CN110079178A - It the protectant preparation method of transparent hydrophobic and its is applied in historical relic's protection - Google Patents
It the protectant preparation method of transparent hydrophobic and its is applied in historical relic's protection Download PDFInfo
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000011449 brick Substances 0.000 claims abstract description 44
- 239000003223 protective agent Substances 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 23
- 239000011737 fluorine Substances 0.000 claims abstract description 23
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 21
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000003607 modifier Substances 0.000 claims abstract description 13
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 12
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract 2
- 239000000654 additive Substances 0.000 claims description 17
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 230000000996 additive effect Effects 0.000 claims description 16
- 239000004615 ingredient Substances 0.000 claims description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- 229920005989 resin Polymers 0.000 claims description 8
- 238000007598 dipping method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000005507 spraying Methods 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052681 coesite Inorganic materials 0.000 claims 8
- 229910052906 cristobalite Inorganic materials 0.000 claims 8
- 229910052682 stishovite Inorganic materials 0.000 claims 8
- 229910052905 tridymite Inorganic materials 0.000 claims 8
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000004575 stone Substances 0.000 abstract description 5
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 238000004886 process control Methods 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 19
- 238000004364 calculation method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 5
- 230000007935 neutral effect Effects 0.000 description 5
- 230000006378 damage Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000032683 aging Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 150000003961 organosilicon compounds Chemical class 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
Description
技术领域technical field
本发明涉及一种涂层材料或者中性固化性组合物其制备方法及其应用，特别是涉及一种无机-有机疏水涂层材料或者中性固化性组合物其制备方法及其应用，应用于复合材料或者文物保护技术领域。The present invention relates to a coating material or a neutral curable composition, a preparation method and application thereof, in particular to an inorganic-organic hydrophobic coating material or a neutral curable composition, a preparation method and application thereof. Composite materials or cultural relics protection technology field.
背景技术Background technique
目前，Paraloid B-72(简称B-72)丙烯酸树脂在文物方面应用比较广泛，效果比较好，具有可逆性。(张秉坚,张栋梁,铁景沪.测量文物保护材料可逆率的探索性研究[J].中国材料进展,2012,31(11):33-36.)然而，丙烯酸树脂也有一定的不足，比如会有容易泛黄，开裂等现象。研究人员通过杂交，官能团接枝和特殊添加剂的使用来优化有机涂层。中国专利石质彩绘加固剂(CN201310329984.3)公布了使用Paraloid B-72加入一定量的PrimalSF-016、乙酸乙酯、UV-531、光稳定剂770组成制备出石质彩绘加固剂的方法。此发明具有耐水、耐酸、耐碱、抗老化能力等优点。但都是高分子物质，与无机物相容性较差。专利申请号为CN201210252652.5的固化性组合物以及有机硅化合物的制备方法通过使两种硅化合物在碱性条件下水解共缩聚而得到的有机硅化合物具有优异的稳定性，并且对基材的粘合性能优异。但制备方法比较繁琐，得到的涂层具有碱性，在一定程度上破坏文物。因此，寻求一种可靠、温和和制备工艺简单的保护剂尤为重要，成为亟待解决的技术问题。At present, Paraloid B-72 (B-72 for short) acrylic resin is widely used in cultural relics, with good effect and reversibility. (Zhang Bingjian, Zhang Dongliang, Tie Jinghu. Exploratory research on measuring the reversibility of cultural relics protection materials [J]. Progress in Chinese Materials, 2012, 31(11): 33-36.) However, acrylic resins also have certain shortcomings, such as It is easy to yellow, crack and so on. The researchers optimized the organic coating through hybridization, functional group grafting and the use of special additives. The Chinese patent stone color painting reinforcement agent (CN201310329984.3) discloses a method for preparing a stone color painting reinforcement agent by adding a certain amount of PrimalSF-016, ethyl acetate, UV-531, and light stabilizer 770 to Paraloid B-72. The invention has the advantages of water resistance, acid resistance, alkali resistance and aging resistance. However, they are all macromolecular substances and have poor compatibility with inorganic substances. The curable composition and the preparation method of the organosilicon compound with the patent application number CN201210252652.5 The organosilicon compound obtained by hydrolyzing and copolycondensing two silicon compounds under alkaline conditions has excellent stability, and has excellent stability to the substrate. Excellent adhesion properties. However, the preparation method is cumbersome, and the obtained coating is alkaline, which damages the cultural relics to a certain extent. Therefore, it is particularly important to seek a reliable, mild and simple protective agent, which has become an urgent technical problem to be solved.
