KR20100137057A - Nano composite epoxy adhesive for preservation of stone cultural heritage - Google Patents

Abstract

PURPOSE: A nano composite epoxy adhesive for preservation of stone cultural heritage is provided to prevent secondary damage caused by water condensation by increasing water permeability through nano pores and yellowing caused by ultraviolet rays and moisture by saturated carbon. CONSTITUTION: A nano composite epoxy adhesive for preservation of stone cultural heritage comprises: a mixture of 40~99.99wt% epoxy resin and 0.01~60wt% nano cluster filler with an epoxy group and nano pores; and a room temperature curable hardener in an equivalence ratio of 0.8~1.2. The epoxy resin is hydrogenated bisphenol A type epoxy, hydrogenated bisphenol F type epoxy, biphenol type epoxy, phenol novolac epoxy, and cresol novolac epoxy, which have two or more epoxy groups in molecule.

Description

Nano composite epoxy adhesive for preservation of stone cultural heritage

An object of the present invention relates to the composition of the adhesive for the preservation of the stone cultural property, using the epoxy resin, the nano-cluster filler having an epoxy group and nano-pores, a curing agent, a reactive diluent and a curing accelerator does not occur yellowing phenomenon is stable in color, It is a nano composite epoxy adhesive for preservation of stone cultural properties, which has excellent adhesiveness and has a breathing effect that discharges water formed inside the stone to the outside because the filler component of the adhesive has nano pores. To the technical field of adhesive compositions for

The stone cultural properties designated as national treasures and treasures of Korea are about 1470 points, and the stone pagoda is the largest proportion of Korean cultural assets, with about 53.8% of all national treasures, 42.7% of treasures, and 38.9% of important cultural properties. They are mainly granite, and most of them are very large and are located outdoors, and physical factors such as weather-freeze-melting, biological factors such as moss-microorganisms, chemical development such as acid rain-environmental pollution along with industrial development The damage to stone cultural properties is accelerating to a serious extent due to factors.

In this regard, even if the same stone cultural property, the effect is different depending on the type of adhesive applied, and the same adhesive has a different effect depending on the type of stone of the stone cultural property, so the adhesive of the stone cultural property is appropriate according to the type of rock and its preservation state. The treatment agent and treatment technology should be selected, and when selecting the adhesive, not only the reversibility of the treatment but also the permeability of the resin and the ease of operation and stability of the treatment agent are important factors. In addition, there should be no noticeable change in finish tones as well as strength, and weather resistance of the resin should be fully considered.

In addition, in Europe, most of the carbon-based stone cultural properties that contain limestone, marble, calcite, while Korea's stone cultural properties are mostly made of granite, it is difficult to preserve the damaged stone cultural properties. That is, as mentioned above, the adhesive for stone preservation should be selected according to the type of stone and the degree of weathering, and the same adhesive has different effects depending on the type of stone of the stone cultural properties. As a result of introducing the adhesive and processing technology for the old European stone cultural property without verification, the effect was insignificant or the damage to the stone cultural property was further damaged. Particularly, when the adhesive penetrates deep into the weathered stone cultural property and no adhesion occurs, the bonded part is lost. At this time, the second part is damaged not only by the adhesive but also with the part of the weathered stone, which greatly damages the cultural property. It caused a problem that occurred.

The method of repairing the peeled and peeled off parts with adhesive due to natural weathering and artificial factors is more than 90% of the number of preservation treatments. Cement has been mainly used as an adhesive in the past, but epoxy resins have been mainly used since problems such as peeling, peeling and whitening of cement due to differences in composition between cement and stone cultural properties have been raised. The epoxy resin has a characteristic of changing its chemical and physical structure by adding a hardening agent and additives, and converting it into a thermosetting material having a three-dimensional structure that is insoluble in heat or solvent, and the most commonly used epoxy resin is epichlorohydrin ( Diphenylolpropane (DPP), popularly known as Epichlorohydrine (ECH) and Bisphenol A (BPA), is a diglycidyl ether type produced by condensation reactions and other substances instead of DPP. Epoxy resins with improved properties have also been commercially produced using these as raw materials.

