Silicone composition capable of indicating leakage by color change in response to hydrogen gas, and film comprising the same

Abstract

The present invention relates to a hydrogen gas-sensitive silicon composition and a film containing the same. A hydrogen gas-sensitive silicone composition according to the present invention comprises: a siloxane base comprising one or more vinyl groups; an adhesive comprising siloxane; a crosslinking agent comprising Si-H bonds that react with the siloxane base; a sensitizer comprising a transition metal oxide and a palladium-based catalyst; and a moisture stabilizer for suppressing the leaching or deterioration of the sensitizer due to moisture. The composition of the present invention stably incorporates a sensitizer within a silicone matrix formed by the crosslinking reaction between a siloxane base and a crosslinking agent, thereby enabling the visual recognition of the chemical's presence through a color change upon contact with hydrogen gas. Additionally, the dispersion stability of the sensitizer, the mechanical properties of the film, and long-term stability can be improved by means of an adhesive, a silicone-based additive, a viscosity modifier, or a moisture stabilizer. The silicone composition according to the present invention can be applied and cured on a substrate to be provided in the form of a film, and said film can exhibit a rapid and clear color change in response to hydrogen gas while maintaining adhesion to the substrate. Accordingly, the present invention can be usefully applied in various industrial fields, such as hydrogen gas leak detection, industrial equipment monitoring, and safety indicator films.

Description

Technology Field

[0001] The present invention relates to a silicone composition capable of detecting leakage by color upon reaction with hydrogen gas, and a film comprising the same. Specifically, the present invention relates to a silicone composition comprising a component that reacts with hydrogen gas within a silicone matrix, and a film comprising the same. Background Technology

[0002] Hydrogen gas is used as an essential core material across the entire next-generation eco-friendly energy industry, including semiconductor processes, hydrogen vehicle charging stations, fuel cell systems, and energy storage systems (ESS). However, hydrogen gas is not only colorless and odorless but also has a very small molecular size, making it highly susceptible to leakage and having a wide explosive range; consequently, even the slightest leak poses a significant risk of leading to a major accident. Accordingly, the importance of color-changing-based detection technology, which enables the rapid and intuitive visual identification of hydrogen gas leaks, is steadily increasing.

[0003] Hydrogen sensing technology primarily utilizes the reduction reaction of transition metal oxides. These color-changing materials must be used in conjunction with metal catalysts, such as palladium (Pd), which dissociate hydrogen molecules, and have traditionally been supported on paper, non-woven fabrics, or simple polymer matrices to form films. However, this approach has limitations, such as the easy leaching of sensitizers and catalyst precursors upon exposure to moisture or external solvents, or reduced reaction rates and uneven color changes resulting from the uneven dispersion of nanoparticles within the matrix.

[0004] In particular, paper or non-woven fabric-based sensors have low processability and weak mechanical strength, so when applied to equipment with complex shapes such as curved pipes or valves, the adhesion is poor, and there is a problem that they are prone to losing reliability as sensors due to reduced durability upon long-term exposure.

[0005] Meanwhile, although silicon is widely used as an industrial protective film due to its excellent heat resistance, chemical resistance, and flexibility, it is difficult to stably immobilize polar particles, such as hydrogen sensitizers (metal oxides and catalyst precursors), within a hydrophobic silicon matrix. If sensitizers are simply mixed into a silicon composition, particle sedimentation or uneven distribution occurs depending on the viscosity or curing conditions of the composition, leading to problems with inconsistent sensing performance.

[0006] Furthermore, if external moisture penetrates, the activity of the catalyst may be degraded or the responsive components may leak out, potentially causing environmental pollution. Therefore, there is an urgent need to develop novel hydrogen gas-sensitive silicon compositions and films utilizing them that can ensure stable reactivity through an optimal curing process, along with advanced matrix design technology capable of blocking contamination by moisture and solvents while allowing selective hydrogen gas permeability. Prior art literature

[0007] Republic of Korea Registered Patent No. 10-0457798 The problem to be solved

[0008] The present invention is proposed to solve the above-mentioned problems, and

[0009] The objective is to provide a responsive silicone film composition that exhibits a clear color change upon contact with hydrogen gas, while suppressing the migration or leaching of the responsive component, thereby enabling stable long-term use.

[0010] Furthermore, another objective of the present invention is to provide a responsive silicone film composition capable of simultaneously achieving high reaction sensitivity to hydrogen gas while also ensuring ease of use, including the physical properties and mechanical strength of the film. Additionally, another objective of the present invention is to provide a responsive silicone film in which the composition and formulation are designed so that the hydrogen gas reaction solution is uniformly dispersed within the silicone matrix and does not negatively affect the curing reaction of the silicone or the mechanical properties of the film. Furthermore, another objective of the present invention is to provide a responsive silicone film that is applicable to various polymer substrates and can be easily applied in industrial settings through a coating process. means of solving the problem

[0011] One example of the present invention provides a hydrogen gas-sensitive silicone composition comprising: a siloxane base comprising one or more vinyl groups; an adhesive comprising siloxane; a crosslinking agent comprising Si-H bonds that react with the siloxane base; a sensitizer comprising a transition metal oxide and a palladium-based catalyst; and a moisture stabilizer for inhibiting the leaching or deterioration of the sensitizer by moisture.

[0012] Another example of the present invention provides a method for manufacturing a hydrogen gas-sensitive silicone film, comprising the steps of: preparing a silicone composition by mixing a siloxane base containing one or more vinyl groups, an adhesive containing siloxane, a crosslinking agent containing a Si-H bond that reacts with the siloxane base, a sensitizing agent containing a transition metal oxide and a palladium-based catalyst, and a moisture stabilizer; applying the silicone composition to which the crosslinking agent has been added onto a substrate; and forming a hydrogen gas-sensitive silicone film by curing the silicone composition. Effects of the invention

[0013] The responsive silicon film composition according to the present invention provides the effect of uniformly dispersing the responsive agent within the silicon matrix and effectively suppressing its elution by including a hydrogen gas responsive agent within an addition silicon network.

[0014] Accordingly, the responsive silicone film according to the present invention exhibits a rapid and vivid color change upon contact with hydrogen gas, while ensuring excellent reliability by preventing migration of the responsive agent or performance degradation even during long-term use.

[0015] Furthermore, the present invention can simultaneously secure the film's usability (physical properties and strength) and hydrogen gas reaction sensitivity while maintaining the stability of the sensitizer. Moreover, the visibility of the color change is improved, allowing for easy detection of leaks even in industrial sites with limited lighting.

