Adhesives and barrier layers containing them, highly transparent and flexible high-barrier films and film-like sealing and display materials

Abstract

To provide adhesives and barrier layers containing them, highly transparent and flexible high-barrier films, and film-like sealing and display materials. [Solution] This adhesive has high epoxycyclohexylsiloxane activity and good crosslinking properties. The aminosiloxane and epoxycyclohexylsiloxane components undergo a thermal crosslinking reaction to form a three-dimensional silicon structure in the film layer formed by the polyvinyl alcohol-based film-forming resin. This effectively fills the gaps between molecules in the polyvinyl alcohol-based film-forming resin, significantly improving the water and oxygen barrier function and also improving the scratch resistance of the film layer formed by the polyvinyl alcohol-based film-forming resin. The reaction between epoxidized-terminated hydroxylpolybutadiene and other components in the adhesive not only improves the water and oxygen barrier ability of the film layer formed by the polyvinyl alcohol-based film-forming resin, but also effectively improves the flexibility of the film layer at low temperatures.

Description

[Technical Field]

[0001] The present invention relates to the technical field of high-performance film materials, and more particularly to adhesives and barrier layers containing them, highly transparent and flexible high-barrier films, and film-like sealing and display materials. [Background technology]

[0002] Polymer film materials are widely used in various fields, but because intermolecular gaps exist between polymer molecules in polymer film materials, they cannot completely block the passage of small molecular volumes such as water and oxygen molecules. Therefore, in manufacturing fields such as food processing, pharmaceutical packaging, aerospace, solar power generation, new energy batteries, display materials, and electronic product encapsulation, there is a demand for polymer film materials with high barrier properties that do not affect product performance. In particular, polymer film materials required in high-end manufacturing fields such as aerospace, perovskite solar cell products, quantum dot films, and chip manufacturing have extremely high requirements for barrier properties against small molecules such as water and oxygen, as well as particularly high requirements for transparency and flexibility of high-barrier film materials. For this reason, there has been an urgent need to develop highly transparent and flexible film materials with excellent water vapor barrier and oxygen barrier properties.

[0003] The methods currently employed in conventional technology are as follows:

[0004] Multilayer composite technology: Patent documents 1 (Dutch Shell) and 2 (Yuyuan, Jiangsu Province) employ a technique of multilayer composite construction using two or more films with different barrier properties. This multilayer composite technology increases the diffusion pathways for small molecules, thereby slowing down the time it takes for them to pass through. Even after prolonged use, small molecules can permeate the film layers, and during the production process, multilayer composite films are prone to problems such as bubbles, cracks, and wrinkles, ultimately affecting the barrier performance of the film.

[0005] Biaxial stretching technology: Patent document 3 uses biaxial stretching to enhance the orderliness of molecular chains, resulting in denser lamination and the ability to block small molecules. However, its drawback is that after high-temperature biaxial stretching, the crystallization stresses in the longitudinal and transverse directions become mismatched during the cooling process, making it easy for crystal dislocation defects to form and creating gaps through which molecules can pass, thus reducing barrier performance. Furthermore, if stretching alone is relied upon, gaps between molecules still exist, ultimately failing to ensure barrier performance.

[0006] Coating technology: This method involves coating the surface of a film with a barrier layer. One method involves coating metal films such as barrier films or solar cells, as described in Patent Document 4 (DuPont). While this improves the barrier properties of the film, the film is opaque and cannot transmit visible light, lasers, electron beams, or microwaves, affecting subsequent processing. Another method involves coating with inorganic oxides, such as those described in Patent Document 5 (Toppan Printing Co., Ltd.). While transparency is achieved, this method relies solely on the inorganic coating, resulting in insufficient barrier performance for the film. Furthermore, the inorganic coating is brittle and easily scratched. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] U.S. Publication No. US728,004 19850429 [Patent Document 2] Chinese Patent No. CN202220521066.5 [Patent Document 3] European Patent No. EP9840132119980603 [Patent Document 4] Chinese Patent No. CN201821178089.0 [Patent Document 5] Chinese Patent No. CN93120385 Publication [Overview of the project] [Problems that the invention aims to solve]