发明内容SUMMARY OF THE INVENTION
为了解决现有技术问题，本发明的目的在于克服已有技术存在的不足，提供一种透明疏水保护剂的制备方法及其在文物保护中应用，能实现安全、可控、简单的古砖类文物保护涂层制备和使用，可以减缓古砖、古代砖雕的风化侵蚀和纸质文物破坏问题。In order to solve the problems of the prior art, the purpose of the present invention is to overcome the deficiencies of the prior art, and to provide a preparation method of a transparent hydrophobic protective agent and its application in the protection of cultural relics, which can realize safe, controllable and simple ancient bricks. The preparation and use of cultural relic protection coatings can slow down the weathering erosion of ancient bricks and ancient brick carvings and the destruction of paper cultural relics.
为达到上述目的，本发明采用如下技术方案：To achieve the above object, the present invention adopts the following technical solutions:
一种透明疏水保护剂，其成分按照质量百分比配比如下：A transparent hydrophobic protective agent, the composition of which is formulated according to the mass percentage as follows:
改性纳米SiO2 10wt％～12wt％；Modified nano-SiO 2 10wt%～12wt%;
改性B-72 88wt％～90wt％；Modified B-72 88wt%～90wt%;
所述改性纳米SiO2的粒度尺寸为20～50nm；The particle size of the modified nano-SiO 2 is 20-50 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 13.5～19.6wt％；B-72 13.5～19.6wt%;
丙酮 77.3～85.16wt％；Acetone 77.3～85.16wt%;
含氟添加剂 0.99～3.9wt％。Fluorine-containing additive 0.99～3.9wt%.
优选上述含氟添加剂采用氟碳树脂。Preferably, a fluorocarbon resin is used as the above-mentioned fluorine-containing additive.
一种本发明透明疏水保护剂的制备方法，包括如下步骤：A preparation method of a transparent hydrophobic protective agent of the present invention, comprising the following steps:
a.原料准备：按照照质量百分比配比如下准备原料组分：a. Raw material preparation: Prepare the raw material components according to the mass percentage ratio as follows:
改性纳米SiO2 10wt％～12wt％；Modified nano-SiO 2 10wt%～12wt%;
改性B-72 88wt％～90wt％；Modified B-72 88wt%～90wt%;
所述改性纳米SiO2的粒度尺寸为20～50nm；The particle size of the modified nano-SiO 2 is 20-50 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 13.5～19.6wt％；B-72 13.5～19.6wt%;
丙酮 77.3～85.16wt％；Acetone 77.3～85.16wt%;
含氟添加剂 0.99～3.9wt％。Fluorine-containing additive 0.99～3.9wt%.