[0016] In addition, the responsive silicone film according to the present invention can be applied to various polymer substrates and manufactured under general heat-curing conditions, so it can be widely utilized across chemical facilities, piping, storage containers, and work environments. Brief explanation of the drawing

[0017] Figure 1 is a photograph comparing the color change of a hydrogen gas-sensitive silicon film before (left) and after (right) exposure to hydrogen gas. Figure 2 shows the results of structural analysis of WO3 and WO3-Pd complexes, where (A) is the X-ray diffraction (XRD) pattern of WO3, (B) is the scanning electron microscope (SEM) image of WO3, (C) is the transmission electron microscope (TEM) image of the WO3-Pd complex, and (D) is the energy dispersive X-ray spectroscopy (EDX) analysis result of the WO3-Pd complex. Figure 3 is a photograph showing the change in the appearance of the reaction solution during the synthesis process of the WO3-Pd complex using a chemical reducing agent. Figure 4 is a photograph comparing the color change of hydrogen gas-sensitive silicon films before and after exposure to hydrogen gas according to the type of dispersion solvent of the sensitizer reaction solution, showing the results of films using methanol (MeOH), acetone, and tetrahydrofuran (THF) as dispersion solvents, respectively. Figure 5 is a photograph comparing the appearance of silicon films before and after exposure to hydrogen gas, prepared according to the order of component input, type of WO3 raw material, and palladium content conditions during WO3-Pd synthesis. Figure 6 is a photograph comparing the color change of a hydrogen gas-sensitive silicone film before and after exposure to hydrogen gas according to the type of moisture stabilizer, showing the results under conditions of hydrophobic fumed silica (R972) addition, release agent addition, silica-zirconium composite aerogel (Z2H1) dispersion addition, and no additive addition, respectively. Figure 7a is a photograph showing the color change of a silicon film containing a WO3-Pd sensitizer synthesized using a chemical reducing agent (L(+)-ascorbic acid) before and after exposure to hydrogen gas, and (1) and (2) are results for specimens prepared independently, respectively. Figure 7b is a photograph showing the color change of a silicon film containing a WO3-Pd sensitizer synthesized by UV photoreduction before and after exposure to hydrogen gas, and (3) and (4) are results for specimens prepared independently, respectively. Specific details for implementing the invention

[0018] This document may use ordinal numbers such as “first” and “second” when referring to multiple components. There is no priority among the components.

[0019] In this document, if a specific commercially available product is used as a certain ingredient, the characteristics of that ingredient may refer to the characteristics listed in the product's Technical Data Sheet (TDS) or Certification of Analysis.

[0020] In this document, if the physical properties of a specific material vary depending on temperature and pressure, the measurement criteria for those physical properties may be 25 ℃ and 101.325 kPa.

[0021] In this document, the numerical range “within the range of A to B” means “A or greater and B or less.”

[0022] The numbers mentioned in this document are rounded values. For example, 1.5 is a number within the range of 1.45 to 1.54.

[0023] The term "about," which modifies numerical values, content, viscosity, or size, etc., described in the specification and claims of the present invention, is used to mean that it includes the range of ordinary measurement error or manufacturing process tolerance within the context in which the said numerical value is mentioned. Unless specifically otherwise stipulated, "about" may be interpreted to include a variation range of ±10% of the stated numerical value. For example, "about 100 cSt" should be understood to include a range of 90 to 110 cSt. The said term encompasses all unavoidable numerical variations that may occur due to the formulation of the chemical composition, the purity of the raw materials, the precision of the measuring equipment, or the experimental environment (temperature, humidity, etc.). Furthermore, the term is used with the intent to encompass all ranges that exhibit the same or equivalent functional effects as the technical effects intended by the present invention, even if there are minute differences from the stated numerical values.

[0024] The present document describes the invention in more detail below.

[0026] The siloxane used in the present invention may be an oligomer or polymer containing siloxane repeating units and may be appropriately selected considering the film-forming ability, flexibility, and responsiveness of the composition. The siloxane is a siloxane containing vinyl groups and is not particularly limited as long as it is capable of forming a cross-linked structure through reaction with a cross-linking agent.

[0027] The above siloxane may be a siloxane comprising one or more alkyl substituents, and the alkyl substituent may be an alkyl group having 1 or more carbon atoms, 1 to 8 carbon atoms, or 1 to 10 carbon atoms. In one embodiment, the alkyl substituent may be a methyl group, an ethyl group, a propyl group, a butyl group, or a combination thereof, preferably a methyl group, and the siloxane may preferably be dimethylsiloxane. In addition, the number of carbon atoms of the alkyl substituent may be selected considering the flexibility of the siloxane chain, the viscosity of the composition, and the diffusion characteristics of hydrogen gas.

[0028] The above siloxane may comprise a single type of siloxane or may comprise two or more siloxanes having different molecular weights, structures, or substituents. For example, the above siloxane may be a mixture of siloxanes having different molecular weights, thereby allowing the viscosity of the composition, the applicability, and the mechanical properties of the film to be controlled.

[0029] In addition, the siloxane may have a linear structure, a branched structure, or a combination thereof, and may include a cyclic siloxane as needed. Such structural forms may be selected depending on the processability of the composition and the physical properties of the film after curing.

[0030] In one embodiment, the siloxane may include a modified siloxane to control hydrophilicity or hydrophobicity. For example, the siloxane may include a polyether-modified siloxane, an alkyl-modified siloxane, or a combination thereof, and such modification may be used for the purpose of improving the dispersibility of the sensitizer or the stability of the composition.

[0031] The above siloxane may be a low molecular weight siloxane, a high molecular weight siloxane, or a mixture thereof, and may have a liquid or viscous composition at room temperature. The molecular weight, viscosity, and number of repeating units of the siloxane may be appropriately selected within a range capable of achieving the objectives of the present invention, but are not limited thereto.

[0033] One example of the present invention provides a hydrogen gas-sensitive silicone composition comprising: a siloxane base comprising one or more vinyl groups; an adhesive comprising siloxane; a crosslinking agent comprising Si-H bonds that react with the siloxane base; a sensitizing agent comprising a transition metal oxide and a palladium-based catalyst; and a moisture stabilizer.

[0034] The above silicone composition has a three-dimensional network structure as its basic framework, formed by the addition crosslinking reaction of a siloxane base containing vinyl groups and a crosslinking agent containing Si-H bonds. The siloxane used in the present invention may be an oligomer or polymer containing siloxane repeating units, and preferably may be dimethylsiloxane containing one or more methyl substituents. The type of substituent and molecular weight of the siloxane may be appropriately selected from linear, branched, or cyclic siloxanes, or mixed, taking into consideration the viscosity, coating properties, and hydrogen gas diffusion characteristics of the composition.