[0008] To solve the above problems, the present invention provides an adhesive and a barrier layer containing the same, a highly transparent and flexible high-barrier film, and a film-like sealing and display material. The adhesive provided in this application has high epoxycyclohexylsiloxane activity and good crosslinking properties. The aminosiloxane and epoxycyclohexylsiloxane components undergo a thermal crosslinking reaction to form a three-dimensional silicon structure in the film layer formed of the polyvinyl alcohol-based film-forming resin, effectively filling the gaps between molecules of the polyvinyl alcohol-based film-forming resin, significantly improving the water and oxygen barrier function, and also improving the scratch resistance of the film layer formed of the polyvinyl alcohol-based film-forming resin. The reaction between epoxidized-terminated hydroxylpolybutadiene and other components in the adhesive not only improves the water and oxygen barrier ability of the film layer formed of the polyvinyl alcohol-based film-forming resin, but also effectively improves the flexibility of the film layer at low temperatures. [Means for solving the problem]

[0009] The object of the present invention is achieved by the following means: an adhesive comprising a polyvinyl alcohol-based film-forming resin as component A, an aminosiloxane as component B, an epoxycyclohexylsiloxane as component C, and an epoxidized-terminated hydroxypolybutadiene as component D.

[0010] When calculated using molar ratios, the optimal ratio of moles of active hydrogen in amino groups to moles of epoxy groups in the adhesive component is 1:1.

[0011] The polyvinyl alcohol-based film-forming resin is polyvinyl butyral, and the structural formula of the aminosiloxane is as follows:

[0012] [ka]

[0013] The structural formula of epoxycyclohexylsiloxane is as follows:

[0014] [Chemical]

[0015] For a total of 100 parts by weight of the three components of Component A, Component B, and Component C, Component A accounts for 60 - 90%, and the total of Component B and Component C accounts for 10 - 40%. Calculated by molar ratio, Component B:Component C ≥ 2, and the addition amount of the reinforcing resin Component D is 1 - 5% of the total weight of the three components of Component A, Component B, and Component C.

[0016] The molecular weight of polyvinyl butyral is 70,000 - 250,000, and the degree of acetalization is 79 - 93%. The weight average molecular weight of epoxidized terminal hydroxy polybutadiene is 2,000 - 4,000.

[0017] The adhesive also contains diluents which are alcohol-based and ester-based solvents.

[0018] A barrier layer, and the barrier layer is formed by thermally cross-linking at a temperature of 80 - 120°C after applying the adhesive.

[0019] A highly transparent and flexible high-barrier film, which consists of a polymer substrate, a primer layer, a silicon oxide deposition layer, and a barrier layer in order from bottom to top, and the barrier layer is the said barrier layer.

[0020] The material of the polymer substrate is polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyethylene or polypropylene, and the thickness of the substrate is 10 - 150 μm.

[0021] The primer layer contains a silicon-containing linear polyurethane resin that does not contain a benzene ring structure.

[0022] The silicon oxide deposition layer is a silicon dioxide deposition layer obtained by plasma enhanced chemical vapor deposition, and the thickness of the silicon oxide deposition layer is 40 - 80 nm.

[0023] The amount of barrier layer to be applied is 1-2 g / m². 2 The drying temperature is 80-120°C.

[0024] The silicon-containing linear polyurethane resin, which does not contain a benzene ring structure, is a polyurethane adhesive obtained by polymerizing dicyclohexylmethane diisocyanate, polyether diol, and hydroxyl organosilicon at both ends, extending the chain with dimethylolpropionic acid, and encapsulating the ends with silanol. The application rate is 1-2 g / m². 2 That is the case.

[0025] The thickness of the silicon oxide deposit layer is 50-60 nm.

[0026] A film-like sealing and display material, wherein the sealing and display material is manufactured from the high-barrier film. [Effects of the Invention]

[0027] Compared to conventional technologies, the present invention provides an adhesive and a barrier layer containing the same, a highly transparent and flexible high-barrier film, and a film-like sealing and display material. The adhesive provided in this application has high epoxycyclohexylsiloxane activity and good crosslinking properties. The aminosiloxane and epoxycyclohexylsiloxane components undergo a thermal crosslinking reaction to form a three-dimensional silicon structure in the film layer formed of the polyvinyl alcohol-based film-forming resin, effectively filling the gaps between molecules of the polyvinyl alcohol-based film-forming resin, significantly improving the water and oxygen barrier function, and also improving the scratch resistance of the film layer formed of the polyvinyl alcohol-based film-forming resin. The reaction between epoxidized-terminated hydroxylpolybutadiene and other components in the adhesive not only improves the water and oxygen barrier ability of the film layer formed of the polyvinyl alcohol-based film-forming resin, but also effectively improves the flexibility of the film layer at low temperatures. Furthermore, the adhesive of this application, after crosslinking, and the barrier layer formed therefrom, not only possess good water vapor barrier and oxygen barrier properties, but also high transparency, excellent flexibility, low ultraviolet absorption, resistance to yellowing, and good scratch resistance.

