Epoxy adhesive solution composition, preparation method of epoxy adhesive solution and modified cellular board

Abstract

The invention provides an epoxy adhesive solution composition, a preparation method of an epoxy adhesive solution and a modified cellular board. The epoxy adhesive liquid composition comprises the following components in parts by weight: 53-58 parts of epoxy resin, 2-10 parts of a silane coupling agent, 1-10 parts of a curing agent, 1-5 parts of blocked isocyanate and 60-70 parts of water, wherein a blocking group of the blocked isocyanate is selected from hydroxyl, oximido, acylamino, amino, imidazolyl, pyrazolyl or piperazinyl. By introducing the blocked isocyanate with the specific structure, the epoxy adhesive liquid can be subjected to pre-crosslinking reaction in the early drying treatment process, the modulus and high temperature resistance of a formed dry film are improved, and the phenomenon of glue overflow in the subsequent curing stage is inhibited; therefore, the structural integrity and the bonding strength of the adhesive layer in the modified cellular board under the high-temperature condition are improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of adhesives, in particular to an epoxy adhesive glue solution composition, a preparation method of the epoxy adhesive glue solution and a modified honeycomb panel. BACKGROUND

[0002] Honeycomb structural materials are widely used in fields such as construction, rail transit, aerospace, etc. due to their low density, high specific strength, corrosion resistance and good impact resistance. Honeycomb core adhesive is a key material for producing honeycomb structural materials, which needs to have good bonding performance, durability and environmental resistance to ensure the stability and safety of honeycomb structural materials under various conditions. At present, the commonly used system of honeycomb core adhesive is a two-component solvent type phenolic resin or epoxy resin system.

[0003] Li Gongchun et al. conducted a study on J-71 aluminum honeycomb sandwich adhesive (Chemistry and Adhesion, 1997). Phenolic resin was used as the skeleton material, nitrile rubber was used as the toughening agent, and aromatic amine curing agent was selected to prepare a honeycomb core adhesive with high mechanical strength. The shear strength at 20℃ is 30.0MPa, the plate-peeling strength is 14.0kN / m, and the multi-node T-peeling strength is 3.4kN / m. However, the characteristic of phenolic resin that will precipitate formaldehyde during the curing process makes the adhesive containing phenolic resin have a serious environmental pollution problem.

[0004] The existing patent (publication number CN107779147A) discloses a high-strength epoxy honeycomb adhesive and a preparation method thereof. The first component is an epoxy resin matrix and a carboxyl-terminated modified nitrile rubber toughening agent, and the second component is a toughening curing agent aromatic modified amine and a coupling agent γ-aminopropyl triethoxysilane. A high-toughness epoxy system honeycomb adhesive is prepared, which improves the problem of brittleness of the existing epoxy honeycomb adhesive. However, the epoxy phenolic resin-nitrile rubber system is prone to softening at high temperatures, making it difficult to maintain high bonding strength, which can lead to the destruction of the honeycomb core structure at high temperatures, and cannot meet the requirements of the aerospace field for the high-temperature resistance of the honeycomb core structural material.

[0005] Su Kai et al. developed a high-temperature-resistant paper honeycomb node adhesive (Chemistry and Adhesion, 2018). Phenolic cyanate ester was used as the main resin, polyisocyanamide was used as the main resin modifier, and nitrile rubber elastomer with active end groups was used as the toughening agent. A high-temperature-resistant honeycomb core adhesive was prepared by using core-shell rubber as an auxiliary toughening agent. The shear strength of the adhesive at 250℃ can reach 8.3MPa after 500h of heat aging at 250℃.

[0006] Su et al. developed a high-performance aramid paper honeycomb node adhesive (Chemistry and Adhesion, 2017). The main body resin is epoxy resin E51, the modifier is self-made high-ortho phenolic resin, and the toughening agent is butyronitrile rubber with active end groups. A honeycomb core adhesive with high temperature resistance and humidity resistance is prepared. The shear strength of the adhesive after 150℃, 400h thermal aging is 13.9MPa, and the shear strength after 55℃, 95%-100% relative humidity, 1000h humid heat aging is 13.7MPa, which is not much different from the shear strength before aging (14.1MPa), indicating that it has good high temperature resistance.

[0007] However, the toughening agent in the honeycomb core adhesive in the above prior art is mostly fat-soluble rubber, which has poor solubility in aqueous systems. Organic solvents such as ethyl acetate, acetone, butanone, toluene, etc. are usually needed to dissolve or disperse them. At present, the commonly used organic solvents for honeycomb core adhesive include ethyl acetate, acetone, butanone, toluene, etc. These organic solvents pose a serious threat to the environment and human health.

[0008] In summary, the development of an epoxy adhesive without organic solvent and with excellent high temperature resistance and its preparation method is of great significance to reduce environmental pollution, protect the health of operators and improve the stability and durability of the adhesive layer in the honeycomb structure material at high temperature (≥150℃). SUMMARY

[0009] The main purpose of the present application is to provide an epoxy adhesive glue solution composition, a preparation method of epoxy adhesive glue solution and a modified honeycomb board, to solve the problem of poor high temperature resistance of the epoxy adhesive for honeycomb core in the prior art, which leads to the decrease of bonding strength at high temperature.

[0010] In order to achieve the above purpose, the present application provides an epoxy adhesive glue solution composition, which comprises, by weight: 53-58 parts of epoxy resin, 2-10 parts of silane coupling agent, 1-10 parts of curing agent, 1-5 parts of blocked isocyanate and 60-70 parts of water; wherein the blocking group of the blocked isocyanate is selected from hydroxyl, oxime, amide, amino, imidazole, pyrazole or piperazine.

[0011] Further, the epoxy adhesive glue solution composition comprises, by weight: 53-56 parts of epoxy resin, 2-5 parts of silane coupling agent, 1.5-5 parts of curing agent, 1-5 parts of blocked isocyanate and 60-70 parts of water.

[0012] Further, the epoxy adhesive glue solution composition further comprises a cosolvent; preferably, the epoxy adhesive glue solution composition comprises 0.5-20 parts by weight of the cosolvent; more preferably, the cosolvent is selected from one or more of propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether, dipropylene glycol methyl ether acetate, propylene glycol diacetate and dipropylene glycol methyl ether.

[0013] Further, the epoxy resin has a number average molecular weight of 2000-20000 and an epoxy value of 0.05-0.45 mol / 100g; preferably, the epoxy resin is selected from one or more of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, hydrogenated epoxy resin and phenol type epoxy resin.

[0014] Further, the curing agent is selected from one or more of aromatic amine compound, dicyandiamide compound, imidazole compound, acid anhydride compound, organic acid hydrazide compound and polythiol compound.