[0036] Siloxan base

[0037] A hydrogen gas-sensitive silicon composition according to one example of the present invention comprises a siloxane base containing one or more vinyl groups. The siloxane base is a main component that forms a cross-linked structure through an addition reaction with Si-H bonds included in a cross-linking agent, and forms the basic framework of a silicon film formed after curing.

[0038] The above siloxane base may be a polysiloxane containing vinyl groups, and in one embodiment, may include a vinyl-terminated polydimethylsiloxane. Additionally, some of the hydrogen atoms bonded to carbon atoms included in the polysiloxane are deuterium, C1 to C8 alkyl groups, C1 to C8 alkenyl groups, C1 to C8 alkynyl groups, C3 to C 12 It can be substituted with a cycloalkyl group or a combination thereof.

[0039] The above siloxane base may be a polysiloxane containing vinyl groups, for example, polydimethylsiloxane, preferably a polydimethylsiloxane containing vinyl groups at the ends. The above siloxane base has excellent flexibility and can stably maintain its film shape against external impact or deformation even after curing.

[0040] The above siloxane base may be included in a range of 20 to 50 parts by weight, 20 to 45 parts by weight, 20 to 40 parts by weight, 25 to 50 parts by weight, 25 to 45 parts by weight, 25 to 40 parts by weight, 30 to 50 parts by weight, 30 to 45 parts by weight, 30 to 40 parts by weight, 35 to 50 parts by weight, 35 to 45 parts by weight, and 35 to 40 parts by weight, with respect to 100 parts by weight of the composition, and within this range, the flexibility, mechanical strength, and stability after curing of the film can be secured in a balanced manner. If the content of the above siloxane base is excessively low, the formation of the cross-linking network becomes insufficient, which may reduce the mechanical strength or shape stability of the film. Conversely, if the content of the siloxane base is excessively high, the content of the responsive agent or adhesive decreases relatively, which may lead to a decrease in responsiveness or adhesion performance to the substrate.

[0041] The above siloxane base comprises a polysiloxane containing vinyl groups, preferably a polysiloxane containing vinyl groups at the ends, and can form a three-dimensional crosslinked structure through an addition reaction with Si-H bonds included in the crosslinking agent. Since this crosslinked structure does not generate by-products during the curing process, it is advantageous for securing the mechanical strength and chemical resistance of the film while maintaining the chemical stability of the sensitizer.

[0043] adhesive

[0044] The composition of the present invention includes an adhesive comprising a siloxane to stably attach the film to a substrate while maintaining the flexibility and film-forming properties of the silicone matrix. The adhesive has excellent compatibility with the silicone matrix, thereby imparting adhesiveness so that the film is stably attached to the substrate after the composition is applied and cured.

[0045] In one embodiment, the adhesive may be a silicone adhesive composition comprising MQ siloxane resin. The MQ siloxane resin is (R 1 3SiO 1 / 2 ) a M units indicated as and (SiO 4 / 2 ) b It is selected from the Q unit indicated by . The above R 1 may independently be an alkyl group having 1 to 8 carbon atoms or an aryl group. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, and hexyl, and examples of the aryl group include phenyl, naphthyl, benzyl, tolyl, xylyl, and xenyl. a and b represent integers greater than 0, and the ratio of a / b is 0.5 to 1.5. The MQ silicone resin may further contain one or more of D units and T units, provided that 80 mol% or more, or 90 mol% or more, of the total MQ silicone resin consists of M and Q units. The MQ silicone resin may be, for example, trimethylsiloxysilicate, but is not limited thereto.

[0046] MQ siloxane resin provides both adhesiveness and flexibility within the siloxane network, contributing to the suppression of film peeling or cracking even when a sensitizer is present.

[0047] The above adhesive may be included in a range of 10 to 40 parts by weight, 10 to 35 parts by weight, 10 to 30 parts by weight, 10 to 25 parts by weight, 15 to 40 parts by weight, 15 to 35 parts by weight, 15 to 30 parts by weight, 15 to 25 parts by weight, 20 to 40 parts by weight, 20 to 35 parts by weight, 20 to 30 parts by weight, and 20 to 25 parts by weight. If the amount falls outside this range, a decrease in adhesive performance or a decrease in the mechanical stability of the film may occur. Additionally, the MQ siloxane resin may be included in a range of 10 to 60 parts by weight per 100 parts by weight of the adhesive. If the content of the above adhesive is excessively low, the film may peel off from the substrate or the adhesive reliability may be reduced. On the other hand, if the adhesive content is excessively high, the crosslinking density of the silicone matrix decreases, which may reduce the mechanical strength or chemical resistance of the film.

[0049] crosslinking agent

[0050] The composition of the present invention includes a crosslinking agent comprising a Si-H bond that reacts with the siloxane base. The crosslinking agent causes an addition reaction with the vinyl group of the siloxane base to form a three-dimensional crosslinked structure within the silicon matrix.

[0051] The crosslinking agent may be a methylhydrogen polysiloxane, an ethylhydrogen polysiloxane, or a polysiloxane containing Si-H bonds, and preferably may be a methylhydrogen polysiloxane. In addition, in one embodiment, it may be a solvent-free polysiloxane having a viscosity of 10 to 100 cSt.

[0052] The above-mentioned crosslinking agent may be included in a range of 5 to 30 parts by weight, 5 to 25 parts by weight, 5 to 20 parts by weight, 10 to 30 parts by weight, 10 to 25 parts by weight, 10 to 20 parts by weight, 15 to 30 parts by weight, 15 to 25 parts by weight, and 15 to 20 parts by weight, based on 100 parts by weight of the composition, and within this range, the crosslinking reaction with the siloxane base may be controlled so that it is neither excessive nor insufficient. The crosslinking agent containing the Si-H bond may participate in the crosslinking reaction and simultaneously function as a component that imparts surface release properties to the cured film. If the content of the crosslinking agent is excessively low, the crosslinking reaction with the siloxane base may not proceed sufficiently, resulting in poor curing of the film or residual tackiness. Conversely, if the content of the crosslinking agent is excessively high, the crosslinking density may increase excessively, potentially causing the film to become brittle or reducing the reactivity of the sensitizer.