b.按照所述步骤a配方配料，在室温下，以纳米二氧化硅为原料，HMDS为改性剂，无水乙醇和异丙醇为溶剂，进行搅拌20～24小时均匀混合，制备得到改性纳米二氧化硅；将改性B-72组分的各成分进行成分均匀混合得到含氟改性剂改性的B-72丙烯酸树脂；然后将改性纳米二氧化硅加入到含氟改性剂改性的B-72丙烯酸树脂中，得到透明疏水保护剂。本发明方法是一种温和、简便、能很好地用于古砖保护的透明疏水保护剂制备的方法。b. According to the formula ingredients of step a, at room temperature, using nano-silica as raw material, HMDS as modifier, absolute ethanol and isopropanol as solvents, stir and evenly mix for 20 to 24 hours, and prepare the modified B-72 acrylic resin modified by fluorine-containing modifier is obtained by uniformly mixing the components of the modified B-72 component; then the modified nano-silica is added to the fluorine-containing modified In the B-72 acrylic resin modified by the agent, a transparent hydrophobic protective agent was obtained. The method of the invention is a mild and simple method for preparing a transparent hydrophobic protective agent which can be well used for the protection of ancient bricks.
一种本发明透明疏水保护剂的在文物保护中的应用，将透明疏水保护剂用喷涂或浸渍的方法均匀涂覆在古砖、古代砖雕、其他硅酸盐材质或者纸质文物表面上，在室温下自然晾干，最终制得用于古砖、古代砖雕、其他硅酸盐材质或者纸质文物保护的透明疏水涂层，进行古砖、古代砖雕、其他硅酸盐材质或者纸质文物保护。An application of the transparent hydrophobic protective agent of the present invention in the protection of cultural relics, the transparent hydrophobic protective agent is evenly coated on the surface of ancient bricks, ancient brick carvings, other silicate materials or paper cultural relics by spraying or dipping, Dry naturally at room temperature, and finally obtain a transparent hydrophobic coating for the protection of ancient bricks, ancient brick carvings, other silicate materials or paper cultural relics, for ancient bricks, ancient brick carvings, other silicate materials or paper Quality cultural relics protection.
本发明与现有技术相比较，具有如下显而易见的突出实质性特点和显著优点：Compared with the prior art, the present invention has the following obvious outstanding substantive features and significant advantages:
1.本发明使用的是中性材料，中间不用酸碱进行催化，而且都是室温下进行，反应简单，温和；总体来说，此保护剂制备方法简单并且能对硅酸盐、石质和纸质物文物起到保护作用；1. What the present invention uses is neutral material, does not need acid-base catalysis in the middle, and it is all carried out at room temperature, and the reaction is simple and mild; Paper cultural relics play a protective role;
2.本发明的温和、简便的透明疏水保护剂主要应用于古砖、古代砖雕或者其他硅酸盐文物的保护；本发明保护剂呈中性，不会对砖造成腐蚀，能够有效防止紫外线对砖的老化破坏以及雨水对砖的腐蚀破坏，从而达到对砖类文物的保护要求，并有良好的效果；该保护剂也可以用于石质、纸质物文物的保护；2. The mild and simple transparent hydrophobic protective agent of the present invention is mainly used in the protection of ancient bricks, ancient brick carvings or other silicate cultural relics; the protective agent of the present invention is neutral, will not cause corrosion to bricks, and can effectively prevent ultraviolet rays The aging damage of bricks and the corrosion and damage of rainwater to bricks, so as to meet the protection requirements of brick cultural relics, and have a good effect; the protective agent can also be used for the protection of stone and paper cultural relics;
3.本发明透明疏水保护剂为无机-有机疏水材料，成本低，具有良好的疏水性，不易脱落，对古砖、古代砖雕具有良好的保护作用。3. The transparent hydrophobic protective agent of the present invention is an inorganic-organic hydrophobic material, which has low cost, good hydrophobicity, is not easy to fall off, and has a good protective effect on ancient bricks and ancient brick carvings.