Epoxy has been widely used as a preservation and restoration material for cultural properties of world conservation science around 1950 since it was applied to preservation of cultural properties around 1930 for its high adhesiveness, low shrinkage and curing at room temperature. Since it was used to restore the three-layer stone tower adhesion of Silsangsa Pagoda, Araldite AW106 from Ciba-Geigy and hardener HY 837 have been mainly used for the preservation of stone cultural properties. However, due to the problems of araldite adhesives, L-30 and L-40, which have been jointly developed with the National Research Institute of Cultural Heritage and Poonglim Industry since 1998, are used for the preservation of stone cultural properties.

In addition, Ciba-Geigy's initial epoxy adhesive used various Araldite, but Araldite based on Bisphenol A has yellow surface where repair surface changes yellow due to environmental conditions such as UV and humidity. Problems such as the occurrence of cracks and the like have occurred, and recently, new epoxy resins have been researched and developed. Namely, epoxy resins include bisphenol A-based oligomers, diphenylolmethane (DPM) known as bisphenol F, and 2,2-di (4-hydroxycyclohexyl) propane hydrogenated with an aromatic ring of bisphenol A. Oligomers, phenol novolac and Cresol novolac and environmentally friendly water-based epoxy have been developed, but conventional adhesives have a dense chemical structure and low water permeability. Secondary damage occurs due to water condensation, color stability of the treated part is lowered due to color difference between stone and adhesive, and yellowing phenomenon occurs due to UV moisture after time. Since the adhesive has low stone permeability in relation to the viscosity of the adhesive, when the adhesive part is lost, There is a problem of secondary damage, which is lost together, which greatly damages cultural property.

The present invention is designed to solve the problems of the prior art as described above,

An adhesive that prevents secondary damage due to water condensation caused by condensation of water inside the stone by increasing water permeability through the nano pores by mixing the epoxy cluster, which is the main component of the adhesive, with an epoxy group and a nanocluster filler having nano pores. Epoxy resin has a color stability that does not cause yellowing due to UV and moisture over time by using a saturated carbon system without double bonds or triple bonds, and by using a reactive nanocluster filler In addition to being able to control the strength of the adhesive, it provides a high mechanical stability of the adhesive, so that the adhesive has a low stone permeability in relation to the viscosity of the adhesive. Stone culture It provides a nano composite epoxy adhesive for represervation.

The present invention in the nano composite epoxy adhesive for preservation of stone cultural properties,

A nanocomposite epoxy adhesive for preservation of stone cultural properties formed by adding a curing agent at room temperature to an equivalent ratio of 0.8 to 1.2 in a mixture of 40 to 99.99 wt% epoxy resin and 0.01 to 60 wt% epoxy cluster nanoparticle filler. In order to selectively reduce the viscosity of the adhesive, and may further include 0.01 to 40wt% reactive diluent based on the weight of the mixture of the epoxy resin and the filler, in order to obtain faster and more robust adhesive properties depending on the process environment On the basis of the mixture weight of the epoxy resin and the filler relates to a nano composite epoxy adhesive for preserving the stone cultural properties characterized in that it further comprises 0.01 ~ 4wt% of the curing accelerator.

The present invention improves the permeability of water through the nano pores by mixing a nanocluster filler having an epoxy group and nano pores in the epoxy resin which is the main component of the adhesive to prevent secondary damage due to water condensation caused by the water inside the stone does not escape to the outside In addition, the epoxy resin has a color stability that does not cause yellowing due to ultraviolet rays and moisture over time by using a saturated carbon system without double bonds or triple bonds, and by using reactive nanocluster fillers, By providing high mechanical stability as well as adhesive strength control, the stone's permeability of the adhesive is low in relation to the viscosity of the adhesive, which prevents secondary damage that causes loss of the bonded portion, such as weathered stone, and greatly damages the cultural property. It is effective.

Hereinafter, the present invention will be described in detail with reference to the drawings as a nano composite epoxy adhesive for preservation of stone cultural properties.