[0054] Sensitizer

[0055] The composition of the present invention comprises a sensitizer comprising a transition metal oxide whose optical properties change upon reaction with hydrogen gas and a catalyst precursor that aids in the dissociation of hydrogen molecules. When the sensitizer comes into contact with hydrogen gas (H₂), it exhibits a color change through a reduction reaction, thereby enabling immediate visual recognition of whether gas is leaking.

[0056] The above-mentioned color-changing matrix comprises a transition metal oxide that changes color reversibly or irreversibly upon the injection of hydrogen ions. Specifically, the transition metal oxide may be an oxide comprising one or more metals selected from the group consisting of tungsten (W), titanium (Ti), tin (Sn), zinc (Zn), molybdenum (Mo), vanadium (V), chromium (Cr), and manganese (Mn); specifically, it may be one or more oxides selected from the group consisting of tungsten trioxide (WO3), molybdenum trioxide (MoO3), vanadium pentoxide (V2O5), titanium dioxide (TiO2), niobium pentoxide (Nb2O5), and tantalum pentoxide (Ta2O5). Preferably, tungsten trioxide (WO3) and molybdenum oxide (MoO3) may be used. The transition metal oxide reacts with hydrogen gas to form tungsten bronze (H x By forming compounds such as WO3, it functions as a color-producing agent that enables the presence of gas to be visually identified.

[0057] The above catalyst precursor comprises a metal-based catalyst that dissociates hydrogen molecules into hydrogen atoms, and specifically may include one or more metals selected from the group consisting of palladium (Pd), platinum (Pt), rhodium (Rh), ruthenium (Ru), iridium (Ir), nickel (Ni), copper (Cu), and cobalt (Co), or compounds thereof. Preferably, a palladium-based catalyst or a platinum-based catalyst may be used considering the reaction rate and room temperature stability.

[0058] The above palladium-based catalyst plays a role in inducing and promoting the color development reaction of the above-mentioned color change matrix by dissociating chemically stable hydrogen molecules (H2) into energetically activated hydrogen atoms (H). In the present invention, the palladium-based catalyst may include at least one of palladium precursor compounds such as palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), and palladium nitrate (Pd(NO3)2), or metallic palladium (Pd) in the form of nanoparticles.

[0059] The above palladium-based catalyst induces a spill-over phenomenon in which hydrogen molecules are decomposed into an atomic state and transferred into the lattice of an adjacent transition metal oxide. Through this catalytic action, the composition of the present invention can exhibit a rapid color change response to hydrogen gas at room temperature without the need for separate high-temperature heating. Furthermore, by positioning the palladium-based catalyst in close proximity to the color change matrix within the silicon matrix, it maintains high sensitivity even at low hydrogen concentrations.

[0060] Meanwhile, since these transition metal oxides and catalyst components exist in a particulate state, they may not be uniformly dispersed within a highly hydrophobic silicon matrix, and localized aggregation or precipitation may occur. To solve this problem, the composition of the present invention may include one or more dispersants selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), and polyethyleneimine (PEI). The dispersant controls the interfacial energy of the nanoparticle surface to ensure that the particles are evenly dispersed in the solution without clumping, and increases the interfacial affinity with the siloxane base to suppress the phenomenon of the responsive component being leached out by the external environment (moisture, etc.).

[0061] The above-mentioned sensitizer may be included in a range of 1 to 20 parts by weight per 100 parts by weight of the total composition, and within this range, a fast response speed and high color visibility can be ensured. According to experimental results, under specific curing conditions, the sensitizer can exhibit a vivid color change within about 10 seconds immediately after hydrogen exposure. If the content of the sensitizer is excessively low, the color change upon contact with hydrogen gas is weak, resulting in reduced visibility; if it is excessively high, the mechanical properties of the silicone matrix may be degraded, or long-term stability may decrease due to particle re-aggregation.

[0062] The above-mentioned discoloration matrix and catalyst precursor can be mixed in appropriate proportions depending on the concentration of hydrogen gas to be detected and the target reaction rate. For example, when tungsten trioxide (WO3) and palladium chloride (PdCl2) are mixed and used, their weight ratio may be in the range of 1:0.001 to 1:0.1. In addition, methanol (MeOH), ethanol (EtOH), or isopropyl alcohol (IPA) may be used as solvents to dissolve them, and in particular, when methanol (MeOH) is used, the best effect is exhibited in terms of dispersion stability of WO3-Pd particles and uniform distribution within the silicon matrix.

[0063] The above-mentioned sensitizer may additionally include a dispersant. The dispersant ensures that the aforementioned transition metal oxide and metal-based catalyst particles are uniformly distributed within a hydrophobic silicon matrix without aggregation and serves to suppress leaching by the external environment. Specifically, the dispersant may include one or more polymer compounds selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), and polyethyleneimine (PEI). The dispersant prevents re-aggregation and sedimentation of particles by forming steric hindrance or electrostatic repulsion on the particle surface, and performs an anchor function by increasing interfacial affinity with the siloxane base to fix the sensitizing component so that it does not leak out even when exposed to moisture.

[0064] The above-mentioned sensitizer may include an organic solvent, and specifically, the organic solvent may include one or more selected from the group consisting of alcohol-based solvents having 1 to 10 carbon atoms, ketone-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, ether-based solvents, glycol ether-based solvents, and nitrile-based solvents.

[0065] More specifically, the organic solvent may be one or more selected from the group consisting of alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), n-propanol, and n-butanol; ketone-based solvents such as acetone, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK); ester-based solvents such as ethyl acetate and butyl acetate; aromatic hydrocarbon-based solvents such as toluene and xylene; nitrile-based solvents such as acetonitrile; and glycol ether-based solvents such as propylene glycol methyl ether (PGME), propylene glycol methyl ether acetate (PGMEA), and diethylene glycol monoethyl ether.

[0066] Preferably, the solvent may be an alcohol-based solvent such as methanol, ethanol, isopropyl alcohol (IPA), or ethyl acetate (EA), either alone or in combination. The solvent controls the viscosity of the liquid silicone composition to a level suitable for application and helps the responsive components to settle uniformly within the micropores of the silicone matrix by volatilizing during the drying and curing process.

[0067] The above solvent is included in an amount sufficient to dissolve the responsive components, but it is preferable that most of it be removed during the curing process so as not to affect the physical properties of the entire composition. Since excessive use of solvent can form unwanted bubbles inside the film after curing or reduce mechanical strength, it can be controlled to an appropriate ratio (5 to 20 parts by weight) relative to 100 parts by weight of the composition.