具体实施方式Detailed ways
以下结合具体的实施例子对上述方案做进一步说明，本发明的优选实施例详述如下：The above scheme will be further described below in conjunction with specific embodiments, and preferred embodiments of the present invention are described in detail as follows:
实施例一：Example 1:
在本实施例中，一种透明疏水保护剂，其成分按照质量百分比配比如下：In the present embodiment, a kind of transparent hydrophobic protective agent, its composition is proportioned as follows according to mass percentage:
改性纳米SiO2 12wt％；Modified nano-SiO 2 12wt%;
改性B-72 88wt％；Modified B-72 88wt%;
所述改性纳米SiO2的粒度尺寸为20nm；The particle size of the modified nano-SiO 2 is 20 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 14.56wt％；B-72 14.56wt%;
丙酮 82.53wt％；Acetone 82.53wt%;
含氟添加剂 2.91wt％。含氟添加剂采用氟碳树脂。Fluorine-containing additive 2.91wt%. The fluorine-containing additive adopts fluorocarbon resin.
在本实施例中，一种本实施例透明疏水保护剂的制备方法，包括如下步骤：In the present embodiment, a preparation method of the transparent hydrophobic protective agent of the present embodiment includes the following steps:
a.原料准备：按照照质量百分比配比如下准备原料组分：a. Raw material preparation: Prepare the raw material components according to the mass percentage ratio as follows:
改性纳米SiO2 12wt％；Modified nano-SiO 2 12wt%;
改性B-72 88wt％；Modified B-72 88wt%;
所述改性纳米SiO2的粒度尺寸为20nm；The particle size of the modified nano-SiO 2 is 20 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 14.56wt％；B-72 14.56wt%;
丙酮 82.53wt％；Acetone 82.53wt%;
含氟添加剂 2.91wt％。含氟添加剂采用氟碳树脂。Fluorine-containing additive 2.91wt%. The fluorine-containing additive adopts fluorocarbon resin.
b.按照所述步骤a配方配料，在室温下，以纳米二氧化硅为原料，HMDS为改性剂，无水乙醇和异丙醇为溶剂，进行搅拌24小时均匀混合，制备得到改性纳米二氧化硅；含氟添加剂采用氟碳树脂；将改性B-72组分的各成分进行成分均匀混合得到含氟改性剂改性的B-72丙烯酸树脂；然后将改性纳米二氧化硅加入到含氟改性剂改性的B-72丙烯酸树脂中，得到透明疏水保护剂。b. According to the formula in step a, at room temperature, using nano-silicon dioxide as raw material, HMDS as modifier, absolute ethanol and isopropanol as solvent, stirring for 24 hours and uniformly mixing to prepare modified nanometer Silica; fluorocarbon resin is used as the fluorine-containing additive; the components of the modified B-72 component are uniformly mixed to obtain the B-72 acrylic resin modified by the fluorine-containing modifier; then the modified nano-silica It is added to the B-72 acrylic resin modified by the fluorine-containing modifier to obtain a transparent hydrophobic protective agent.
将本实施例透明疏水保护剂用喷涂或浸渍的方法均匀涂覆在古砖上，在室温下自然晾干，最终制得用于古砖文物保护的透明疏水涂层。The transparent hydrophobic protective agent of this embodiment is evenly coated on the ancient bricks by spraying or dipping, and is naturally dried at room temperature to finally obtain a transparent hydrophobic coating for the protection of ancient brick cultural relics.
试验分析测试：Test Analysis Test:
测量本实施例保护剂涂覆到砖上的接触角为142.3°，而仅用B72涂覆在砖上，接触角为94.1°，说明本实施例透明疏水涂层能够有效阻止雨水带入的酸性有害物质。原砖的平均孔径为2.2μm，而涂覆了本实施例保护剂的砖的平均孔径为2μm，二者相差较小，说明涂覆了本实施例保护剂的涂层对砖内部结构影响不大。按照GB/T9286－1998测试涂层粘附性，粘附性强度达到0级。说明本实施例保护剂具有良好的疏水性，且不易脱落，能有效的保护古砖、古代砖雕。The contact angle of the protective agent applied to the brick in this example is 142.3°, while only B72 is applied to the brick, and the contact angle is 94.1°, indicating that the transparent hydrophobic coating in this example can effectively prevent the acidity brought in by rainwater harmful materials. The average pore size of the original brick is 2.2 μm, while the average pore size of the brick coated with the protective agent of this embodiment is 2 μm. big. The adhesion of the coating was tested according to GB/T9286-1998, and the adhesion strength reached grade 0. It shows that the protective agent in this embodiment has good hydrophobicity, is not easy to fall off, and can effectively protect ancient bricks and ancient brick carvings.