[0028] When using an adhesive as a barrier layer for a highly transparent and flexible high-barrier film, the aminosiloxane and epoxycyclohexylsiloxane components can increase the bonding strength with the silicon dioxide deposition layer.

[0029] The highly transparent and flexible high-barrier film provided in this invention achieves the objectives of high transparency, flexibility, and high barrier properties by utilizing a silicon-containing linear polyurethane resin primer layer that does not contain a benzene ring structure, silicon dioxide obtained by plasma-enhanced chemical vapor deposition, and a transparent and flexible silane epoxy crosslinked barrier layer technology to block water vapor and oxygen. The silicon-containing linear polyurethane resin primer layer that does not contain a benzene ring structure has low UV absorption, does not yellow, and has superior transparency and flexibility compared to a thermosetting primer layer. The polyurethane primer layer contains a silicon structure that is advantageous for the subsequent deposition of silicon dioxide, thereby increasing the robustness of the deposited layer. The silicon dioxide deposited layer is a silicon dioxide deposited layer obtained by plasma-enhanced chemical vapor deposition, which has high transparency and excellent water vapor and oxygen barrier properties. The barrier layer of this invention not only has excellent water vapor and oxygen barrier properties, good transparency and flexibility, but also has a strong bonding force with the silicon dioxide deposited layer, which can protect the fragile silicon dioxide deposited layer. [Brief explanation of the drawing]

[0030] [Figure 1] This is a schematic diagram of the highly transparent and flexible high-barrier film of the present invention. [Modes for carrying out the invention]

[0031] An adhesive comprising a polyvinyl alcohol-based film-forming resin as component A, an aminosiloxane as component B, an epoxycyclohexylsiloxane as component C, and an epoxidized-terminated hydroxypolybutadiene as component D.

[0032] The aminosiloxane and epoxycyclohexylsiloxane components undergo a thermal crosslinking reaction to form a three-dimensional silicon structure within the film layer formed by the polyvinyl alcohol-based film-forming resin. This effectively fills the gaps between molecules in the polyvinyl alcohol-based film-forming resin, significantly improving the water and oxygen barrier function and enhancing the scratch resistance of the film layer. The reaction between epoxidized-terminated hydroxylpolybutadiene and other components in the adhesive not only improves the water and oxygen barrier capacity of the film layer formed by the polyvinyl alcohol-based film-forming resin, but also effectively improves the flexibility of the film layer at low temperatures.

[0033] When calculated using molar ratios, the optimal ratio of moles of active hydrogen in amino groups to moles of epoxy groups in the adhesive component is 1:1.

[0034] Examples of polyvinyl alcohol-based film-forming resins include polyvinyl acetal, preferably polyvinyl butyral. Polyvinyl butyral has excellent film-forming properties, high transparency of the film layer, and good flexibility. Polyvinyl butyral has better moisture resistance than polyvinyl alcohol, possesses good water vapor and oxygen barrier properties, and also has good light resistance, heat resistance, and cold resistance. Because it contains many hydroxyl groups and aldehyde functional groups that form hydrogen bonds with the silicon dioxide surface, it has very high adhesion to the silicon dioxide interface.

[0035] Component A is polyvinyl butyral with a high molecular weight and high acetalization degree, selected to improve moisture resistance. The molecular weight of the polyvinyl butyral is 70,000 to 250,000, and the acetalization degree is 79 to 93%.

[0036] The structural formula of aminosiloxane is as follows:

[0037] [ka]

[0038] Component B is a siloxane-containing diamine that does not contain ester or ether bonds. The siloxane bonds have glass-like transparency due to the organosilicon, and the terminal amino groups react with component C of the adhesive to undergo epoxy crosslinking, improving the adhesion and barrier properties of the barrier layer.

[0039] The structural formula of epoxycyclohexylsiloxane is as follows:

[0040] [ka]

[0041] Component C is tetraepoxycyclohexylsiloxane, and its epoxy groups, bonded by four cyclohexyl groups, possess efficient crosslinking properties. This allows it to undergo stereocrosslinking with the amino groups of the siloxane-containing diamine in component B, significantly improving the adhesion and barrier properties of the barrier layer.