[0069] Palladium-based catalysts

[0070] One example of the present invention comprises a sensitizer comprising a transition metal oxide and a palladium-based catalyst. In the present invention, the palladium-based catalyst is formed by reducing a palladium precursor compound through a suitable reduction means to metal palladium (Pd 0 It can be obtained by converting it into nanoparticles. As a palladium precursor, palladium salts or complexes such as palladium chloride (PdCl2), palladium acetate (Pd(OAc)2), palladium nitrate (Pd(NO3)2), and palladium acetylacetonate (Pd(acac)2) can be used, and can be appropriately selected considering water dispersibility and ease of handling. Preferably, palladium chloride (PdCl2), which has excellent solubility in aqueous or alcohol-based solvents, can be used, but is not limited thereto.

[0071] The above palladium precursor is Pd 0 The reduction method for conversion into nanoparticles is not particularly limited and may be carried out, for example, by (i) photoreduction using ultraviolet (UV) irradiation, (ii) chemical reduction using a chemical reducing agent, or a combination thereof. In this case, it is preferable that the reduction reaction be carried out in a transition metal oxide dispersion, and the Pd produced thereby 0 A composite can be obtained in which nanoparticles are directly supported on the surface of transition metal oxide particles.

[0072] The order in which transition metal oxides and palladium-based catalyst precursors are added can affect the responsiveness. In one embodiment, a sequential addition method may be used in which the transition metal oxide is first dispersed in an organic solvent together with a dispersant, and then the palladium-based catalyst precursor is added. When the palladium precursor is added while the dispersant is adsorbed onto the surface of the transition metal oxide in this manner, palladium nanoparticles are precipitated more uniformly on the surface of the transition metal oxide, which has the advantage of improving the number of hydrogen-sensitive active sites and the degree of dispersion. If the palladium precursor is added before the dispersant, palladium may be adsorbed onto the surface before the dispersant coats the surface of the transition metal oxide, which may reduce the uniformity of nanoparticle loading and result in reduced hydrogen-sensitive performance compared to the sequential addition method.

[0073] The above dispersion treatment can be performed using an ultrasonicator. The primary dispersion time after adding the transition metal oxide and the dispersant to the organic solvent is not particularly limited, but may be 30 minutes to 5 hours, preferably 1 hour to 3 hours, and more preferably about 2 hours. The secondary dispersion time after adding the palladium-based catalyst precursor may be 10 minutes to 2 hours, preferably 20 minutes to 1 hour, and more preferably about 40 minutes. By securing sufficient dispersion time in this way, the palladium precursor is uniformly distributed on the surface of the transition metal oxide, and subsequently, in the reduction step, Pd 0 Uniform precipitation and loading of nanoparticles become possible.

[0074] During the above primary dispersion treatment, dispersant molecules can be sufficiently adsorbed onto the surface of the transition metal oxide particles to form an interfacial coating layer. The dispersant is adsorbed through hydrogen bonding or coordination bonding with the hydroxyl groups (-OH) on the surface of the transition metal oxide particles, thereby allowing the particle surface to be coated with an organic polymer protective layer. If the primary dispersion time is too short, the adsorption of the dispersant is incomplete, leaving uncoated areas on the transition metal oxide surface. Consequently, the palladium precursor subsequently introduced is adsorbed unevenly onto these uncoated areas, resulting in a final Pd 0 The loading uniformity of nanoparticles may be reduced. On the other hand, if the dispersion treatment is performed for too long, excessive pulverization of transition metal oxide particles or damage to their crystal structure may occur due to ultrasonic energy, which may also be undesirable in terms of process efficiency.

[0075] The above secondary dispersion treatment can uniformly distribute the palladium-based catalyst precursor onto the surface of transition metal oxide particles already interface-coated by a dispersant. At this time, the polymer protective layer formed by the dispersant contains palladium precursor ions (Pd 2+ It can play a role in controlling the adsorption rate of the palladium precursor, thereby allowing the palladium precursor to be uniformly distributed across the entire surface of the transition metal oxide without excessive local concentration. If the secondary dispersion time is too short, the dispersion of the palladium precursor may be insufficient, leading to local precipitation and aggregation; if it is too long, desorption or rearrangement of the already adsorbed dispersant may occur, which may instead reduce the uniformity of the loading.

[0076] As such, the method of first sufficiently dispersing the dispersant with the transition metal oxide and then sequentially adding the palladium-based catalyst precursor (hereinafter referred to as the "dispersant pre-addition sequential addition method"), compared to the method of adding the palladium precursor first or adding all components simultaneously, has a Pd on the surface of the transition metal oxide. 0The loading uniformity and loading efficiency of nanoparticles can be significantly improved, which can directly contribute to the improvement of the hydrogen sensitization rate and discoloration uniformity of the final film.

[0077] (i) UV photoreduction method

[0078] In the case of the photoreduction method using ultraviolet irradiation, when ultraviolet light is irradiated onto a reaction solution mixed with WO3 and a palladium precursor, the palladium precursor is converted into metallic palladium (Pd) by light energy. 0 As it is reduced to nanoparticles, it is supported on the surface of WO3 particles. During this process, WO3 is excited as a photocatalyst, and oxygen vacancy can be formed on the surface, which enhances the surface bonding strength of Pd nanoparticles and can subsequently function as an active site for hydrogen spillover reactions.

[0079] As the above ultraviolet light source, a UV lamp emitting ultraviolet light in the wavelength range of 200 to 400 nm can be used, and the irradiation time and light intensity can be appropriately adjusted according to the concentration of the palladium precursor, the volume of the reaction solution, and the desired amount of Pd loaded. In one embodiment, UV irradiation can be performed in an open system or under a nitrogen atmosphere, and the irradiation time may be, for example, in the range of 30 minutes to 6 hours, but is not limited thereto.

[0080] (ii) Chemical reduction method

[0081] In the case of the method using a chemical reducing agent, by adding the reducing agent to a dispersion mixed with a palladium precursor and a transition metal oxide, palladium ions (Pd 2+ ) metallic palladium (Pd 0It can be reduced to ). The reducing agent is not particularly limited as long as it is capable of reducing palladium ions to a metallic state, and, for example, ascorbic acid (vitamin C), sodium borohydride (NaBH₄), citric acid, tannic acid, hydrazine, polyols, etc., can be used alone or in combination. Preferably, L(+)-ascorbic acid, which has excellent reaction selectivity, produces few byproducts, and is biocompatible, may be used.