实施例二：Embodiment 2:
在本实施例中，一种透明疏水保护剂，其成分按照质量百分比配比如下：In the present embodiment, a kind of transparent hydrophobic protective agent, its composition is proportioned as follows according to mass percentage:
改性纳米SiO2 10wt％；Modified nano-SiO 2 10wt%;
改性B-72 90wt％；Modified B-72 90wt%;
所述改性纳米SiO2的粒度尺寸为50nm；The particle size of the modified nano-SiO 2 is 50 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 14.56wt％；B-72 14.56wt%;
丙酮 82.53wt％；Acetone 82.53wt%;
含氟添加剂 2.91wt％。含氟添加剂采用氟碳树脂。Fluorine-containing additive 2.91wt%. The fluorine-containing additive adopts fluorocarbon resin.
在本实施例中，一种本实施例透明疏水保护剂的制备方法，包括如下步骤：In the present embodiment, a preparation method of the transparent hydrophobic protective agent of the present embodiment includes the following steps:
a.原料准备：按照照质量百分比配比如下准备原料组分：a. Raw material preparation: Prepare the raw material components according to the mass percentage ratio as follows:
改性纳米SiO2 10wt％；Modified nano-SiO 2 10wt%;
改性B-72 90wt％；Modified B-72 90wt%;
所述改性纳米SiO2的粒度尺寸为50nm；The particle size of the modified nano-SiO 2 is 50 nm;
按照改性纳米SiO2组分总量为100％计算，改性纳米SiO2中各成分质量百分比配比为：According to the calculation of the total amount of modified nano-SiO 2 components being 100%, the mass percentage ratio of each component in the modified nano-SiO 2 is:
按照改性B-72组分总量为100％计算，改性B-72中各成分质量百分比配比为：According to the calculation of the total amount of modified B-72 components being 100%, the mass percentage ratio of each component in the modified B-72 is:
B-72 14.56wt％；B-72 14.56wt%;
丙酮 82.53wt％；Acetone 82.53wt%;
含氟添加剂 2.91wt％。含氟添加剂采用氟碳树脂。Fluorine-containing additive 2.91wt%. The fluorine-containing additive adopts fluorocarbon resin.
b.按照所述步骤a配方配料，在室温下，以纳米二氧化硅为原料，HMDS为改性剂，无水乙醇和异丙醇为溶剂，进行搅拌24小时均匀混合，制备得到改性纳米二氧化硅；含氟添加剂采用氟碳树脂，将改性B-72组分的各成分进行成分均匀混合得到含氟改性剂改性的B-72丙烯酸树脂；然后将改性纳米二氧化硅加入到含氟改性剂改性的B-72丙烯酸树脂中，得到透明疏水保护剂。b. According to the formula in step a, at room temperature, using nano-silicon dioxide as raw material, HMDS as modifier, absolute ethanol and isopropanol as solvent, stirring for 24 hours and uniformly mixing to prepare modified nanometer Silica; the fluorine-containing additive adopts fluorocarbon resin, and the components of the modified B-72 component are uniformly mixed to obtain the B-72 acrylic resin modified by the fluorine-containing modifier; then the modified nano-silica It is added to the B-72 acrylic resin modified by the fluorine-containing modifier to obtain a transparent hydrophobic protective agent.