[0015] Further, the blocked isocyanate is prepared by nucleophilic addition-elimination reaction of a blocking agent and isocyanate in the presence of a solvent; preferably, in the nucleophilic addition-elimination reaction, the molar ratio of the blocking agent to the isocyanate is (2.5-5.5):1; preferably, the ratio of the volume of the solvent to the weight of the isocyanate is (0.5-5) mL:1g; preferably, the solvent is selected from one or more of toluene, acetone and ethyl acetate; preferably, the temperature of the nucleophilic addition-elimination reaction is 50-80℃ and the time is 0.5-5h; preferably, the blocking agent is selected from imidazole compound, pyrazole compound, phenol compound, piperazine compound, amide compound, oxime compound or amine compound; the isocyanate is selected from one or more of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

[0016] Further, the epoxy adhesive glue solution composition further comprises an auxiliary agent; preferably, the epoxy adhesive glue solution composition further comprises 0.2-8 parts by weight of the auxiliary agent; more preferably, the auxiliary agent comprises a leveling agent and / or a defoaming agent; more preferably, the auxiliary agent comprises 0.1-5 parts by weight of the leveling agent and 0.1-3 parts by weight of the defoaming agent; more preferably, the leveling agent is a modified organosiloxane solution; further preferably, the modified organosiloxane solution comprises a dispersant and a polyether-modified organosiloxane, and has a solid content of 85-95wt%; the dispersant is selected from water and / or dipropylene glycol monomethyl ether.

[0017] Further, the epoxy adhesive glue solution composition further comprises a promoter; preferably, the epoxy adhesive glue solution composition further comprises 0.1-5 parts by weight of the promoter; preferably, the promoter is selected from one or more of the group consisting of fatty amines, derivatives of urea, imidazole compounds and guanidine compounds.

[0018] To achieve the above object, another aspect of the present application further provides a preparation method of an epoxy adhesive glue solution, which comprises: first mixing 53-58 parts by weight of an epoxy resin, 2-10 parts by weight of a silane coupling agent, 1-10 parts by weight of a curing agent, 1-5 parts by weight of a blocked isocyanate and 60-70 parts by weight of water to obtain an epoxy adhesive glue solution; wherein the blocking group of the blocked isocyanate is selected from a hydroxyl group, an oxime group, an amide group, an amino group, an imidazole group, a pyrazole group or a piperazine group.

[0019] Further, the stirring rate of the first mixing is 500-800 r / min, and the time is 30-60 min.

[0020] Further, the preparation method comprises: second mixing a water-soluble solvent with water to obtain a mixed solution; and third mixing the mixed solution, the epoxy resin, the silane coupling agent, the curing agent, the blocked isocyanate and an auxiliary agent to obtain the epoxy adhesive glue solution; preferably, the amount of the auxiliary agent is 0.2-8 parts by weight; preferably, the stirring rate of the second mixing is 100-200 r / min, and the time is 10-30 min; preferably, the stirring rate of the third mixing is 500-800 r / min, and the time is 1-2 h.

[0021] Still another aspect of the present application provides a modified honeycomb panel, which comprises, in sequence, a honeycomb structure layer, an adhesive layer and a panel layer, wherein the adhesive layer is obtained by coating and curing an epoxy adhesive glue solution, and the epoxy adhesive glue solution is prepared by the preparation method of the epoxy adhesive glue solution provided by the present application.

[0022] Further, the curing comprises a drying treatment and a hot-pressing curing treatment in sequence; preferably, the temperature of the drying treatment is 100-200℃, and the time is 30-120 s; preferably, the temperature of the hot-pressing curing treatment is 200-240℃, the pressure is 2.5-3.5 MPa, and the time is 1-5 min.

[0023] Compared with the traditional solvent type epoxy adhesive, the epoxy adhesive composition provided by the technical scheme of the present application uses epoxy resin as the base resin, can endow the prepared epoxy adhesive with excellent bonding strength and durability, and the system is completely dispersed by water as the dispersion medium, which fundamentally inhibits the emission of organic volatile substances (VOCs), thereby reducing the pollution to the environment and the potential threat to human health, and is conducive to realizing green production. The introduction of the silane coupling agent can effectively improve the bonding strength of the prepared adhesive glue solution, and when applied in the modified honeycomb panel, can improve the peeling strength between the adhesive layer and the honeycomb structure layer and the panel layer, and improve the stability and durability thereof under high temperature environment. The introduction of the curing agent in the above specific amount can promote the formation of the crosslinked network of the epoxy adhesive glue solution during curing, and improve the bonding strength and durability of the adhesive layer in the modified honeycomb panel; and the introduction of the blocked isocyanate containing the specific blocking group can cause the epoxy adhesive glue solution to occur pre-crosslinking reaction during the process of forming a dry film in the early stage of drying treatment, improve the modulus and high temperature resistance of the formed dry film, inhibit the overflow phenomenon caused by the softening of the dry film due to high temperature in the subsequent curing stage, and improve the structural integrity and bonding strength of the adhesive layer in the modified honeycomb panel under high temperature conditions.

[0024] Compared with other ranges, the weight fractions of the components in the epoxy adhesive glue solution composition are limited in the above specific ranges, which can improve the synergistic effect between the components in the epoxy adhesive glue solution composition, improve the processing performance and coating performance of the epoxy adhesive glue solution composition, promote the formation of a more uniform and dense adhesive layer, and when applied in the modified honeycomb panel, can improve the bonding strength and high temperature resistance of the adhesive layer and the adhesion between the adhesive layer and the honeycomb structure layer and the panel layer, and also can improve the utilization rate of the raw materials of the components and reduce the production cost.

[0025] In summary, the epoxy adhesive glue solution prepared from the above epoxy adhesive glue solution composition provided by the present application has excellent bonding strength and high temperature resistance, and can still maintain high bonding strength in high temperature (≥ 150℃) environment, which can meet the strict requirements of aerospace, rail transportation and other high-end application fields for epoxy adhesives, and the above epoxy adhesive glue solution provided by the present application is a water-based epoxy adhesive glue solution, which does not contain organic solvents in the system, can reduce the pollution to the environment, protect the health of the operators, can realize green production, and provides strong technical support for manufacturing high-performance and environmentally friendly modified honeycomb panels. DETAILED DESCRIPTION

[0026] It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict. The present application will be described in detail below with reference to the embodiments.

[0027] As described in the background, the existing cellular core epoxy adhesive has the problems of polluting the environment, endangering human health and reducing the bonding strength at high temperature due to poor high temperature resistance. In order to solve the above technical problems, the first aspect of the present application provides an epoxy adhesive glue solution composition, which comprises, by weight parts: 53-58 parts of epoxy resin, 2-10 parts of silane coupling agent, 1-10 parts of curing agent, 1-5 parts of blocked isocyanate and 60-70 parts of water; wherein the blocking group of the blocked isocyanate is selected from hydroxyl, oxime, amide, amino, imidazole, pyrazole or piperazine.