A nanocomposite epoxy adhesive for preservation of stone cultural properties formed by adding a curing agent at room temperature to an equivalent ratio of 0.8 to 1.2 in a mixture of 40 to 99.99 wt% epoxy resin and 0.01 to 60 wt% epoxy cluster nanoparticle filler. In order to selectively reduce the viscosity of the adhesive, and may further include 0.01 to 40wt% reactive diluent based on the weight of the mixture of the epoxy resin and the filler, in order to obtain faster and more robust adhesive properties depending on the process environment The present invention relates to a nanocomposite epoxy adhesive for masonry cultural property preservation, characterized in that it further comprises 0.01 ~ 4wt% of a curing accelerator based on the mixture weight of the epoxy resin and the filler.

40-99.99wt% epoxy resin, which is the main component in the present invention, has no unsaturated bonds such as double bonds or triple bonds and has two or more epoxy groups in the molecule in order to reduce heterogeneity with masonry cultural properties and improve color stability. Hydrogenated bisphenol A epoxy (hydrogenated bisphenol A epoxy), hydrogenated bisphenol F epoxy, biphenol type epoxy, phenol novolac epoxy, cresol novolac epoxy resin is used. In addition, preferably in order to maintain an appropriate adhesive strength in the epoxy resin of the epoxy resin of the above-mentioned epoxy resin in the case of using an epoxy having an equivalent of 100 or less, the crosslinking density is very high to show a hard property and the adhesive strength is also reduced, equivalent In the case of using an epoxy of 1000 or more, the adhesive strength is increased, but the glass transition temperature is lowered. Therefore, in order to evenly improve all the physical properties, an epoxy resin having an average equivalent weight of 100 to 1,000 is used.

In addition, the nanocluster filler having nanopores 0.01 to 60 wt% of a polyhedral oligomeric silsesquioxane (POSS) derivative having one or more silica nanostructures or epoxy groups having an average particle diameter of 1 to 10,000 nm on the surface thereof % Is included. The purpose of using the filler is to improve the mechanical properties and to introduce a structure with pores to provide a passage for discharging the water condensed inside the stone cultural property to the outside, as well as to reduce the thermal expansion rate, decrease the curing shrinkage rate, and improve wear resistance In addition, it is possible to obtain the effect of improving the flame retardancy, and if the content of the filler is less than 0.01wt%, it does not affect the mechanical properties including structural properties, and if it exceeds 60wt%, the viscosity is increased and it is uneven when stirring with other components. Mix 0.01 ~ 60wt% because it may form a limit or decompose the polymer during the process. In addition, silicate nanostructures having epoxy groups and nano pores and polyhedral oligomeric silsesquioxane (POSS) derivatives having at least one epoxy group on the surface are nanometer-sized particles with nano pores and have an epoxy group on the surface. Since it has the above, it has the advantage of being easily mixed-dispersed with the epoxy resin which is an organic type polymer resin. In addition, polyhedral oligomeric silsesquioxane (POSS) derivatives having at least one epoxy group on the surface thereof are preferably epoxycyclohexyl POSS (C ₈ H ₁₃ O ₂ ) _n (SiO _1.5 ) _n n = 8 , 10,12, (n = 8, 10)), glycidyl _{POSS (glycidyl POSS, (C 6} H 11 O 2) n (SiO 1 .5) n n = 8,10,12, (n = 8 GlycidylEthyl POSS, C ₂₀ H ₄₆ O ₁₄ Si ₈ ), Glycidylisobutyl POSS (C ₃₄ H ₇₄ O ₁₄ Si ₈ ) _, GlycidylPhenyl POSS, C ₄₈ H ₄₆ O ₁₄ Si ₈ ), Chloropropylisobutyl POSS, C ₄₈ H ₄₆ ClO ₁₂ Si ₈ ), Methacrylisobutyl POSS, C ₃₅ H ₇₄ O ₁₄ Si ₈ ), Methacrylate _{POSS (Methacryl POSS, (C 7} H 11 O 2) n (SiO 1 .5) n n = 8,10,12, (n = 8, 10)), an acrylic POSS (POSS Acrylo, (C _{8 H 9 O 2) n (SiO} 1 .5) n n = 8,10,12, (n = 8, 10)), isobutyl-POSS (POSS Acryloisobutyl, C ₃₄ H ₇₂ O ₁₄ Si _8-acryloyl), TriSilanolisobutyl POSS (C ₂₈ H ₆₆ O ₁₂ Si ₇ ), TriSilanolisoctyl POSS (C ₅₆ H ₁₂₂ O ₁₂ Si ₇ ) _, TriSilanolPhenyl POSS (C ₄₂ H ₃₈ O ₁₂ Si ₇ ), Tetrasilanolphenyl POSS (TetraSilanolPhenyl POSS, C ₄₈ H ₄₄ O ₁₄ Si ₈ ) It may be used including one or more types, but is not limited thereto.