[0042] Component B, a siloxane-containing diamine, and component C, tetraepoxycyclohexylsiloxane, can form a dense silicon-containing film with polyvinyl butyral. The silicon atoms effectively fill the voids between polyvinyl butyral molecules, effectively blocking the permeation of water vapor and oxygen. At the same time, the barrier layer contains a siloxane structure, which has high affinity with the silicon dioxide deposition layer of the high-barrier film, making it less likely for the barrier layer to detach during future use.

[0043] Component D, epoxidized-terminated hydroxypolybutadiene, is a reactive liquid rubber with excellent hydrophobicity and flexibility at low temperatures. Epoxidized-terminated hydroxypolybutadiene undergoes crosslinking reactions with aminosiloxanes, resulting in excellent water-sealing properties, increased film density, and improved water vapor barrier properties of the film layer. Simultaneously, its elastic butadiene structure effectively improves film flexibility at low temperatures, helping high-barrier films maintain excellent flexibility even when used in extremely cold environments. The weight-average molecular weight of component D, epoxidized-terminated polybutadiene, is 2000-4000.

[0044] The main component of the adhesive is a transparent component, providing high flexibility.

[0045] Of the total 100 parts by weight of the three components A, B, and C of the adhesive, component A accounts for 60-90%, the combined total of components B and C accounts for 10-40%, and the amount of component D added is 1-5% of the total weight of the three components A, B, and C.

[0046] To facilitate film formation by applying the adhesive, the adhesive also contains a diluent, and the diluent is preferably an alcohol-based or ester-based solvent. Preferred solvents include ethanol, n-propanol, isopropanol, ethyl acetate, and butyl acetate, which have excellent low toxicity and are environmentally friendly.

[0047] The coating amount of the high-barrier film of the present invention refers to the number of grams of solids contained per square meter of the coated film layer, excluding solvent components.

[0048] A barrier layer is formed by applying the adhesive to form a film and then thermally crosslinking it.

[0049] The amount of barrier layer to be applied is 1-2 g / m². 2 The drying temperature is 80-120°C.

[0050] As shown in Figure 1, the film is highly transparent and flexible, and consists of a polymer substrate 1, a primer layer 2, a silicon oxide deposition layer 3, and a barrier layer 4, in that order from bottom to top, with the barrier layer above the silicon oxide deposition layer 3 being the aforementioned barrier layer.

[0051] First, the polymer substrate for the highly transparent and flexible high-barrier film of the present invention will be described.

[0052] The polymer substrate for the highly transparent and flexible high-barrier film of the present invention is a thin film made from an organic polymer. These may be single-layer or multi-layer thin films made from one or more polymer materials by methods such as casting, stretching, co-extrusion, or blow molding, and necessary functional additives such as plasticizers and antistatic agents may be added. Examples of polymer materials include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyimide (PI), polyethylene (PE), polypropylene (PP), polyvinyl alcohol (PVA), ethylene-vinyl alcohol copolymer (EVOA), polyvinyl chloride (PVC), polyvinylidene chloride (PVDC), and fluorine-containing polyethylene. Preferably, the polymer substrate for the highly transparent and flexible high-barrier film of the present invention is a thin film made from polymer materials such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyethylene, or polypropylene, as this film material has excellent flexibility and light transmittance. The thickness of the polymer substrate for the high-barrier film of the present invention is preferably 10 to 150 μm.

[0053] The primer layer of the high-barrier film of the present invention will be described below.

[0054] The primer layer of a high-barrier film not only improves the bonding strength between the polymer substrate and the silicon dioxide deposition layer, but can also enhance the gas barrier effect of the film material. The primer layer can be selected from acrylic resin, polyester resin, phenolic resin, epoxy resin, polyurethane resin, silane resin, silicone resin, nitrile rubber, etc. The primer layer of the present invention uses a silicon-containing linear polyurethane resin that does not contain a benzene ring structure, and is an adhesive prepared from isocyanate and hydroxyl compounds. Preferably, it is a polyurethane adhesive obtained by polymerizing diisocyanate dicyclohexylmethane and a polyether diol (for example, polypropylene glycol PPG(2000) is a polyether diol), and hydroxyl organosilicon at both ends, extending the chain with dimethylolpropionic acid, and encapsulating the ends with silanol. It has excellent transparency, flexibility and adhesion, does not contain a benzene ring, has low UV absorption, is resistant to yellowing, contains polyether segments and organosilicon, has good barrier properties, and has good robustness with the silicon dioxide deposition layer. The amount of primer layer to be applied is 1-2 g / m². 2 That is the case.