[0028] The above-mentioned epoxy adhesive composition provided by the present application comprises specific weight parts of epoxy resin, silane coupling agent, curing agent, blocked isocyanate and water. Compared with traditional solvent-based epoxy adhesive, the present application uses epoxy resin as the base resin, which can give the prepared epoxy adhesive excellent bonding strength and durability, and the system is completely dispersed with water as the dispersion medium, which fundamentally inhibits the emission of organic volatile substances (VOCs), thereby reducing the pollution to the environment and the potential threat to human health, and is conducive to realizing green production. The introduction of silane coupling agent can effectively improve the bonding strength of the prepared adhesive glue solution, and when applied in the modified honeycomb panel, it can improve the peeling strength between the adhesive layer and the honeycomb structure layer and the panel layer, and improve its stability and durability at high temperature. The introduction of the above-mentioned specific amount of curing agent can promote the formation of cross-linked network during the curing of the epoxy adhesive glue solution, improve the bonding strength and durability of the adhesive layer in the modified honeycomb panel; and the introduction of the blocked isocyanate containing specific blocking groups can cause the epoxy adhesive glue solution to undergo pre-crosslinking reaction during the process of forming a dry film in the early stage of drying treatment, improve the modulus and high temperature resistance of the formed dry film, inhibit the occurrence of glue overflow due to softening at high temperature in the subsequent curing stage, and improve the structural integrity and bonding strength of the adhesive layer in the modified honeycomb panel under high temperature conditions.

[0029] Compared with other ranges, limiting the weight parts of each component in the epoxy adhesive glue solution composition in the above-mentioned specific range can improve the synergistic effect between each component in the epoxy adhesive glue solution composition, improve the processing performance and coating performance of the epoxy adhesive glue solution composition, promote the formation of a more uniform and dense adhesive layer, and when applied in the modified honeycomb panel, it can improve the bonding strength and high temperature resistance of the adhesive layer and its adhesion with the honeycomb structure layer and the panel layer, and also can improve the utilization rate of the above-mentioned raw materials of each component, and reduce the production cost.

[0030] In summary, the epoxy adhesive glue solution prepared from the epoxy adhesive glue solution composition provided by the present application has excellent bonding strength and high-temperature resistance, and can still maintain high bonding strength in a high-temperature (≥ 150℃) environment, thereby meeting the strict requirements of high-end application fields such as aerospace and rail transportation on epoxy adhesives. The epoxy adhesive glue solution provided by the present application is a water-based epoxy adhesive glue solution, which does not contain organic solvents in the system, thereby reducing environmental pollution, protecting the health of operators, realizing green production, and providing strong technical support for manufacturing high-performance and environmentally friendly modified honeycomb panel materials.

[0031] In a preferred embodiment, the epoxy adhesive glue solution composition comprises, by weight parts, 53-56 parts of epoxy resin, 2-5 parts of silane coupling agent, 1.5-5 parts of curing agent, 1-5 parts of blocked isocyanate, and 60-70 parts of water. Compared with other ranges, limiting the amount of each component in the epoxy adhesive glue solution composition in the above range is beneficial to improve the synergistic effect between each component, improve the processing performance and coating performance of the epoxy adhesive glue solution composition, and is beneficial to form a more uniform and dense adhesive layer, which is applied to the modified honeycomb panel material, and is beneficial to improve the bonding strength and high-temperature resistance of the adhesive layer and the adhesion between the adhesive layer and the honeycomb structure layer and the panel layer. At the same time, it can also improve the utilization rate of each component raw material and reduce the production cost.

[0032] In a preferred embodiment, the epoxy adhesive glue solution composition further comprises a cosolvent. The introduction of the cosolvent in the epoxy adhesive glue solution composition is beneficial to improve the compatibility of each component in the epoxy adhesive glue solution composition and its dispersibility in water, reduce the viscosity of the epoxy adhesive glue solution composition, and improve its processing performance and coating performance.

[0033] In order to further improve the compatibility of each component in the epoxy adhesive glue solution composition and its dispersibility in water, reduce the viscosity of the epoxy adhesive glue solution composition, and further improve the processing performance and coating performance of the epoxy adhesive glue solution composition, preferably, the epoxy adhesive glue solution composition comprises 0.5-20 parts of cosolvent, by weight parts.

[0034] In a preferred embodiment, the co-solvent includes but is not limited to one or more of the group consisting of propylene glycol methyl ether (PM), propylene glycol methyl ether acetate (PMA), propylene glycol n-butyl ether (PnB), dipropylene glycol methyl ether acetate (DPMA), propylene glycol diacetate (PGDA) and dipropylene glycol methyl ether (DPM). Compared with other types, the co-solvent of the above type has better solubility, which is conducive to improving the compatibility of each component in the epoxy adhesive glue solution composition and its dispersibility in water, reducing the viscosity of the epoxy adhesive glue solution composition, improving the processing performance and coating performance of the epoxy adhesive glue solution composition, and is conducive to forming a more uniform, smooth and dense adhesive layer. Specifically, the co-solvent includes but is not limited to one or more of the following types: PM, PMA, PnB, DPMA and PGDA produced by Dow Chemical, PMA and DPMA produced by Jiangsu Yida Chemical Co., Ltd., DPM produced by Guangzhou Ruisheng New Material Technology Co., Ltd., PM produced by Shenzhen Junhua Technology Co., Ltd.

[0035] In a preferred embodiment, the number average molecular weight of the epoxy resin in the water-based epoxy resin is 2000-20000, and the epoxy value is 0.05-0.45 mol / 100g. The weight average molecular weight and the epoxy value of the epoxy resin include but are not limited to the above range, which is limited in the above range, which is conducive to improving the dispersibility of the epoxy resin in water, improving its compatibility with other components, improving the flowability and coating performance of the epoxy adhesive glue solution composition, and at the same time, it is also conducive to improving the crosslinking density of the adhesive layer formed thereby, and its application in modified honeycomb panel materials can improve the bonding strength of the adhesive layer and the peeling strength between the adhesive layer and the panel layer.

[0036] In a preferred embodiment, the epoxy resin includes but is not limited to bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, hydrogenated epoxy resin, phenol type epoxy resin. Compared with other types, the use of the above types of epoxy resin is conducive to improving the dispersibility of the epoxy resin in water, improving its compatibility with other components, and at the same time, it is also conducive to improving the crosslinking density of the epoxy adhesive, promoting the formation of a more uniform and dense adhesive layer, and its application in modified honeycomb panel materials is conducive to improving the bonding strength and durability of the adhesive layer. Specifically, the epoxy resin includes but is not limited to one or more of the following types: 828, jER828EL, jER1750 and 630 produced by Mitsubishi Chemical, MY0500, MY0510 and MY0600 produced by Huntsman, 5003-W-55, 3540-WY-55A and 5108-W-60 produced by Wise Materials, and EM-1006 produced by Japan Adikko.

[0037] In a preferred embodiment, the silane coupling agent is an epoxy-modified organosilicon compound. Compared with other types, the introduction of the silane coupling agent with the above specific structure into the epoxy adhesive glue solution can on the one hand enable the epoxy group in the silane coupling agent to react with the active hydrogen or other active sites in the epoxy resin to form additional crosslinking points, thereby significantly enhancing the crosslinking density inside the epoxy adhesive; on the other hand, the silane group in the silane coupling agent can form a chemical bond on the surface of the substrate, thereby improving the adhesion between the adhesive layer formed by the epoxy adhesive glue solution and the substrate; the synergistic effect of the above dual action mechanism can effectively improve the bonding strength and peel strength of the prepared adhesive layer, and improve its stability and durability in a high-temperature environment.