[0082] The amount of reducing agent added can be controlled within the range of 1 to 10 equivalents relative to the moles of the palladium precursor, and the reduction reaction can proceed even at room temperature. Once the reduction reaction is complete, a change in the color of the reaction solution from clear or pale yellow to brown or dark brown, along with an increase in turbidity, may be observed, which is due to Pd 0 This indicates that nanoparticles are supported on the surface of WO3 (see Fig. 3). Subsequently, residual reducing agent and reaction by-products are removed through centrifugation and washing processes, and the WO3-Pd composite powder can be obtained by drying.

[0083] Chemical reduction methods have a faster reduction rate compared to UV photoreduction methods, and Pd 0 The WO3 surface loading efficiency of the nanoparticles is excellent, which can be advantageous for achieving higher catalytic activity and hydrogen sensitization reaction rates (see Figs. 7a and 7b).

[0084] Pd formed in this way 0 The nanoparticles have a particle size at the nanometer (nm) level and form a composite uniformly supported at high density on the surface of WO3 particles. In this structure, Pd 0 Nanoparticles enable a rapid and clear discoloration reaction even under room temperature and pressure conditions by dissociating hydrogen molecules (H₂) into hydrogen atoms (H) and inducing a spillover reaction that transfers hydrogen into the adjacent WO3 lattice.

[0085] In addition, the above-mentioned sensitizer is introduced into the composition in a form containing a palladium compound in a precursor state, and the reduction step is performed during or prior to the coating and curing process, thereby allowing Pd to be present in the final film. 0 It is also possible to induce the formation of nanoparticles. In this case, Pd 0 Since nanoparticles are formed within a silicon matrix, their bonding with the micropore structure within the matrix is ​​strengthened, which can more effectively suppress the detachment or migration of nanoparticles.

[0087] moisture stabilizer

[0088] The composition of the present invention may further include a moisture stabilizer to suppress the leaching or deterioration of the sensitizer even in environments exposed to moisture. The moisture stabilizer stabilizes the micropores of the silicone matrix or forms a protective environment around the sensitizer, thereby maintaining color stability even during long-term use.

[0089] The above moisture stabilizer may include one or more selected from the group consisting of silane coupling agents, metal alkoxide-based sols, polymer protective agents, and inorganic porous particles containing metal compounds. For example, silane-based compounds such as aminosilane, epoxysilane, etc., or alkoxide compounds such as zirconium, titanium, etc. may be used.

[0090] Preferably, the moisture stabilizer may comprise a silica-metal composite aerogel having a structure in which a metal element is bonded within a silica lattice and / or a hydrophobic composite aerogel in which the surface of the composite aerogel is substituted with a hydrophobic functional group. In this case, the metal element may be one or more selected from the group consisting of zirconium (Zr), aluminum (Al), titanium (Ti), magnesium (Mg), and combinations thereof, and these metal elements may form a structural framework by forming coordination bonds or covalent bonds within the silica network.

[0091] More specifically, the moisture stabilizer is preferably a silica-zirconium composite aerogel having a structure in which zirconium (Zr) elements are chemically integrated within a silica lattice structure. Unlike a standard silica aerogel where zirconium components are simply coated or physically mixed onto the surface, this structure involves the substitution or incorporation of zirconium elements during the silica (SiO₂) network formation process in the aerogel formation stage to form a single-phase composite lattice containing Si-O-Zr bonds. Due to these structural characteristics, it exhibits strong chemical bonding forces, resulting in excellent stability against changes in the external environment. Furthermore, its superior thermal and chemical stability prevents unnecessary side reactions with other components within the silicon composition, while the high reactivity characteristic of zirconium enables electrostatic interaction or chemical anchoring with sensitizer molecules.

[0092] The above silica-zirconium composite aerogel has an average pore size of 5 to 15 nm (e.g., about 8 nm) and a specific surface area (BET) of 120 to 220 m² 2It can have a three-dimensional nanoporous structure with a specific surface area of ​​1 / g. This microporous structure with a high specific surface area can act as a physical trap, physically trapping sensitizer molecules introduced into the pores within a complexly intertwined three-dimensional network structure so that they cannot easily escape to the outside even if moisture is introduced. Additionally, zirconium elements and functional groups exposed on the pore walls form a strong adsorption force with the sensitizer molecules, acting as an anchoring agent that firmly fixes the sensitizer within the silica lattice. If the specific surface area is too low, the area of ​​the pore walls exposed per unit mass of the aerogel decreases, which reduces the contact area with the sensitizer molecules and the physical capture efficiency. Furthermore, since anchoring sites provided by zirconium elements are not sufficiently secured, the effect of inhibiting the release of the sensitizer in a moist environment may become insufficient. On the other hand, if the specific surface area is too high, the pore walls of the aerogel become excessively thin, and during the mixing and curing process of the silicone composition, the pore structure may collapse or the particles themselves may be crushed, which may actually reduce the moisture barrier effect and structural stability.

[0093] In addition, the composite aerogel takes the form of methylated silica in which at least some of the hydroxyl groups (-OH) on the surface are substituted with hydrophobic functional groups such as alkyl groups, thereby fundamentally excluding the access of polar water molecules. That is, the entrance and inner wall of the nanopores form a strong hydrophobic barrier to block external liquid water, while hydrogen gas in the form of fine gases is designed to freely diffuse into the pores and react with the sensitizer. As a result, the moisture stabilizer of the present invention simultaneously satisfies conflicting properties of 'gas permeability' and 'liquid water barrier properties,' thereby maintaining high sensitivity without a decrease in discoloration performance even in water or high-humidity environments.

[0094] Meanwhile, the moisture stabilizer may be directly added in powder form during the preparation of the composition, or preferably mixed in the form of a dispersion dispersed in an organic solvent. However, if the moisture stabilizer is directly added in powder form, uniform dispersion within the silicone matrix may be difficult due to the characteristics of the highly hydrophobic aerogel particles; consequently, there is a concern that the contact area with surrounding chemical components may decrease, thereby reducing reactivity. Furthermore, there is a possibility of reduced process precision, such as a decrease in the capture efficiency of the sensitizer or uneven surface roughness of the film after curing, due to localized agglomeration of the particles.

[0095] Therefore, in order to maximize the physical trapping efficiency of the sensitizer by ensuring that nanoporous aerogel particles are finely dispersed within the silicon matrix without aggregation and to secure a sufficient reaction surface area with the sensitizer, it is more desirable to mix in the form of a dispersion pre-dispersed in an organic solvent. The introduction of such a dispersion form not only facilitates the control of the overall viscosity of the composition but also enables the moisture stabilizer to more uniformly exert an 'anchoring' effect that inhibits the leaching of the sensitizer.