Meanwhile, the room temperature curing type curing agent is an amine-based isophorone diamine, polypropylene glycol bis 2-aminopropyl ether {poly (propylene glycol) bis (2-aminopropyl ether)}, 4,4'-diaminodiphenyl methane, 3, 3 ', 5,5'-tetramethyl-4,4'-diaminodiphenyl methane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenyl methane, 3,3 ' -Dimethyl-5,5'-dimethyl-4,4'-diaminodiphenyl methane, 3,3'-diamino benzophenone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodi Phenols, amines, anhydrides of phenyl sulfones, 4,4'-diaminodiphenyl sulfones, aromatic amines, aliphatic amines, alicyclic amines, resol or novolac phenols of 3,4,4'-triaminediphenyl sulfone At least one of a cargo, an acid anhydride, dicyandiamide or trifluoroboron is used.

In addition, the reactive diluent may optionally further comprise 0.01 to 40wt% based on the weight of the mixture of the epoxy resin and the filler for the purpose of reducing the viscosity in the composition. Since the reactive diluent has one or more epoxy groups, the reactive diluent participates in the reaction and enters the cross-linked structure into the cured product. The use of the reactive diluent effectively improves the flowability, the defoaming property, the permeability improvement, or the filler when the adhesive is used. There is an advantage that can be added. Examples of reactive diluents of the present invention include butylglycidyl ether (BGE), phenylglycidyl ether (PGE), aliphatic glycidyl ether (C12-C14), and modi It is possible to use one comprising at least one of the Modifide-Tert-Carboxylic Dlycidyl Esters.

In addition, the main application field of the present invention is an adhesive for preservation of stone cultural properties, in order to obtain faster and more robust adhesive properties depending on the process environment, the curing accelerator is optionally added to the epoxy resin and the filler in the mixture with or without the reactive diluent. 0.01 to 4 wt% based on the weight of the mixture of the above, and as the curing accelerator, the amine complex of boron trifluoride, 2-alkyl-4-methyl imidazole in the imidazole derivative, 2-phenyl-4-alkyl already It is preferable to contain at least 1 sort (s) among phthalic anhydride, trimellitic anhydride, or dicyandiamide of a dazole or organic acid.

The following is an embodiment and comparative example related to the composition of the adhesive for preserving the stone cultural property according to the present invention. In addition, this Example and a comparative example do not restrict this invention.

Example 1

93 g of bisphenol A (ST-3000, Kukdo co. Ltd.), a hydrogenated epoxy resin, and a filler were prepared by adding 7 g of polysiloxane, a silicate nanostructure prepared by the method of FIG. 1, to a mechanical stirrer (600 rpm). Stir for minutes to prepare an epoxy resin and add isophoronediamine (IPDA, Kukdo co. Ltd.), a room temperature curing type curing agent, in an equivalent ratio, based on the mixture of hydrogenated bisphenol A and polysiloxane, to prepare a mechanic stirrer (600 rpm). Prepare the glue by stirring for 10 minutes. The nanocomposite epoxy adhesive is prepared by degassing by placing in a vacuum oven for 10 minutes to remove bubbles of the prepared adhesive.

[Example 2]

93 g of bisphenol A (ST-3000, Kukdo co. Ltd.), a hydrogenated epoxy resin, and a filler were prepared by adding 7 g of polysiloxane, a silicate nanostructure prepared by the method of FIG. 1, to a mechanical stirrer (600 rpm). Stir for minutes to prepare an epoxy resin and add a polypropylene glycol bis 2-aminopropyl ether (D230, Kukdo co. Ltd.) which is a room temperature curing type curing agent in an equivalent ratio based on the mixture of hydrogenated bisphenol A and polysiloxane. Prepare the adhesive by stirring for 10 minutes with a mechanic stirrer (600 rpm). The nanocomposite epoxy adhesive is prepared by degassing by placing in a vacuum oven for 10 minutes to remove bubbles of the prepared adhesive.