[0038] In order to further improve the crosslinking density of the adhesive layer formed by the epoxy adhesive glue solution curing agent, enhance the adhesion between the adhesive layer and the substrate, thereby further improve the bonding strength and peel strength of the adhesive layer, and improve its stability and durability in a high-temperature environment, preferably, the silane coupling agent includes but is not limited to one or more of the group consisting of CP03, OD4, OP300, O1741, O1861, O1872, V172 and V2171 produced by Wacker.

[0039] In a preferred embodiment, the curing agent includes but is not limited to one or more of the group consisting of aromatic amine compounds, dicyandiamide compounds, imidazole compounds, acid anhydride compounds, organic acid hydrazide compounds and polythiol compounds. Compared with other types, the use of the above types of curing agents is conducive to promoting the formation of a more compact crosslinking network structure, thereby facilitating the improvement of the bonding strength and durability of the adhesive layer formed by the curing of the epoxy adhesive glue solution. Specifically, the curing agent includes but is not limited to one or more of the following types: MH700G, HP-08 and HNA-100 produced by Shin Nippon Rika Co., Ltd., Dyhard 100, Dyhard 100S and Dyhard 100SF produced by Azko Chemical Co., Ltd., DDA5 and DDA10 produced by Huntsman, DDH5850 and 3060 produced by Lüe High New Materials, D97 produced by Guangzhou Taiji New Materials Co., Ltd., Dicyanex 1400 produced by Shaoyang Yingchuang Future New Materials Co., Ltd., SH-900, SH-500 and SH-300 produced by Guangzhou Xini Metallurgical Chemical Co., Ltd., R-0598, R-2021F and R-2217Y produced by Richem (Guangdong) Technology Co., Ltd., WEH-102 and WEH-501 produced by Japan ADEKA.

[0040] In a preferred embodiment, the blocked isocyanate is prepared by a nucleophilic addition-elimination reaction of the blocking agent with the isocyanate in the presence of a solvent. By reacting the blocking agent with the isocyanate group (-NCO), the active isocyanate group is changed into an inactive blocked group, which is beneficial to improve the stability of the blocked isocyanate during the processing stage. When the epoxy adhesive solution is coated on the surface of the substrate and the drying process begins, due to the change of temperature and other conditions, the blocked isocyanate decomposes and releases active isocyanate groups (-NCO), which can react with the active sites of other components in the epoxy adhesive solution composition to form a pre-crosslinked structure, which is beneficial to improve the modulus and high temperature resistance of the formed adhesive layer, inhibit the overflow phenomenon caused by the softening of the adhesive layer due to high temperature during the subsequent curing stage, and further improve the structural integrity and bonding strength of the adhesive layer formed by the curing of the epoxy adhesive solution under high temperature conditions.

[0041] In a preferred embodiment, the molar ratio of the blocking agent to the isocyanate in the nucleophilic addition-elimination reaction is (2.5-5.5):1. The molar ratio of the blocking agent to the isocyanate includes but is not limited to the above range, and the limitation within the above range is beneficial to obtain the blocked isocyanate with the specific blocked group described above.

[0042] In order to improve the dispersibility of the blocking agent, the isocyanate and the base, and further improve the reaction efficiency of the nucleophilic addition-elimination reaction, in a preferred embodiment, the ratio of the volume of the solvent to the weight of the isocyanate is (0.5-5) mL:1 g.

[0043] In order to further improve the dispersibility of the blocking agent, the isocyanate and the base, and further improve the reaction efficiency of the nucleophilic addition-elimination reaction, preferably, the solvent is selected from one or more of the group consisting of toluene, acetone and ethyl acetate.

[0044] In a preferred embodiment, the temperature of the nucleophilic addition-elimination reaction is 50-80°C, and the time is 0.5-5h. The temperature and time of the nucleophilic addition-elimination reaction include but are not limited to the above range, and the limitation within the above range is beneficial to improve the reaction efficiency of the nucleophilic addition-elimination reaction, and further obtain the blocked isocyanate with the specific blocked group described above.

[0045] In order to improve the thermal stability of the blocked isocyanate, and facilitate the decomposition and release of active isocyanate groups during the subsequent drying process, promote the pre-crosslinking reaction of the isocyanate with the active sites of other components in the epoxy adhesive solution composition, and further improve the modulus and high temperature resistance of the formed adhesive layer, preferably, the blocking agent includes but is not limited to imidazole compounds, pyrazole compounds, phenolic compounds, piperazine compounds, amide compounds, oxime compounds or amine compounds.

[0046] To further promote the pre-crosslinking reaction between the capped isocyanate and the active sites of other components in the epoxy adhesive glue solution composition, further improve the modulus and high temperature resistance of the formed adhesive layer, and further reduce the glue overflow phenomenon in the subsequent curing process, preferably, the isocyanate includes, but is not limited to, one or more of the group consisting of toluene diisocyanate, diphenyl methane diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0047] In a preferred embodiment, the epoxy adhesive glue solution composition further includes an auxiliary agent. The introduction of the auxiliary agent is beneficial to improve the processing performance and coating performance of the epoxy adhesive glue solution composition, promote the formation of a more uniform and dense adhesive layer, and improve the bonding strength, high temperature resistance, and adhesion between the adhesive layer formed by curing the epoxy adhesive glue solution and the substrate.

[0048] To further improve the processing performance and coating performance of the epoxy adhesive glue solution composition, promote the formation of a more uniform and dense adhesive layer, and improve the bonding strength, high temperature resistance, and adhesion between the adhesive layer formed by curing the epoxy adhesive glue solution and the substrate, preferably, the epoxy adhesive glue solution composition further includes 0.2-8 parts of an auxiliary agent by weight.

[0049] In a preferred embodiment, the auxiliary agent includes a leveling agent and / or a defoaming agent. The introduction of the leveling agent is beneficial to reduce the surface tension of the epoxy adhesive glue solution composition, reduce the orange peel effect and shrinkage, and improve the wettability of the epoxy adhesive glue solution composition, thereby facilitating the formation of an adhesive layer with a smoother and more uniform surface, and improving its bonding strength and adhesion to the substrate. The introduction of the defoaming agent is beneficial to remove bubbles and inhibit the formation of pores on the surface of the adhesive layer, thereby facilitating the formation of a more uniform and dense adhesive layer, and further improving the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive glue solution.

[0050] To further improve the processing performance and coating performance of the epoxy adhesive glue solution composition, further obtain an adhesive layer with a smoother surface and a more uniform and dense surface, and thereby further improve the bonding strength, high temperature resistance, and adhesion between the adhesive layer formed by curing the epoxy adhesive glue solution and the substrate, in a preferred embodiment, the auxiliary agent includes 0.1-5 parts of a leveling agent and 0.1-3 parts of a defoaming agent by weight.