[0096] The above organic solvent may include one or more selected from the group consisting of alcohol-based solvents having 1 to 10 carbon atoms, aromatic hydrocarbon-based solvents, ketone-based solvents, and ester-based solvents. Specifically, alcohol-based solvents such as methanol, ethanol, isopropyl alcohol (IPA), n-butanol, and n-propanol; aromatic hydrocarbon-based solvents such as toluene and xylene; ketone-based solvents such as methyl ethyl ketone (MEK) and acetone; or ester-based solvents such as ethyl acetate may be used. This is intended to prevent a phenomenon in which reactivity with chemicals is significantly reduced when a moisture stabilizer is added directly in powder form, and to improve the physical capture efficiency of the sensitizer by ensuring that nanoporous aerogel particles are uniformly dispersed within the silicon matrix without aggregation.

[0097] The above organic solvent may more preferably be toluene, xylene, ethylbenzene, hexane, heptane, naphtha, methyl ethyl ketone, ethyl acetate, isopropyl alcohol (IPA), etc., but is not limited thereto.

[0098] Furthermore, introducing a moisture stabilizer in the form of a dispersion can prevent the aggregation of hydrophobic particles that may occur when added directly in powder form, and prevent a decrease in reactivity with chemicals. This enables the uniform dispersion of nanoporous aerogel particles within the silicon matrix and improves the efficiency of physically trapping the sensitizer inside the pores.

[0099] The above moisture stabilizer may be included to suppress the leaching or deterioration of the sensitizer due to moisture, and when introduced in the form of a dispersion dispersed in an organic solvent, it may be included in a range of 0.5 to 10 parts by weight, preferably 2 to 6 parts by weight, based on the dispersion, per 100 parts by weight of the composition. The solid content of the moisture stabilizer included in the dispersion may be 0.5 to 10 parts by weight of the total weight of the dispersion, and preferably 1 to 5 parts by weight. If the content of the moisture stabilizer is excessively low, color stability may be reduced during long-term use, and if it is excessively high, an increase in viscosity of the composition or a change in curing characteristics may occur.

[0101] Silicon-based additives

[0102] The composition of the present invention may include a silicon-based additive to control the fluidity of the matrix and improve the dispersion stability of the components. Additionally, the silicon-based additive may be a silicon-based additive surface-modified to be hydrophobic.

[0103] The surface modifier of the above surface modification may include silane, silazane, and siloxane-based compounds, as well as one or more selected from titanate, zirconate, aluminum-based coupling agents, higher fatty acids having hydrophobic functional groups, and fluorine-based organic compounds.

[0104] The surface modification method for forming the above-mentioned hydrophobic silicone-based additive is not particularly limited, but preferably, a silane-based compound, a silazane-based compound, a siloxane-based compound, or a derivative thereof can be used as a reactive agent to form a chemical bond with the silica surface. Through this, the silica surface is covered with alkyl groups such as methyl groups, ethyl groups, and propyl groups, or with silicone polymer chains, and as a result, can be uniformly dispersed without aggregation within the silicone resin, which is a hydrophobic matrix.

[0105] The above-mentioned hydrophobic silicone-based additive may preferably be treated with one or more selected from the group consisting of dimethyldichlorosilane (DDS), hexamethyldisilazane (HMDS), and polydimethylsiloxane (PDMS). In this case, the method of modification with DDS involves modifying the silica surface with dimethylsilyl groups, which facilitates dispersion and can be universally applied to silicone formulation systems of various viscosities. Furthermore, it can prevent pinhole defects on the film surface after coating by rapidly expelling microbubbles introduced during the formulation process to the surface. The method of modification with HMDS involves highly hydrophobicizing the silica surface using an organosilane-based compound. By maintaining a high specific surface area while having low surface energy, it minimizes cohesive forces between particles, exhibiting high thickening and precipitation prevention efficiency with only a small amount of additive. Additionally, it has excellent light transmittance, allowing it to maintain a transparent appearance that does not impair the visual sensitivity of the responsive film. The PDMS modification method involves coating or reacting the silica surface with PDMS chains, a silicon polymer. Since its chemical structure is most similar to the main component silicon matrix, it exhibits excellent interfacial compatibility. Furthermore, through rheological control effects, it reinforces the mechanical strength of the film and provides excellent protection for sensitive components from external corrosion agents, thereby enhancing the long-term reliability of the film.

[0106] The above-mentioned hydrophobic silicon-based additives may be applied using the aforementioned modification methods alone or in combination. For example, in processes where bubble removal is important, DDS-modified silica may be used as the main component, and in cases where high transparency and prevention of precipitation are required, HMDS or PDMS-modified silica may be mixed to achieve optimal properties. The above additive is included in a range of 0.1 to 2 parts by weight, 0.1 to 1.9 parts by weight, 0.1 to 1.8, 0.1 to 1.7 parts by weight, 0.1 to 1.6 parts by weight, 0.5 to 2 parts by weight, 0.5 to 1.9 parts by weight, 0.5 to 1.8 parts by weight, 0.5 to 1.7 parts by weight, 0.5 to 1.6 parts by weight, 1.0 to 2 parts by weight, 1.0 to 1.9 parts by weight, 1.0 to 1.8 parts by weight, 1.0 to 1.7 parts by weight, 1.0 to 1.6 parts by weight, 1.5 to 2 parts by weight, 1.5 to 1.9 parts by weight, 1.5 to 1.8 parts by weight, 1.5 to 1.7 parts by weight, and 1.5 to 1.6 parts by weight, based on 100 parts by weight of the total composition. It is desirable.

[0108] viscosity modifier

[0109] The composition of the present invention may include a viscosity modifier to impart flowability suitable for a coating process and to control the smoothness of the applied liquid film to form a film of uniform thickness. The viscosity modifier includes organic solvents that have excellent compatibility with silicone resins and responsive components and volatilize at an appropriate rate during the curing process to prevent structural defects in the film.

[0110] The viscosity modifier may include one or more organic solvents selected from the group consisting of aromatic hydrocarbons, aliphatic hydrocarbons, ketones, esters, and ethers. Specifically, it may include one or more selected from the group consisting of toluene, xylene, ethylbenzene, hexane, heptane, naphtha, methyl ethyl ketone (MEK), and ethyl acetate (EA), and these may be used alone or in combination depending on the desired viscosity reduction range and drying environment.

[0111] In the present invention, the viscosity modifier may preferably include an aromatic hydrocarbon solvent, and more preferably include one or more selected from the group consisting of toluene, xylene, and ethylbenzene.