[0055] Next, the silicon oxide deposit layer of the highly transparent and flexible high-barrier film of the present invention will be described.

[0056] The highly transparent and flexible high-barrier film of the present invention comprises a silicon dioxide deposited layer. The silicon dioxide film possesses a series of excellent physicochemical properties, including high-temperature stability, chemical stability, low transmittance, and gas barrier properties, as well as high transparency and a low refractive index, thus meeting the electronics industry's demands for high precision and high transparency. The silicon dioxide deposited layer of the high-barrier film of the present invention is a silicon dioxide deposited layer obtained by plasma-enhanced chemical vapor deposition. According to the principle of magnetic confinement of charged particles, plasma-enhanced chemical vapor deposition achieves the objective of confining electrons using a magnetic field, thereby increasing the dissociation rate of gas molecules and increasing the thin film deposition rate. A silicon dioxide thin film is deposited using a mixed gas of an organosilicon compound and oxygen. Selectable organosilicon compounds include hexamethyldisiloxane, tetramethoxysilane, tetraethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diphenyldimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, and tetramethylsilane, with hexamethyldisiloxane being preferred. If the thickness of the silicon dioxide deposition layer is less than 30 nm, the gas barrier performance of the film material is significantly reduced, and if the thickness of the silicon dioxide deposition layer exceeds 100 nm, the ease of winding and transparency of the film material are affected. Therefore, the thickness of the gas silicon dioxide deposition layer of the high-barrier film of the present invention is 40 to 80 nm, preferably 50 to 60 nm.

[0057] Finally, we will describe the barrier layer on the silicon oxide deposit layer of the highly transparent and flexible high-barrier film.

[0058] The barrier layer is characterized by high transparency and good flexibility. The component polyvinyl butyral has excellent film-forming properties, resulting in a film layer with high transparency and good flexibility.

[0059] Epoxycyclohexylsiloxane exhibits high reactivity and excellent crosslinking properties. The aminosiloxane and epoxycyclohexylsiloxane components undergo a thermal crosslinking reaction, forming a three-dimensional silicon structure within the film layer formed by the polyvinyl alcohol-based film-forming resin. This effectively fills the intermolecular gaps in the polyvinyl alcohol-based film-forming resin, significantly improving the water and oxygen barrier function and enhancing the scratch resistance of the film layer. The reaction between epoxidized-terminated hydroxylpolybutadiene and other components in the adhesive not only improves the water and oxygen barrier capacity of the film layer formed by the polyvinyl alcohol-based film-forming resin but also effectively improves the flexibility of the film layer at low temperatures.

[0060] The adhesive of this application, after crosslinking, and the barrier layer formed therefrom, not only possess good water vapor barrier and oxygen barrier properties, but also high transparency, excellent flexibility, low UV absorption, resistance to yellowing, and good scratch resistance. The barrier layer is composed of transparent components, possesses high flexibility, and is resistant to yellowing.

[0061] When using an adhesive as a barrier layer for a highly transparent and flexible high-barrier film, the aminosiloxane and epoxycyclohexylsiloxane components can enhance the bonding strength with the silicon dioxide deposition layer. In particular, epoxycyclohexylsiloxane has high activity and good crosslinking properties, which can increase the bonding strength between the barrier layer and the silicon dioxide deposition layer, thereby protecting the fragile silicon dioxide deposition layer.

[0062] The barrier layer of the present invention is typically applied by known techniques in the art, such as knife application, scraper application, slit die application, roller application, and press application, with an application amount of 0.5 to 2 g / m². 2 The drying temperature is 80-120°C.

[0063] The present invention will be described in detail below with reference to specific examples. These examples are for further explanation of the present invention and are not intended to limit the scope of protection of the present invention. Those skilled in the art can make some non-essential improvements and adjustments based on the above-described content of the present invention.

[0064] The main raw materials are available from the following companies: Polymer substrates: Polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate (PC), polyamide (PA), polyethylene (PE), and polypropylene (PP) thin films are all manufactured by Xiamen Chang Plastics Co., Ltd.; Dicyclohexylmethane diisocyanate (HMDI) is manufactured by Covestro GmbH in Germany, polypropylene glycol (PPG(2000)) is manufactured by Jiangsu Petrochemical Co., Ltd., both-terminated hydroxyl organosilicon is manufactured by Guangzhou Slox New Materials Co., Ltd., tri(tert-pentaoxy)silanol, hexamethyldisiloxane, triethylenediamine, dimethylolpropionic acid, dimethylacetamide, and component C, tetraepoxycyclohexylsiloxane, are manufactured by Merck, Inc., and polyvinyl butyral is manufactured by Monsanto Corporation in the United States. R The components were obtained from the product: component B, a siloxane-containing diamine, was manufactured by Aladdin Biochemical Technology Co., Ltd.; component D, an epoxidized-terminated hydroxypolybutadiene, was obtained from Liming Chemical Research Institute; and ethylene glycol methyl ether was manufactured by Jiangsu Tianyin Chemical Co., Ltd.