[0051] To further reduce the surface tension of the epoxy adhesive glue solution composition, reduce the orange peel effect and shrinkage, and further improve the wettability of the epoxy adhesive glue solution composition, thereby forming a more smooth and uniform adhesive layer, and further improve its bonding strength and adhesion to the substrate, in a preferred embodiment, the leveling agent is a modified organosiloxane solution; preferably, the modified organosiloxane solution includes a dispersant and a polyether-modified organosiloxane, and the solid content is 85-95 wt%; the dispersant includes but is not limited to water and / or dipropylene glycol monomethyl ether. Specifically, the leveling agent includes but is not limited to one or more of the following types: byk333, byk345, byk346, byk348, byk375, byk381 and byk4511 produced by Bichemical, Glide 450 and Rad 2700 produced by TEGO in Germany, DC57, DC29 and DC11 produced by Conding, RainPont 2701, RP-6628 and RP-6633 produced by RainPont in Sichuan.

[0052] To remove bubbles in the epoxy adhesive glue solution, inhibit the formation of pores on the surface of the adhesive layer, thereby forming a more uniform and dense adhesive layer, which is conducive to improving the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive glue solution. In a preferred embodiment, the defoaming agent includes but is not limited to one or more of the following types: BYK-054, BYK-055, BYK-066N, BYK-A535 and BYK-1790 produced by Bichemical, Foamaster MO2111, MO NDW, SI2210, SI2240, ST2400 and ST2412 produced by BASF, AGITAN 100, AGITAN 105, AGITAN 230, AGITAN 282, AGITAN 731 and AGITAN 760N produced by Mingling in Germany, AFCONA 2503 and AFCONA 2524 produced by Evonik Polymer Co., Ltd.

[0053] In a preferred embodiment, the epoxy adhesive glue solution composition further includes an accelerator. The presence of the accelerator is conducive to improving the curing reaction efficiency of the epoxy resin and the curing agent, forming a more uniform and dense cross-linked network structure, thereby improving the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive glue solution.

[0054] To further improve the curing reaction efficiency of the epoxy resin and the curing agent, form a more uniform and dense cross-linked network structure, and further improve the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive glue solution, preferably, the epoxy adhesive glue solution further includes 0.1-5 parts of an accelerator by weight.

[0055] In a preferred embodiment, the accelerator includes one or more of the group consisting of fatty amines, derivatives of urea, imidazole compounds and guanidine compounds. Compared with other kinds, the use of the above-mentioned kinds of accelerators is advantageous to improve the curing reaction efficiency of the epoxy resin and the curing agent, form a more uniform and dense crosslinking network structure, and thus is advantageous to improve the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive glue solution. Specifically, the accelerator includes one or more of the following kinds: Fujicure FXE-1000, FXR-1081 and FXR-1121 produced by T&K TOKA Co., Ltd., UR200, UR300, UR400, UR500, UR700, UR800, URAcc13, URAcc57, PI and PI-FF produced by AzkoNobel Chemical Co., Ltd., SH-A100 and A150 produced by Guangzhou Xinxili Metallurgical Chemical Co., Ltd., LSW-520 produced by Dalian Liansheng New Material Group Co., Ltd., Baxxodur EC151 and EC201 produced by BASF, 2E4MZ, 2E4MZ-CN, 2MZ-A and 2PZ-T produced by Shikoku Chemicals Corporation.

[0056] The second aspect of the present application further provides a preparation method of an epoxy adhesive glue solution, which comprises: mixing 53-58 parts by weight of an epoxy resin, 2-10 parts by weight of a silane coupling agent, 1-10 parts by weight of a curing agent, 1-5 parts by weight of a blocked isocyanate and 60-70 parts by weight of water to obtain an epoxy adhesive glue solution; wherein the blocking group of the blocked isocyanate is selected from a hydroxyl group, an oxime group, an amide group, an amino group, an imidazole group, a pyrazole group or a piperazine group.

[0057] Compared with other methods, the use of the above-mentioned preparation method of the present application can obtain a more uniform epoxy adhesive glue solution, and the above-mentioned epoxy adhesive glue solution does not contain organic solvents, which fundamentally inhibits the emission of organic volatile substances, reduces the pollution to the environment and the potential threat to human health, and is advantageous to realize green production.

[0058] The introduction of silane coupling agents can effectively improve the adhesive strength of the prepared adhesive solution. When applied to modified honeycomb panels, it can enhance the peel strength between the adhesive layer and the honeycomb structure layer and panel layer, improving its stability and durability under high-temperature conditions. The introduction of a specific amount of curing agent can promote the formation of a cross-linked network during the curing of the epoxy adhesive solution, improving the adhesive strength and durability of the adhesive layer in the modified honeycomb panel. Simultaneously, the introduction of end-capped isocyanates containing specific end-capping groups enables the epoxy adhesive solution to undergo a pre-cross-linking reaction during the initial drying process, increasing the modulus and high-temperature resistance of the formed dry film and inhibiting overflow caused by softening at high temperatures during subsequent curing stages. This improves the structural integrity and adhesive strength of the adhesive layer in the modified honeycomb panel under high-temperature conditions.

[0059] Compared to other ranges, limiting the weight percentages of each component in the epoxy adhesive liquid composition within the aforementioned specific range can enhance the synergistic effect between the components in the epoxy adhesive liquid composition, improve the processing and coating properties of the epoxy adhesive liquid composition, promote the formation of a more uniform and dense adhesive layer, and when applied to modified honeycomb panels, improve the bonding strength and high-temperature resistance of the adhesive layer and its adhesion to the honeycomb structure layer and panel layer. At the same time, it can also improve the utilization rate of the raw materials of the aforementioned components and reduce production costs.

[0060] In summary, the epoxy adhesive liquid prepared from the epoxy adhesive liquid composition provided in this application has excellent bonding strength and high temperature resistance. It can maintain high bonding strength even in high temperature (≥150℃) environments, which can meet the stringent requirements of high-end application fields such as aerospace and rail transportation for epoxy adhesives. Moreover, the epoxy adhesive liquid provided in this application is a water-based epoxy adhesive liquid, which does not contain organic solvents, thus reducing environmental pollution, protecting the health of operators, and enabling green production. It provides strong technical support for the manufacture of high-performance, environmentally friendly modified honeycomb panels.

[0061] In a preferred embodiment, the stirring rate of the first mixing is 500–800 r / min, and the time is 30–60 min. The stirring rate and time of the first mixing include, but are not limited to, the above ranges. Limiting them to the above ranges is beneficial to improving the dispersion uniformity of each component material, improving the uniformity of the epoxy adhesive solution, and reducing the formation of air bubbles. This is beneficial to obtaining a more uniform and dense adhesive layer during the subsequent curing process, and further beneficial to improving the bonding strength and durability of the adhesive layer formed by curing the epoxy adhesive solution.