Example 3

5 minutes with mechanic stirrer (600 rpm) by adding 80 g of bisphenol A (ST-3000, Kukdo co. Ltd.), a hydrogenated epoxy resin, and 20 g of polyhedral oligomeric silsesquioxane (EP0408, Hybrid plastics co. Ltd.), a filler. Stir while to prepare the epoxy resin. Based on the mixture of hydrogenated bisphenol A and polyhedral oligomer silsesquioxane, add isophoronediamine (IPDA, Kukdo co. Ltd.), a curing agent at room temperature, in an equivalent ratio, and stir for 10 minutes with a mechanic stirrer (600 rpm). Prepare the glue. The nanocomposite epoxy adhesive is prepared by degassing by placing in a vacuum oven for 10 minutes to remove bubbles of the prepared adhesive.

Example 4

5 minutes with mechanic stirrer (600 rpm) by adding 80 g of bisphenol A (ST-3000, Kukdo co. Ltd.), a hydrogenated epoxy resin, and 20 g of polyhedral oligomeric silsesquioxane (EP0409, Hybrid plastics co. Ltd.), a filler. Stir while to prepare the epoxy resin. Based on the mixture of hydrogenated bisphenol A and polyhedral oligomer silsesquioxane, add isophoronediamine (IPDA, Kukdo co. Ltd.), a curing agent at room temperature, in an equivalent ratio, and stir for 10 minutes with a mechanic stirrer (600 rpm). Prepare the glue. The nanocomposite epoxy adhesive is prepared by degassing by placing in a vacuum oven for 10 minutes to remove bubbles of the prepared adhesive.

Comparative Example 1

The adhesive is prepared using epoxy adhesive AY103-HY956 (Ciba-Geigy Ltd.).

Comparative Example 2

Adhesives are prepared using AW106-HV953U (Ciba-Geigy Ltd.).

[Test]

The following six tests are performed using the above examples and comparative examples.

 1.Measurement of Initial Viscosity and Granite Permeability of Adhesives

1-A. Initial Viscosity Measurement-Using a Vibro viscometer (A & D Company Ltd., SV-10), the average viscosity was measured every 2 seconds at a mean temperature of 27.9 ° C for 5 minutes.

 1-B. Granite Permeability Measurement

0.01 wt% of dye (modern chemical) was added to each of the examples and the comparative examples, and then applied to granite, the adhesive surface was broken, and the cross section was measured to determine permeability.

2. Measure color and curing time after curing

After the Examples and Comparative Examples samples are applied to granite, the time at which curing is completed and the color after curing are measured.

3. Color difference analysis after treatment on gray sandstone, granite, surrogate rock

After applying the Example and Comparative Example samples to the stone, the color difference value with the untreated stone was measured with a photoelectronic colorimeter (color eye 7000A) and commissioned by the International Commission on Illumination (CIE) Lab. Represented by value. The CIE Lab color space is known as a uniform color space for human visual characteristics and is used as a coordinate system for calculating the color difference actually felt by a human. The color difference value (ΔE) was obtained by the following equation.

[Equation 1]

ΔE = ((ΔL *) ² + (Δa *) ² + (Δb *) ²) ^1/2

(ΔL value is brightness, Δa is the relationship between red and green, and Δb is the relationship between yellow and blue)

4. Measurement of d-spacing by X-ray measurement

An X-ray diffractometer (Rigaku Corp., D-MAX 2500-PC) was used to analyze at 40 kV, 100 mA. The diffraction angle was measured while increasing from 2 ° to 5.0 ° / min, the result was calculated the interlayer spacing using the following Bragg equation.

d = λ / 2 sinθ

(d: lattice spacing, λ: wavelength of X-ray, θ: Bragg angle)

5. Adhesion strength measurement

5-A. Compressive strength-Make a negative mold of silicon so that the specimen is 1.27cm in length and length and 2.54cm in height, and mix the epoxy with the sample with the correct equivalent of amine to avoid bubbles. After sufficient reaction time is poured into the silicon negative mold, compressive strength is measured by applying a vertical force using a universal testing machine (Instron 4484, Instron, UK).

