH is 8.03 after the depickling; Tensile strength is 2.32, than having improved 34.9% before the depickling; Percentage elongation is 1.26, than having improved 44.8% before the depickling; Tearability is 184.8, than having improved 51.5% before the depickling; Folding strength is 10, than having improved 100% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 9
Get the about 174g of New York Times newspaper in 1989, the 2L supercritical CO 2 of packing into is handled in the still, at 22MPa, under 36 ℃ the condition, squeeze into entrainer dipotassium tetraborate saturated aqueous solution-alcohol mixed solution (volume ratio is 80:20) 1200ml from auxiliary pump, handle 3.5h, the flow of CO2 fluid is 0.002t/h.Paper pH is 8.19 after the depickling; Tensile strength is 2.14, than having improved 24.4% before the depickling; Percentage elongation is 1.23, than having improved 41.4% before the depickling; Tearability is 192.8, than having improved 58.0% before the depickling; Folding strength is 12, than having improved 140% before the depickling.Aging back pH and intensity keep good, and deacidification effect is good.
Embodiment 10
Get the about 216g of New York Times newspaper in 1989, the 2L supercritical CO of packing into
2Handle in the still,, under 36 ℃ the condition, squeeze into entrainer dipotassium tetraborate saturated aqueous solution-alcohol mixed solution (volume ratio is 60:40) 1600ml, handle 4h, CO from auxiliary pump at 25MPa
2The flow of fluid is 0.002t/h.Supercritical CO
2After the processing, pH value of paper is 8.38, and aging back pH keeps good; The paper tensile strength is 2.72, than having improved 58.2% before the depickling; Percentage elongation is 1.57, and than having improved 80.4% before the depickling, tearability 195.2 is than having improved 60% before the depickling; Folding strength is 14, than having improved 180% before the depickling; Intensity keeps good behind 105 ℃ of aging 72 lab scales.
Embodiment 11
Get the about 108g of New York Times newspaper in 1989, the 2L supercritical CO of packing into
2Handle in the still, at 24MPa, under 39 ℃ the condition, squeeze into entrainer respectively from auxiliary pump, each sodium tetraborate saturated aqueous solution-alcohol mixed solution (volume ratio is 50:50) 700ml handles 1.4h, CO
2The flow of fluid is 0.002t/h.After the first supercritical processing, pH value of paper is 8.33, and aging back pH keeps good; The paper tensile strength is 2.70, than having improved 56.9% before the depickling; Percentage elongation is 1.54, than having improved 77.0% before the depickling; Tearability 204.2 is than having improved 67.2% before the depickling; Folding strength is 13, than having improved 160% before the depickling; Intensity keeps good behind 105 ℃ of aging 72 lab scales.
Embodiment 12
Get the about 114g of New York Times newspaper in 1989, the 2L supercritical CO of packing into
2Handle in the still,, under 35 ℃ the condition, squeeze into entrainer dipotassium tetraborate saturated aqueous solution and alcohol mixed solution (volume ratio is 50:50) 1000ml, handle 2h, CO from auxiliary pump at 22MPa
2The flow of fluid is 0.002t/h.Get the deacidification agent of identical proportioning, equal volume, adopt spraying to handle the paper of equal in quality as reference.After the first supercritical processing, pH value of paper is a 8.49(spraying 8.20), aging back pH keeps good; The paper tensile strength is a 2.82(spraying 2.44), than having improved 63.9% before the depickling; Percentage elongation is a 1.49(spraying 1.42), than having improved 77.0% before the depickling; Tearability 199.7(spraying 171.2), than having improved 63.7% before the depickling; Folding strength is a 14(spraying 11), than having improved 180% before the depickling; Aging back intensity keeps good, keeps effect and is better than infusion method.
Embodiment 13
Get the about 149g of New York Times newspaper in 1989, the 2L supercritical CO of packing into
2Handle in the still, at 21MPa, under 38 ℃ the condition, squeeze into entrainer sodium tetraborate saturated aqueous solution and alcohol mixed solution (volume proportion 75:25) from auxiliary pump, 750ml solution is handled 1.5h, CO altogether
2The flow of fluid is 0.002t/h.Get the deacidification agent of identical proportioning, equal volume, adopt spraying to handle the paper of equal in quality as reference.After the first supercritical processing, the paper tensile strength is a 2.82(spraying 2.44), than having improved 63.9% before the depickling; Percentage elongation is a 1.46(spraying 1.21), than having improved 67.8% before the depickling; Tearability 184.2(spraying 151.2), than having improved 51.5% before the depickling; Folding strength is a 12(spraying 8), than having improved 140% before the depickling; Aging back intensity keeps good, keeps effect and is better than infusion method.
Claims (8)
1. agent is used for the method for paper deacidification as paper deacidification for a solubility tetraborate, it is characterized in that: be meant when 20 ℃ of the room temperatures that as the solubility tetraborate of paper deacidification agent solubility is greater than the tetraborate of 0.002g/ml in the solvent, described solubility tetraborate is the mixture of a kind of solubility tetraborate or several solubility tetraborates, and the solubility tetraborate can randomly mix use with other deacidification agents; The aqueous solution of paper deacidification agent mixes for 100:0～10:90 by volume with dissimilar organic solvents, above-mentioned paper deacidification agent aqueous solution mass concentration scope 0.005%～saturated, paper deacidification agent consumption is 0.001～10 times of paper quality, and deacidification agent solution and paper contact time are 0.2～5h.