[0065] Preparation of the polyurethane adhesive for the primer layer: 26.35 g of dicyclohexylmethane diisocyanate, 55 g of polypropylene glycol PPG (molecular weight 2000), 5 g of organosilicon with hydroxyl groups at both ends (molecular weight 4000), and 1 g of triethylenediamine were added to a 1000 ml four-necked flask equipped with a temperature-controlled heater, mechanical stirrer, drying tube, condensation reflux, and nitrogen protection device, and reacted at 80 °C for 3 hours. Then, 120.72 g of dimethylolpropionic acid and 93.5 g of dimethylacetamide were added and reacted for 3 hours. After that, 24.52 g of tri(tert-pentaoxy) silanol was added and reacted for 2 hours. The temperature was lowered to terminate the reaction. The reaction stock solution was dropped into deionized water containing glacial acetic acid for dispersion, washed several times with deionized water, filtered, and dried. Then, it was prepared into a 10% coating solution using ethylene glycol methyl ether. The prepared coating solution was the polyurethane adhesive for the primer layer, and the material code was PU.

[0066] Preparation of the adhesive: The adhesive was usually used immediately after preparation, stored at 5 °C, and preferably used up within 4 hours. The adhesive codes were N1 to N4.

[0067] Adhesive N1: Component A polyvinyl butyral (Butvar R B-90, Mw = 70,000 - 100,000, degree of acetalization: 79 - 81%) 90 g, Component B compound 2.52 g, Component C compound 7.48 g, Component D (Mw = 4000) compound 1 g, diluent ethanol:ethyl acetate = 1:1 (mass ratio), dilution concentration 20%.

[0068] Adhesive N2: Component A polyvinyl butyral (Butvar R B-76, Mw = 90,000 - 120,000, degree of acetalization: 83 - 93%) 80 g, Component B compound 5.04 g, Component C compound 14.96 g, Component D (Mw = 4000) compound 3 g, diluent n-propanol:ethyl acetate = 1:1 (mass ratio), dilution concentration 20%.

[0069] Adhesive N3: Component A polyvinyl butyral (Butvar RB-74, Mw=120,000~150,000, Acetalization degree: 79~81%) 70g, Component B compound 7.56g, Component C compound 22.44g, Component D (Mw=3000) compound 4g, Diluent isopropanol:ethyl acetate = 1:1 (mass ratio), Dilution concentration is 20%.

[0070] Adhesive N4: Component A: Polyvinyl butyral (Butvar R B-72, Mw=170,000~2,500,000, Acetalization degree: 80%) 60g, Component B compound 10.08g, Component C compound 29.92g, Component D (Mw=2000) compound 5g, Diluent: Ethanol:Butyl acetate = 1:1 (mass ratio), Dilution concentration: 20%.

[0071] Examples of manufacturing highly transparent and flexible high-barrier films. (Example 1) 1. Corona treatment is applied to the coated surface of a 12 μm polyethylene terephthalate thin film on a polymer substrate. 2. Apply 1 g / m² of polyurethane adhesive PU from the primer layer to the corona-treated polymer substrate. 2 Apply with the following amount: 3. Plasma-enhanced chemical vapor deposition of silicon dioxide: Silicon dioxide is deposited onto a corona-treated substrate coated with polyurethane adhesive using a roll-to-roll plasma chemical vapor deposition (PECVD) system. The substrate is activated by argon plasma through the action of an RF electrode in a vacuum chamber. Then, hexamethyldisiloxane vapor and O2 are blown in, and the hexamethyldisiloxane vapor and O2 undergo a chemical reaction under the action of an electric arc, generating gaseous silicon dioxide, which is finally deposited on the substrate. The thickness of the deposited layer is 55 nm. 4. Adhesive N1 is applied to the silicon dioxide deposition layer of a silicon dioxide polymer substrate that has undergone plasma-enhanced chemical vapor deposition, with a barrier layer application amount of 1 g / m². 2 The drying temperature was 110°C.