5-B. Tensile strength-Specimen was treated with sandpaper No. 60 with two stainless panels 13 cm wide, 2.54 cm wide and 0.2 cm high to achieve optimum bonding to the adhesive surface. A spacer was used to apply the same. In addition, the specimens were re-fabricated to 2.54 cm, 1.3 cm and 0.2 cm in height and tensile strength was measured by the method of ISO 4587 using a universal testing machine (Instron 4484, Instron, UK). Test results were expressed as arithmetic mean of fracture stress, and Newton's fracture stress was divided by shear area (330mm ² ).

[result]

1. Measurement of initial viscosity and granite permeability of adhesive.

The initial viscosity (mPas) of the adhesive is usually closely related to the permeability of the stone, and Comparative Example 2, which has a high viscosity as a result of the test, has the lowest granite permeability, and has the same or lower viscosity as Comparative Example 1, Examples 1 and 2 , 3 and 4 have high granite permeability. In other words, the lower the viscosity of the adhesive, the easier it is to penetrate into the granite, the higher the granite permeability (mm) of the adhesive, and the adhesive penetrates deeply into the stone to form an adhesive surface, thereby preventing secondary damage caused by forming an adhesive surface only on the outside. Can be.

2. Result of color and curing time after curing.

The curing time of Examples 1, 2, 3, and 4 according to the present invention is the same as Comparative Examples 1 and 2, and can be used in the same working environment as the conventional adhesive, and Comparative Example 2 is yellow opaque in terms of color stability of the adhesive. While having a color and having a sense of heterogeneity, while Examples 1, 2, 3, and 4 have colorless and transparent colors, they have higher color stability than conventional adhesives.

3. Color difference (E) analysis results after treatment on gray sandstone, granite, and surrogate rock.

The color difference value (E) before and after the adhesive treatment is a measurement method for knowing the degree of change in color due to the adhesive. As shown in Table 1, the color differences of Examples 1, 3, and 4 are compared with those of Comparative Examples 1 and 2. On gray sandstone and granite, Example 2 showed less color difference than conventional adhesive due to inferior surrogate.

4. The result of d-spacing measurement by X-ray measurement.

As can be seen from Table 1, the interchain distances of Examples 1, 2, and 4 were longer than those of the conventional adhesive. It can be seen that the distance between chains is increased by the nanocluster filler having nano pores among the adhesive components of the embodiment, and this interchain distance serves to increase the free volume of the adhesive component and the stone together with the nanocluster filler having nano pores. It discharges the water condensed in the inside to the outside, and it shows the effect of preventing the stone damage caused by the phase change of water.

5. Result of adhesive strength measurement.

As can be seen from Table 1, the compressive strength of Examples 2 and 3 except for Example 1, which exhibits adhesive strength, has almost the same strength as that of Comparative Example 1, so there is no problem of adhesive strength, and the strength of the breakage of the adhesive Tensile strength (Tensile strength) indicates that the high value compared to Comparative Example 2, similar to 1 in the comparison, or in the case of Example 1 all showed a result having a high value.

Table 1.

1 is a method for producing a polysiloxane (polysiloxane) filler of the silicate nanostructure of Example 1.

FIG. 2 is a reaction scheme for synthesizing polysiloxane fillers, which are silicate nanostructures having epoxy groups and nanopores. FIG.

3 is a structural diagram of glycidyl POSS in a nanocluster filler having epoxy groups and nanopores.