2. the method for claim 1, it is characterized in that: used organic solvent is one or more in methyl alcohol, ethanol, propyl alcohol, isopropyl alcohol or the glycerine.
3. the method for claim 1 is characterized in that: the mode that depickling is implemented in above-mentioned paper deacidification agent comprises all depickling behaviors that this solubility deacidification agent is contacted with paper of immersion, sprinkling, atomizing or supercritical fluid depickling.
4. the method for claim 1, it is characterized in that: handled paper is Modern Paper or ancient paper.
5. the method for claim 1, it is characterized in that: handled paper is single-sheet stationery or multipage paper or books.
6. the method for claim 1, it is characterized in that: above-mentioned paper deacidification agent mass concentration scope is 0.14～3.52%, and paper deacidification agent solution volume value is 0.005～10 times of paper quality, and deacidification agent solution and paper contact time are 0.6～2.5h.
7. the method for claim 1, it is characterized in that: used organic solvent is an ethanol, the volume ratio of water and ethanol is 90:10～30:70.
8. the method for claim 1, it is characterized in that: above-mentioned several solubility tetraborates are lithium tetraborate, sodium tetraborate, dipotassium tetraborate or calcium tetraborate.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147353A (en) * | 2013-03-29 | 2013-06-12 | 广东工业大学 | Ultrasound-assisted method for deacidification of paper |
| CN104652172A (en) * | 2015-02-04 | 2015-05-27 | 广州乾程化工科技发展有限公司 | Paper historical relic deacidifying and reinforcing protective material and preparation method thereof |
| CN105274900A (en) * | 2015-12-02 | 2016-01-27 | 广东工业大学 | One-step paper deacidification strengthening and enhancing agent and method |
| CN107313295A (en) * | 2017-07-23 | 2017-11-03 | 复旦大学 | A kind of acidifying and the guard method of brittle paper fibre |
| CN108004847A (en) * | 2017-11-28 | 2018-05-08 | 华南理工大学 | A kind of new ancient books depickling restorative procedure |
| CN108360296A (en) * | 2018-03-06 | 2018-08-03 | 杭州众材科技有限公司 | A kind of paper sheet deacidification agent and its preparation method and application |
| CN109371754A (en) * | 2018-09-25 | 2019-02-22 | 首都博物馆 | A kind of paper sheet deacidification agent composition and the acid stripping method for being acidified paper |
| CN110106743A (en) * | 2019-05-31 | 2019-08-09 | 华南理工大学 | A kind of method of preparation and use being acidified aging paper document depickling reinforcing agent |
| CN110552241A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Method for deacidifying and enhancing acidified and aged paper documents by using sodium silicate or borax and polyamide epichlorohydrin compound |
| CN114934403A (en) * | 2022-05-18 | 2022-08-23 | 杭州众材科技股份有限公司 | Paper bacteriostatic deacidification agent, preparation method and application |
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| CN101538816A (en) * | 2009-04-27 | 2009-09-23 | 广东工业大学 | Paper deacidification method |
| CN102086613A (en) * | 2010-11-17 | 2011-06-08 | 广州市余平图文实业有限公司 | Preparation method of paper sheet deacidification agent |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103147353A (en) * | 2013-03-29 | 2013-06-12 | 广东工业大学 | Ultrasound-assisted method for deacidification of paper |
| CN104652172A (en) * | 2015-02-04 | 2015-05-27 | 广州乾程化工科技发展有限公司 | Paper historical relic deacidifying and reinforcing protective material and preparation method thereof |
| CN105274900A (en) * | 2015-12-02 | 2016-01-27 | 广东工业大学 | One-step paper deacidification strengthening and enhancing agent and method |
| CN107313295A (en) * | 2017-07-23 | 2017-11-03 | 复旦大学 | A kind of acidifying and the guard method of brittle paper fibre |
| CN108004847A (en) * | 2017-11-28 | 2018-05-08 | 华南理工大学 | A kind of new ancient books depickling restorative procedure |
| CN108360296A (en) * | 2018-03-06 | 2018-08-03 | 杭州众材科技有限公司 | A kind of paper sheet deacidification agent and its preparation method and application |
| CN109371754A (en) * | 2018-09-25 | 2019-02-22 | 首都博物馆 | A kind of paper sheet deacidification agent composition and the acid stripping method for being acidified paper |
| CN109371754B (en) * | 2018-09-25 | 2020-12-25 | 首都博物馆 | Paper deacidification agent composition and deacidification method for acidified paper |
| CN110106743A (en) * | 2019-05-31 | 2019-08-09 | 华南理工大学 | A kind of method of preparation and use being acidified aging paper document depickling reinforcing agent |
| CN110552241A (en) * | 2019-07-12 | 2019-12-10 | 华南理工大学 | Method for deacidifying and enhancing acidified and aged paper documents by using sodium silicate or borax and polyamide epichlorohydrin compound |
| CN114934403A (en) * | 2022-05-18 | 2022-08-23 | 杭州众材科技股份有限公司 | Paper bacteriostatic deacidification agent, preparation method and application |
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