[0072] (Examples 2-12) Based on the high-barrier film manufacturing process of Example 1, the parameters of the polymer substrate, primer layer, silicon oxide deposition layer, and barrier layer were changed according to the data shown in the high-barrier film manufacturing parameter table in Table 1 to produce the high-barrier films of Examples 2 to 12.

[0073] (Comparative Examples 1-6) Based on the high-barrier film manufacturing process of Example 1, the parameters of the polymer substrate, primer layer, silicon oxide deposition layer, and barrier layer were changed according to the data shown in Table 1 to produce the high-barrier films of Comparative Examples 1 to 6.

[0074] Preparation of the plasma-free silicon dioxide deposition layer in Comparative Example 4: Silicon dioxide was deposited on a corona-treated substrate coated with polyurethane adhesive using a roll-to-roll plasma chemical vapor deposition (PECVD) system. The substrate activation step with argon plasma was canceled, and only hexamethyldisiloxane vapor and O2 were blown in. The hexamethyldisiloxane vapor and O2 underwent a chemical reaction under the action of an electric arc to generate gaseous silicon dioxide, which was finally deposited on the substrate. The thickness of the deposited layer was 60 nm.

[0075] The performance of the high-barrier films in the above examples and comparative examples was evaluated by the following test methods.

[0076] 1. Measurement of the film thickness of a thin film coating. The measurement was performed using a Filmites F20-UV optical film thickness analyzer, in accordance with the national standard GB / T33051-2016 "Method for measuring the thickness of the hardened layer of surface-hardened thin films with optical functional properties".

[0077] 2. Measurement of light transmittance (T) of thin films The test was conducted using a DIFFUSION M57D haze meter, manufactured in the UK, in accordance with the national standard GB / T2410-2008, "Measurement of light transmittance and haze of transparent plastics using a haze meter."

[0078] 3. Measurement of oxygen permeability (OTR) of thin films According to the oxygen permeability (OTR) test method described in the ASTM D3985 standard, MOCON OX-TRAN in the United States R Tested with a 2 / 48 oxygen permeability analyzer.

[0079] 4. Measurement of water vapor transmission rate (WVTR) of thin films Water vapor transmission rate (WVTR) was tested using a MOCON PERMATRAN-W 3 / 34 WVTR analyzer in accordance with the water vapor transmission rate (WVTR) test method described in the ASTM F1249 standard.

[0080] 5. Measurement of coating adhesion of thin films Adhesion was measured according to the international standard ISO 2409 cross-cut method, and evaluated on a six-level classification system from 0 to 5, with classification 0 being the worst and classification 5 being the best.

[0081] 6. Measurement of the flexibility of thin coating films at low temperatures. The thin film samples were placed in a -50°C environment, and a 10cm x 10cm thin film sample was folded in half horizontally 500 times using a film bending machine (the surface of the thin film sample was folded in half in its natural state, immediately released, and then the back side was folded in half. The time required to complete one alternating front-to-back fold was 0.8 seconds, and each completed front-to-back fold was counted as one). After that, the direction of the fold of the thin film was reversed, and it was folded in half vertically 500 times, after which the water vapor barrier performance was measured and evaluated according to the degree of decrease in water vapor barrier performance, and evaluated on a scale of 1 to 10, with classification 1 being the worst flexibility and classification 10 being the best flexibility.

[0082] The performance evaluation results of the high-barrier films in the examples and comparative examples are shown in Table 2, High-Barrier Film Performance Evaluation Table.

[0083] [Table 1]

[0084] [Table 2]

[0085] Table 2 shows the performance comparison results of the examples and comparative examples, demonstrating that the highly transparent and flexible high-barrier film produced by the technology of the present invention can exhibit better performance in important indicators such as light transmittance, oxygen transmittance, water vapor transmittance, coating adhesion, and flexibility at low temperatures compared to other high-barrier films. The present invention achieves its objectives through a series of comprehensive solutions. Specifically, the polymer substrate uses highly transparent and flexible polymer materials such as polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyethylene, and polypropylene, and the primer layer uses a flexible silicone-based polyurethane that does not contain benzene rings, resulting in excellent barrier properties and high robustness with the silicon dioxide deposition layer. The silicon dioxide deposition layer uses silicon dioxide obtained by plasma-enhanced chemical vapor deposition, resulting in excellent transparency, adhesion, and barrier properties. The barrier layer, using aminosiloxane, epoxycyclohexylsiloxane, and epoxidized-terminated hydroxypolybutadiene crosslinked-reinforced polyvinyl butyral adhesive, not only possesses excellent transparency and flexibility, but the silicon atoms effectively fill the intermolecular voids, effectively blocking the permeation of water vapor and oxygen. The silicon-crosslinked polyvinyl butyral adhesive also has a strong bonding force with the silicon dioxide deposition layer, protecting the fragile silicon dioxide deposition layer. The polybutadiene-reinforced film layer exhibited better barrier properties and flexibility at low temperatures.