[0062] In a preferred embodiment, the preparation method comprises: mixing the cosolvent with water to obtain a mixed solution; mixing the mixed solution, the epoxy resin, the silane coupling agent, the curing agent, the blocked isocyanate and the auxiliary agent to obtain the epoxy adhesive glue solution. Compared with other methods, the use of the above method is beneficial to improve the uniformity of the dispersion of each component material, improve the uniformity of the epoxy adhesive glue solution, thereby facilitating the formation of a more uniform and dense adhesive layer in the subsequent curing process, and further facilitating the improvement of the bonding strength and durability of the adhesive layer formed by the curing of the epoxy adhesive glue solution.

[0063] In a preferred embodiment, the stirring rate of the second mixing is 100-200 r / min, and the time is 10-30 min. The stirring rate and time of the second mixing include but are not limited to the above range, and the limitation within the above range is beneficial to obtain a uniform mixed solution, thereby facilitating the improvement of the uniformity of the dispersion of each component material in the subsequent third mixing process, and further facilitating the improvement of the uniformity of the epoxy adhesive glue solution.

[0064] In a preferred embodiment, the stirring rate of the third mixing is 500-800 r / min, and the time is 1-2 h. The stirring rate and time of the third mixing include but are not limited to the above range, and the limitation within the above range is beneficial to improve the uniformity of the dispersion of each component material, reduce the formation of bubbles, and improve the uniformity of the epoxy adhesive glue solution, thereby facilitating the formation of a more uniform and dense adhesive layer in the subsequent curing process, and further facilitating the improvement of the bonding strength and durability of the adhesive layer formed by the curing of the epoxy adhesive glue solution.

[0065] The third aspect of the present application also provides a modified honeycomb panel, which comprises a honeycomb structure layer, an adhesive layer and a panel layer arranged in sequence, wherein the adhesive layer is obtained by coating and curing an epoxy adhesive glue solution, and the epoxy adhesive glue solution is prepared by the above-mentioned preparation method of the epoxy adhesive glue solution provided by the present application. The epoxy adhesive glue solution prepared by the above-mentioned preparation method of the epoxy adhesive glue solution provided by the present application has excellent bonding strength and high-temperature resistance, and can still maintain a relatively high bonding strength in a high-temperature (≥ 150℃) environment. When it is applied to the modified honeycomb panel, it can improve the peeling strength between the adhesive layer and the honeycomb structure layer and the panel layer, and ensure that it still maintains a relatively high bonding strength at high temperatures, thereby meeting the strict requirements of aerospace, rail transportation and other high-end application fields for honeycomb structural materials. Moreover, the above-mentioned epoxy adhesive glue solution provided by the present application is a water-based epoxy adhesive glue solution, and does not contain organic solvents in the system, which can reduce environmental pollution, protect the health of operators, realize green production, and provide strong technical support for the manufacture of high-performance and environmentally friendly modified honeycomb panel.

[0066] In order to obtain a more uniform and dense adhesive layer and improve the bonding strength and durability of the adhesive layer, in a preferred embodiment, the curing comprises a drying treatment and a hot-pressing curing treatment in sequence.

[0067] In a preferred embodiment, the drying treatment is performed at a temperature of 100-200℃ for 30-120s. The temperature and time of the drying treatment, which are not limited to the above range, are limited in the above range to facilitate the removal of water in the epoxy adhesive glue solution and the promotion of the pre-crosslinking reaction between the blocked isocyanate and the active sites of other components in the epoxy adhesive glue solution, thereby reducing the glue overflow in the subsequent curing process.

[0068] In a preferred embodiment, the hot-pressing curing treatment is performed at a temperature of 200-240℃, a pressure of 2.5-3.5MPa, and a time of 1-5min. The temperature, pressure, and time of the hot-pressing curing treatment, which are not limited to the above range, are limited in the above range to facilitate the improvement of the efficiency of the hot-pressing curing treatment and the promotion of the formation of a more uniform and dense adhesive layer, thereby improving the bonding strength and durability thereof.

[0069] The present application will be further described in detail below in conjunction with specific examples, which should not be construed as limiting the scope of the present application.

[0070] Example 1

[0071] A preparation method of an epoxy adhesive glue solution, specifically comprising the following steps:

[0072] (1) Prepare each component raw material in the epoxy adhesive glue solution composition according to Table 1;

[0073] (2) Mix the water-based epoxy resin emulsion (including epoxy resin and water), silane coupling agent, curing agent, blocked isocyanate, accelerator, leveling agent, and defoaming agent, and stir at a rate of 25℃ and 560r / min for 30min to obtain a mixture;

[0074] (3) Mix the cosolvent with water, and stir at a rate of 25℃ and 150r / min for 30min to obtain a mixture solution;

[0075] (4) Mix the mixture obtained in step (2) with the mixture solution obtained in step (3), and stir at a rate of 25℃ and 780r / min for 1h to obtain an epoxy adhesive glue solution.

[0076] Table 1

[0077]

[0078] Example 2

[0079] The difference from Example 1 is that in step (1), the types and amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific types and amounts are shown in Table 2; the other steps are the same as those in Example 1.

[0080] Table 2

[0081]

[0082] Example 3

[0083] The difference from Example 1 is that in step (1), the types and amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific types and amounts are shown in Table 3; the other steps are the same as those in Example 1.

[0084] Table 3

[0085]

[0086] Example 4

[0087] The difference from Example 1 is that in step (1), the types and amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific types and amounts are shown in Table 4; the other steps are the same as those in Example 1.

[0088] Table 4

[0089]

[0090] Example 5

[0091] The difference from Example 1 is that in step (1), the types and amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific types and amounts are shown in Table 5; the other steps are the same as those in Example 1.

[0092] Table 5

[0093]

[0094] Example 6

[0095] The difference from Example 1 is that in step (1), the leveling agent is not introduced into the epoxy adhesive glue solution composition; the other steps are the same as those in Example 1.

[0096] Example 6 does not introduce a leveling agent, so the epoxy adhesive glue solution prepared has poor adhesion during the coating process, and obvious "shrinkage" phenomenon occurs, resulting in partial lack of glue. After adding the leveling agent, the adhesion of the epoxy adhesive glue solution to the substrate is good, and there is no lack of glue phenomenon.

[0097] Examples 7 to 12

[0098] The difference from Example 1 is that in step (1), the amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific amounts are shown in Table 6 (the types and sources of the components are the same as those in Example 1); the remaining steps are the same as those in Example 1.

[0099] Table 6

[0100]

[0101] Comparative Example 1

[0102] The difference from Example 1 is that in step (1), no silane coupling agent is introduced into the epoxy adhesive glue solution composition; the remaining steps are the same as those in Example 1.

[0103] Comparative Example 2

[0104] The difference from Example 1 is that in step (1), no blocked isocyanate is introduced into the epoxy adhesive glue solution composition; the remaining steps are the same as those in Example 1.

[0105] Comparative Example 2 does not introduce blocked isocyanate, which leads to serious glue overflow during subsequent curing, but the mechanical properties of Comparative Example 2 are not greatly affected after curing, and the comprehensive performance does not decrease significantly.