将本实施例透明疏水保护剂用喷涂或浸渍的方法均匀涂覆在古砖上，在室温下自然晾干，最终制得用于古砖文物保护的透明疏水涂层。The transparent hydrophobic protective agent of this embodiment is evenly coated on the ancient bricks by spraying or dipping, and is naturally dried at room temperature to finally obtain a transparent hydrophobic coating for the protection of ancient brick cultural relics.
试验分析测试：Test Analysis Test:
测量本实施例保护剂涂覆到砖上的接触角为134.64°，而仅用B72涂覆在砖上，接触角为94.1°，说明本实施例透明疏水涂层能够有效阻止雨水带入的酸性有害物质。原砖的平均孔径为2.2μm，而涂覆了本实施例保护剂的砖的平均孔径约为2.0μm，二者相差较小，说明涂覆了本实施例保护剂的涂层对砖内部结构影响不大。按照GB/T9286－1998测试涂层粘附性，粘附性强度达到0级。说明本实施例保护剂具有良好的疏水性，且不易脱落，能有效的保护古砖、古代砖雕。The contact angle of the protective agent applied to the brick in this example is 134.64°, while only B72 is applied to the brick, and the contact angle is 94.1°, indicating that the transparent hydrophobic coating in this example can effectively prevent the acidity brought in by rainwater harmful materials. The average pore diameter of the original brick is 2.2 μm, while the average pore diameter of the brick coated with the protective agent of this embodiment is about 2.0 μm, and the difference between the two is small, indicating that the coating coated with the protective agent of this embodiment has an effect on the internal structure of the brick. Has little effect. The adhesion of the coating was tested according to GB/T9286-1998, and the adhesion strength reached grade 0. It shows that the protective agent in this embodiment has good hydrophobicity, is not easy to fall off, and can effectively protect ancient bricks and ancient brick carvings.
综上所述，本发明上述实施例涉及一种用于古砖、古代砖雕保护的透明疏水保护剂的制备方法。室温下，以纳米二氧化硅为原料，HMDS为改性剂，制备改性纳米二氧化硅。加入用含氟改性剂改性的B-72丙烯酸树脂中，得到保护剂。该方法在常温下进行，反应条件温和，过程可控，制得的涂层具有防水、不易脱落的特点，而且显中性，涂覆到古砖、古代砖雕和其他硅酸盐材质文物表面上，对文物具有良好的保护作用，该保护剂也可以用于石质、纸质物文物的保护。To sum up, the above embodiments of the present invention relate to a method for preparing a transparent hydrophobic protective agent for protecting ancient bricks and ancient brick carvings. At room temperature, nano-silica was used as raw material and HMDS as modifier to prepare modified nano-silica. Add to B-72 acrylic resin modified with fluorine-containing modifier to obtain protective agent. The method is carried out at room temperature, the reaction conditions are mild, and the process is controllable. The prepared coating has the characteristics of being waterproof, not easy to fall off, and is neutral, and can be applied to the surfaces of ancient bricks, ancient brick carvings and other silicate cultural relics. It has a good protective effect on cultural relics, and the protective agent can also be used for the protection of stone and paper cultural relics.
上面对本发明实施例进行了说明，但本发明不限于上述实施例，还可以根据本发明的发明创造的目的做出多种变化，凡依据本发明技术方案的精神实质和原理下做的改变、修饰、替代、组合或简化，均应为等效的置换方式，只要符合本发明的发明目的，只要不背离本发明透明疏水保护剂、其制备方法及其在文物保护中应用的技术原理和发明构思，都属于本发明的保护范围。The embodiments of the present invention have been described above, but the present invention is not limited to the above-mentioned embodiments, and various changes can also be made according to the purpose of the invention and creation of the present invention. Modifications, substitutions, combinations or simplifications should all be equivalent substitution methods, as long as they meet the purpose of the present invention, as long as they do not deviate from the transparent hydrophobic protective agent of the present invention, its preparation method, and its application in cultural relics protection. Technical principles and inventions All ideas belong to the protection scope of the present invention.
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