[0086] The high-barrier film provided in this invention possesses excellent gas barrier and water vapor barrier properties and can be used in the manufacture of oxygen barrier and water vapor barrier packaging materials. It can be used in fields such as food packaging, pharmaceutical packaging, electronic device sealing, perovskite solar cell films, and quantum dot display films.

[0087] The foregoing are merely preferred embodiments of the present invention, and the scope of protection of the present invention is not limited thereto. To those skilled in the art or familiar with the art, the scope of protection of the present invention also includes substituting or modifying the technical means and the technical idea of ​​the invention with equivalents, and making certain modifications and improvements, without departing from the overall technical idea of ​​the present invention. [Explanation of Symbols]

[0088] 1 Polymer base material 2. Primer layer 3. Silicon dioxide deposits 4. Barrier layer

Claims

1. It is an adhesive, It contains a polyvinyl alcohol-based film-forming resin as component A, an aminosiloxane as component B, an epoxycyclohexylsiloxane as component C, and an epoxidized-terminated hydroxypolybutadiene as component D. An adhesive characterized by the following features.

2. The molar ratio of active hydrogen in the amino group to the epoxy group in the adhesive component is 1:

1. The adhesive according to claim 1.

3. The aforementioned polyvinyl alcohol-based film-forming resin is polyvinyl butyral, The aforementioned aminosiloxane has the following structural formula: 【Chemistry 1】 It is a compound of, The epoxycyclohexylsiloxane has the following structural formula: 【Chemistry 2】 It is a compound of The adhesive according to claim 1.

4. Of the total 100 parts by weight of the three components A, B, and C, component A accounts for 60-90%, the total of components B and C accounts for 10-40%, and the amount of reinforcing resin component D added is 1-5% of the total weight of the three components A, B, and C. The molecular weight of the aforementioned polyvinyl butyral is 70,000 to 25,000, and the degree of acetalization is 79 to 93%. The weight-average molecular weight of the epoxidized-terminated hydroxypolybutadiene is 2000 to 4000. The adhesive according to claim 3.

5. It also contains diluents, which are alcohol-based and ester-based solvents. The adhesive according to claim 4.

6. It is a barrier layer, Formed by applying the adhesive according to any one of claims 1 to 5 and then thermal crosslinking at a temperature of 80 to 120°C. A barrier layer characterized by the following features.

7. A highly transparent and flexible high-barrier film comprising, from bottom to top, a polymer substrate, a primer layer, a silicon oxide deposition layer, and a barrier layer, wherein the barrier layer is the barrier layer described in claim 6. A highly transparent, flexible, and barrier-free film characterized by these features.

8. The material of the polymer substrate is polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyamide, polyethylene, or polypropylene, and the thickness of the substrate is 10 to 150 μm. The primer layer comprises a silicon-containing linear polyurethane resin that does not contain a benzene ring structure. The silicon dioxide deposition layer is a silicon dioxide deposition layer obtained by plasma-enhanced chemical vapor deposition, and the thickness of the silicon dioxide deposition layer is 40 to 80 nm. The amount of the barrier layer applied is 1 to 2 g / m². ２ The drying temperature is 80-100°C. The highly transparent and flexible high-barrier film according to claim 7.

9. The silicon-containing linear polyurethane resin, which does not contain the aforementioned benzene ring structure, is a polyurethane adhesive obtained by polymerizing dicyclohexylmethane diisocyanate, polyether diol, and hydroxyl organosilicon at both ends, extending the chain with methylolpropionic acid, and encapsulating the ends with silanol. The application amount is 1 to 2 g / m². ２ And, The thickness of the silicon oxide deposit layer is 50 to 60 nm. The highly transparent and flexible high-barrier film according to claim 7.

10. A film-like sealing and display material, A sealing and display material manufactured from a high-barrier film according to any one of claims 7 to 9. A film-like sealing and display material characterized by the following:

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