[0106] Comparative Examples 3-5

[0107] The difference from Example 1 is that in step (1), the amounts of the components in the epoxy adhesive glue solution composition are different from those in Example 1, and the specific amounts are shown in Table 7 (the types and sources of the components are the same as those in Example 1); the remaining steps are the same as those in Example 1.

[0108] Table 7

[0109]

[0110] The epoxy adhesive glue solutions prepared in all the above examples and comparative examples are tested for the following properties:

[0111] (1) Viscosity: tested at 23°C using a flow cup with a nozzle diameter of 4 mm according to the method described in the German Standard Committee's protective grade standard for electronic device housings DIN 53211;

[0112] (2) Solid content: tested by heating at 120°C for 2 h according to the method described in the national standard GB / T 1725-2007 "Determination of Nonvolatile Matter Content of Color Paint, Varnish and Plastic";

[0113] (3) pH value: tested according to the method described in the national standard GB / T 18012-2021 "Determination of pH Value of Latex";

[0114] (4) Density: tested by a density meter.

[0115] The test results are shown in Table 8.

[0116] Table 8

[0117]

[0118] The epoxy adhesive glue solution prepared in the above all examples and comparative examples was coated on one side surface of the honeycomb structure layer at a coating amount of 8.7 x 10 -4 g / cm 3 The panel layer was then covered on the surface coated with the epoxy adhesive glue solution, and the epoxy adhesive was dried at 150°C for 1 min to form a dry film, thereby obtaining a laminated structure.

[0119] The dry film prepared in the above all examples and comparative examples was tested for the following properties:

[0120] (1) Grid cut test: tested according to the method described in the grid cut test standard for paint layers and similar coatings DIN 53151 formulated by the German Standard Committee; wherein B indicates that the instrument used is a standard multi-blade cutting instrument B with 6 blades and a blade spacing of 1 mm; GT 0 indicates that the cutting edge is complete and smooth, and the grid surface has no paint layer peeling; GT 1 indicates that the grid surface has a paint layer peeling area of about 5% of the grid area;

[0121] (2) Round bar bending test: tested according to the method described in the national standard GB / T 6742-2007 “Color paint and varnish Bending test (cylinder shaft) ”, using a round bar with a diameter of 3 mm;

[0122] (3) Pencil hardness: tested according to the method described in the national standard GB / T 6739-2022 “Color paint and varnish Pencil method for testing paint film hardness”;

[0123] The test results are shown in Table 9.

[0124] Table 9

[0125]

[0126] The laminated structure prepared in the above all examples and comparative examples was subjected to hot-pressing curing treatment at 240°C and 3 MPa for 3 min, thereby obtaining a modified honeycomb panel.

[0127] The adhesive layer in the modified honeycomb panel prepared in the above all examples and comparative examples was tested for the following properties:

[0128] (1) Coating grid cutting: test according to the method described in the grid cutting test standard for paint layers and similar coatings DIN 53151 established by the German Standards Committee;

[0129] (2) Round bar bending test: test according to the method described in the national standard GB / T 6742-2007 “Paint and Varnish Bending Test (Cylinder Axis)”, using a round bar with a diameter of 3 mm;

[0130] (3) Pencil hardness: test according to the method described in the national standard GB / T 6739-2022 “Paint and Varnish Pencil Method for Measuring Paint Film Hardness”;

[0131] (4) Glass transition temperature (Tg): test according to the method described in the national standard GB / T 19466.2-2004 “Plastics Differential Scanning Calorimetry (DSC) Part 2: Determination of Glass Transition Temperature”;

[0132] (5) Shear strength: test according to the method described in the national standard GB / T 7124-2008 “Adhesives Determination of Tensile Shear Strength (Rigid Material to Rigid Material)”, respectively measure the shear strength (silicon steel sheet) at 25°C and 150°C;

[0133] (6) T-peel strength: test according to the method described in the national standard GB / T 2791-1995 “Adhesives T-Peel Strength Test Method Flexible Material to Flexible Material”, respectively measure the T-peel strength (silicon steel sheet), T-peel strength (aluminum honeycomb), T-peel strength (aramid paper honeycomb) at 25°C and T-peel strength (silicon steel sheet) at 150°C;

[0134] (7) Floating roller peel strength: test according to the method described in the national standard GB / T 7122-1996 “High-strength Adhesives Determination of Peel Strength Floating Roller Method”, respectively measure the floating roller peel strength (silicon steel sheet) at 25°C and 150°C;

[0135] (8) Heat aging shear strength: test according to the method described in the national standard GB / T 7124-2008 “Adhesives Determination of Tensile Shear Strength (Rigid Material to Rigid Material)”, after 500h of heat aging at 180°C;

[0136] (9) ATF oil resistance test: test according to the method described in the national standard GB / T 7124-2008 “Adhesives Determination of Tensile Shear Strength (Rigid Material to Rigid Material)”, after 500h of immersion in ATF oil (automatic transmission oil) at 150°C.

[0137] The test results are shown in Tables 10 and 11.

[0138] Table 10

[0139]

[0140] Table 11

[0141]

[0142] From the above description, it can be seen that the above-mentioned embodiments of the present application achieve the following technical effects:

[0143] Comparing Example 1 and Comparative Examples 1 and 2, since no blocked isocyanate is introduced in Comparative Example 2, it causes serious overflow phenomenon in the subsequent curing process, but when Comparative Example 2 is completed, its mechanical properties are not greatly affected, and the comprehensive performance is equivalent to Example 1, while the mechanical properties and adhesive strength of Comparative Example 1 are significantly poorer than Example 1. Therefore, introducing silane coupling agent into the epoxy adhesive glue solution composition can effectively improve the adhesive strength of the prepared adhesive glue solution, thereby improving the peeling strength between the adhesive layer and the honeycomb structure layer and the panel layer prepared therefrom, and improving its stability and durability in high temperature environment. At the same time, introducing blocked isocyanate containing specific blocking groups can cause pre-crosslinking reaction of the epoxy adhesive glue solution during the process of forming a dry film in the early drying process, improve the modulus and high temperature resistance of the formed dry film, inhibit the overflow phenomenon caused by softening due to high temperature in the subsequent curing stage, and improve the structural integrity and adhesive strength of the adhesive layer in the modified honeycomb panel under high temperature conditions.

[0144] Comparing Example 1, 7 to 12 and Comparative Examples 3 to 5, compared to other ranges, limiting the weight fractions of each component in the epoxy adhesive glue solution composition in the above specific range can improve the synergistic effect between each component in the epoxy adhesive glue solution composition, improve the processing performance and coating performance of the epoxy adhesive glue solution composition, promote the formation of a more uniform and dense adhesive layer, and improve the adhesive strength and high temperature resistance of the adhesive layer and its adhesion to the honeycomb structure layer and the panel layer.