Claims (8)

Nanocomposite epoxy adhesive for preservation of stone cultural properties made by adding a room temperature curing type curing agent in an equivalence ratio of 0.8-1.2 to a mixture of 40-99.99wt% epoxy resin and 0.01-60wt% epoxy cluster nanoparticle filler. The method of claim 1, The epoxy resin is hydrogenated bisphenol A epoxy, hydrogenated bisphenol F epoxy, biphenol type epoxy, phenol novolac epoxy, cresol novolac epoxy having no double or triple bond unsaturated bonds and having two or more epoxy groups in a molecule. Nanocomposite adhesive for preservation of stone cultural properties, characterized in that it comprises at least one of the epoxy resin having an average equivalent weight of 100 ~ 1,000. The method of claim 1, The nanocluster filler having the epoxy group and the nano pores is a silica-based nanostructure or polyhedral oligomeric silsesquioxane (POSS) derivative, nanocomposite adhesive for preserving the stone culture material, characterized in that. The method of claim 3, wherein The nanocomposite adhesive for preserving the stone culture material, characterized in that the average particle diameter of the silica-based nanostructure or polyhedral oligomeric silsesquioxane (POSS) derivative having the epoxy group and the nano pores is 1 ~ 10,000nm. The method of claim 3, wherein The epoxy group and the polyhedral oligomeric silsesquioxane has the nanopores (polyhedral oligomeric silsesquioxane, POSS) derivative epoxy cycloalkyl haeksil _{POSS (EpoxyCyclohexyl POSS (C 8 H} 13 O 2) n (SiO 1 .5) n n = 8,10 , 12, (n = 8, 10)), glycidyl _{POSS (glycidyl POSS, (C 6} H 11 O 2) n (SiO 1 .5) n n = 8,10,12, (n = 8, 10 )), GlycidylEthyl POSS, C ₂₀ H ₄₆ O ₁₄ Si ₈ ) _, Glycidylisobutyl POSS, C ₃₄ H ₇₄ O ₁₄ Si ₈ ) _, GlycidylPhenyl POSS , C ₄₈ H ₄₆ O ₁₄ Si ₈ ), Chloropropylisobutyl POSS, C ₄₈ H ₄₆ ClO ₁₂ Si ₈ ), Methacrylisobutyl POSS, C ₃₅ H ₇₄ O ₁₄ Si ₈ ) _, Meta Methacryl POSS, (C ₇ H ₁₁ O ₂ ) _n (SiO _1.5 ) _n n = 8,10,12, (n = 8, 10)), Acrylo POSS, (C ₈ H ₉ O ₂ ) _n (SiO _1.5 ) _n n = 8,10,12, (n = 8, 10)), Acryloisobutyl POSS, C ₃₄ H ₇₂ O ₁₄ Si ₈ ) _, trisilanoxobutyl TriSilanolisobutyl POSS, C ₂₈ H ₆₆ O ₁₂ Si ₇ ) _, TriSilanolisoctyl POSS, C ₅₆ H ₁₂₂ O ₁₂ Si _7, TriSilanolPhenyl POSS, C ₄₂ H ₃₈ O ₁₂ Si ₇ ) _, tetrasilanolphenyl Nanocomposite adhesive for preservation of stone cultural properties, characterized in that it comprises at least one of POSS (TetraSilanolPhenyl POSS, C ₄₈ H ₄₄ O ₁₄ Si ₈ ). The method of claim 1, The room temperature curing type curing agent isophorone diamine, poly (propylene glycol) bis (2-aminopropyl ether)}, 4,4'- diamino diphenyl methane, 3, 3 ', 5 , 5'-tetramethyl-4,4'-diaminodiphenyl methane, 3,3 ', 5,5'-tetraethyl-4,4'-diaminodiphenyl methane, 3,3'-dimethyl-5 , 5'-dimethyl-4,4'-diaminodiphenyl methane, 3,3'-diamino benzophenone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4 Aromatic amines, aliphatic amines, cycloaliphatic amines, phenols, amines, anhydrides, acid anhydrides of, 4'-diaminodiphenyl sulfones, 3,4,4'-triaminediphenyl sulfones, Nanocomposite adhesive for preservation of stone cultural properties, characterized in that it comprises at least one of dicyandiamide or trifluoroboron. The method of claim 1, Nanocomposite epoxy adhesive for masonry cultural properties, characterized in that it further comprises 0.01 ~ 40wt% reactive diluent based on the weight of the mixture of the epoxy resin and the filler. The method according to claim 1 or 7, Nanocomposite epoxy adhesive for preserving the stone cultural properties, characterized in that it further comprises 0.01 ~ 4wt% of the curing accelerator based on the weight of the mixture of the epoxy resin and the filler.

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