[0145] Comparing Example 1 and 6, introducing a leveling agent in the epoxy adhesive glue solution composition is beneficial to reduce the surface tension of the epoxy adhesive glue solution composition, reduce the orange peel effect and shrinkage, and improve the wettability of the epoxy adhesive glue solution composition, thereby facilitating the formation of an adhesive layer with a smoother and more uniform surface, and improving its adhesive strength and adhesion to the substrate.

[0146] In summary, the epoxy adhesive prepared from the epoxy adhesive glue solution provided by the present application has excellent bonding strength and high-temperature resistance, can still maintain high bonding strength in a high-temperature (≥ 150 DEG C) environment, can meet the strict requirements of aerospace, rail transit and other high-end application fields on the epoxy adhesive, and the epoxy adhesive glue solution provided by the present application is a water-based epoxy adhesive glue solution, does not contain organic solvents in the system, can reduce the pollution to the environment, and protects the health of the operating personnel, so as to realize green production.

[0147] It should be noted that the terms "first", "second" and the like in the specification and claims of the present application are used to distinguish similar objects, and do not necessarily have to describe a specific order or sequence. It should be understood that the terms thus used can be interchanged under appropriate circumstances, so that the embodiments of the present application described herein can be implemented in an order other than that described herein.

[0148] The above only describes the preferred embodiments of the present application and is not intended to limit the present application. For those skilled in the art, the present application can have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principles of the present application shall be included in the protection scope of the present application.

Claims

1. An epoxy adhesive sizing composition characterized by, The epoxy adhesive glue solution composition comprises, by weight parts, 53-58 parts of the epoxy resin, 2-10 parts of the silane coupling agent, 1-10 parts of the curing agent, 1-5 parts of the blocked isocyanate, and 60-70 parts of water; wherein the blocking group of the blocked isocyanate is selected from the group consisting of hydroxyl, oxime, amide, amino, imidazole, pyrazole or piperazine.

2. The epoxy adhesive sizing composition of claim 1, wherein, The epoxy adhesive glue solution composition comprises, by weight parts, 53-56 parts of the epoxy resin, 2-5 parts of the silane coupling agent, 1.5-5 parts of the curing agent, 1-5 parts of the blocked isocyanate, and 60-70 parts of water; Preferably, the epoxy adhesive glue solution composition further comprises a cosolvent; more preferably, the epoxy adhesive glue solution composition comprises, by weight parts, 0.5-20 parts of the cosolvent; further preferably, the cosolvent is selected from one or more of the group consisting of propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether, dipropylene glycol methyl ether acetate, propylene glycol diacetate and dipropylene glycol methyl ether.

3. The epoxy adhesive sizing composition according to claim 1 or 2, characterized in that, The epoxy resin has a number average molecular weight of 2000-20000 and an epoxy value of 0.05-0.45 mol / 100g; Preferably, the epoxy resin is selected from one or more of the group consisting of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, hydrogenated epoxy resin and phenol type epoxy resin.

4. The epoxy adhesive sizing composition according to any one of claims 1 to 3, characterized in that, The curing agent is selected from one or more of the group consisting of aromatic amine compound, dicyandiamide compound, imidazole compound, acid anhydride compound, organic acid hydrazide compound and polythiol compound; Preferably, the blocked isocyanate is prepared by nucleophilic addition-elimination reaction of a blocking agent and isocyanate in the presence of a solvent; More preferably, in the nucleophilic addition-elimination reaction, the molar ratio of the blocking agent to the isocyanate is (2.5-5.5):1; More preferably, the ratio of the volume of the solvent to the weight of the isocyanate is (0.5-5) mL:1g; further preferably, the solvent is selected from one or more of the group consisting of toluene, acetone and ethyl acetate; More preferably, the nucleophilic addition-elimination reaction has a temperature of 50-80℃ and a time of 0.5-5h; More preferably, the blocking agent is selected from imidazole compound, pyrazole compound, phenol compound, piperazine compound, amide compound, oxime compound or amine compound; and the isocyanate is selected from one or more of the group consisting of toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate.

5. The epoxy adhesive sizing composition according to any one of claims 1 to 4, characterized in that, The epoxy adhesive glue solution composition further comprises an auxiliary agent; preferably, the epoxy adhesive glue solution composition further comprises, by weight parts, 0.2-8 parts of the auxiliary agent; Preferably, the auxiliary agent comprises a leveling agent and / or a defoaming agent, more preferably, the auxiliary agent comprises 0.1-5 parts of the leveling agent and 0.1-3 parts of the defoaming agent; More preferably, the leveling agent is a modified organosiloxane solution; further preferably, the modified organosiloxane solution comprises a dispersant and a polyether-modified organosiloxane; the solid content of the modified organosiloxane solution is 85-95 wt%; the dispersant is selected from water and / or dipropylene glycol monomethyl ether.

6. The epoxy adhesive sizing composition of claim 5, wherein, The epoxy adhesive glue solution composition further comprises a promoter; Preferably, the epoxy adhesive glue solution composition further comprises 0.1-5 parts by weight of the promoter; Preferably, the promoter is selected from one or more of the group consisting of fatty amines, derivatives of urea, imidazole compounds and guanidine compounds.

7. A method for preparing an epoxy adhesive glue solution, characterized in that, The preparation method comprises: first mixing 53-58 parts by weight of an epoxy resin, 2-10 parts by weight of a silane coupling agent, 1-10 parts by weight of a curing agent, 1-5 parts by weight of a blocked isocyanate and 60-70 parts by weight of water to obtain the epoxy adhesive glue solution; wherein the blocking group of the blocked isocyanate is selected from hydroxyl, oxime, amide, amino, imidazole, pyrazole or piperazine.

8. The method for preparing the epoxy adhesive solution according to claim 7, characterized in that, The stirring rate of the first mixing is 500-800 r / min, and the time is 30-60 min; Preferably, the preparation method comprises: second mixing a cosolvent with the water to obtain a mixed solution; third mixing the mixed solution, the epoxy resin, the silane coupling agent, the curing agent, the blocked isocyanate and an auxiliary agent to obtain the epoxy adhesive glue solution; more preferably, the amount of the auxiliary agent is 0.2-8 parts by weight; Preferably, the stirring rate of the second mixing is 100-200 r / min, and the time is 10-30 min; Preferably, the stirring rate of the third mixing is 500-800 r / min, and the time is 1-2 h.

9. A modified honeycomb board material, characterized by, The modified honeycomb panel material comprises, in sequence, a honeycomb structure layer, an adhesive layer and a panel layer, wherein the adhesive layer is obtained by coating and curing an epoxy adhesive glue solution, and the epoxy adhesive glue solution is prepared by the preparation method of the epoxy adhesive glue solution according to claim 7 or 8.

10. The modified honeycomb board material of claim 9, wherein, The curing comprises a drying process and a hot-pressing curing process in sequence; Preferably, the temperature of the drying process is 100-200℃, and the time is 30-120 s; Preferably, the temperature of the hot-pressing curing process is 200-240℃, the pressure is 2.5-3.5 MPa, and the time is 1-5 min.

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