[0112] In this case, toluene has excellent solubility for siloxane bases, allowing it to function as a primary solvent that rapidly lowers the viscosity of the entire mixture. Its high volatility enables rapid removal of the solvent during the initial drying stage immediately after coating, thereby increasing process efficiency and allowing the responsive components to be immobilized within the silicon matrix. Xylene is a high-boiling point solvent with a higher boiling point (approx. 140°C) compared to toluene; it can function as a regulator to delay the drying speed. In large-area coating processes, it prevents surface roughness caused by rapid solvent evaporation and induces the solvent to evaporate slowly, providing sufficient time for the liquid film to spread, which can improve the smoothness of the final film. Ethylbenzene functions as an auxiliary solvent that finely adjusts evaporation behavior while maintaining solubility similar to toluene. It is used in combination when precise control of the drying profile is desired depending on specific coating equipment or temperature and humidity environments, and it can uniformly deposit responsive particles by controlling the free volume between silicon polymer chains.

[0113] The above viscosity modifier is 0.1 to 10 parts by weight, 0.1 to 9 parts by weight, 0.1 to 8 parts by weight, 0.1 to 7 parts by weight, 0.1 to 6 parts by weight, 0.1 to 5.5 parts by weight, 0.1 to 5 parts by weight, 0.1 to 4.5 parts by weight, 0.1 to 4 parts by weight, 1 to 10 parts by weight, 1 to 9 parts by weight, 1 to 8 parts by weight, 1 to 7 parts by weight, 1 to 6 parts by weight, 1 to 5.5 parts by weight, 1 to 5 parts by weight, 1 to 4.5 parts by weight, 1 to 4 parts by weight, 2 to 10 parts by weight, 2 to 9 parts by weight, 2 to 8 parts by weight, 2 to 7 parts by weight, 2 to 6 parts by weight, 2 to 5.5 parts by weight, 2 to 5 parts by weight, based on 100 parts by weight of the total composition. It may be included in the range of 1 to 4.5 parts by weight, 2 to 4 parts by weight, 3 to 10 parts by weight, 3 to 9 parts by weight, 3 to 8 parts by weight, 3 to 7 parts by weight, 3 to 6 parts by weight, 3 to 5.5 parts by weight, 3 to 5 parts by weight, 3 to 4.5 parts by weight, and 3 to 4 parts by weight. If the content of the viscosity modifier is too low, the viscosity of the composition may become excessively high, making thin film coating difficult; if it is too high, there is a risk that air bubbles may remain in the film after curing or excessive thickness shrinkage may occur, thereby reducing mechanical strength.

[0115] platinum-based catalysts

[0116] The composition of the present invention may further include a platinum-based catalyst to promote the crosslinking reaction between the siloxane base and the crosslinking agent.

[0117] The above platinum-based catalyst may be included to promote the crosslinking reaction between the siloxane base and the crosslinking agent, and may be included in a range of 0.01 to 2 parts by weight, preferably 0.05 to 1 part by weight, per 100 parts by weight of the composition. If the content of the catalyst is excessively low, the curing reaction may become insufficient, and if it is excessively high, the crosslinking reaction may proceed too quickly, which may reduce workability.

[0119] Hydrogen gas-sensitive silicone film

[0120] A hydrogen gas-sensitive silicon composition according to one embodiment of the present invention can be provided in the form of a film by being applied and cured on a substrate. The film has a three-dimensional silicon network formed by a crosslinking reaction between a siloxane base and a crosslinking agent as a basic framework, and contains a sensitizing agent including a transition metal oxide and a palladium-based catalyst inside.

[0121] When the above film comes into contact with hydrogen gas, the color of the film changes according to the chemical properties of the sensitizer, thereby enabling visual perception of external stimuli. At this time, since the sensitizer remains contained within the silicon matrix, the shape of the film is maintained even after the color change, and the leaching of the sensitizer to the outside can be suppressed.

[0122] Since the film of the present invention possesses the flexibility characteristic of a silicone matrix, it can maintain a stable film shape without cracking or breakage even under bending or external forces. Furthermore, by including an adhesive containing siloxane, the film can be stably attached to a substrate without a separate adhesive layer. Accordingly, peeling, lifting, or detachment of the film from the substrate is suppressed, allowing it to maintain a reliable attachment state even during long-term use.

[0123] In one embodiment, the film may be transparent or translucent, and may be provided in an opaque form by including a white pigment such as TiO2 as needed. When a white pigment is included, the color change caused by hydrogen gas can be observed more clearly, thereby improving visibility. In this case, the pigment may be included in an amount of 0.01 to 2 parts by weight, preferably 0.1 to 1 part by weight, per 100 parts by weight of the composition.

[0124] The thickness of the above film can be appropriately adjusted according to the application, coating method, and viscosity of the composition, and, for example, may be in the range of tens of micrometers (μm) to hundreds of micrometers (μm). If the film thickness is excessively thin, the visibility of the responsive color may be reduced, and conversely, if it is excessively thick, the response speed may be reduced or the flexibility of the film may be decreased.

[0126] The hydrogen gas-sensitive silicon composition of the present invention, configured as described above, can be realized in the form of a film by being coated onto various polymer substrates and then cured, and exhibits a rapid and clear color change upon contact with hydrogen gas. Furthermore, since the film maintains its shape without structural damage, it can be usefully utilized as an indicator for chemical leak detection, a protective film, or a safety monitoring component.

[0128] Manufacturing method

[0129] Another example of the present invention provides a method for manufacturing a hydrogen gas-sensitive silicone film, comprising the steps of: preparing a silicone composition by mixing a siloxane base containing one or more vinyl groups, an adhesive containing siloxane, a crosslinking agent containing a Si-H bond that reacts with the siloxane base, a sensitizing agent containing a transition metal oxide and a palladium-based catalyst, and a moisture stabilizer; applying the silicone composition, to which the crosslinking agent is added, onto a substrate; and forming a hydrogen gas-sensitive silicone film by curing the silicone composition.

[0130] A hydrogen gas-sensitive silicone film according to one embodiment of the present invention can be manufactured by applying the hydrogen gas-sensitive silicone composition onto a substrate and then curing it.

[0131] Specifically, a silicone composition is prepared by mixing a siloxane base containing one or more vinyl groups, an adhesive containing siloxane, a crosslinking agent containing Si-H bonds that react with the siloxane base, a sensitizer containing a transition metal oxide and a palladium-based catalyst, and a moisture stabilizer.

[0132] At this time, the method for manufacturing a hydrogen gas-sensitive silicon film of the present invention may include the following steps.

[0133] Preparation step of the sensitizer reaction solution : First, a transition metal oxide and a dispersant, which are the color change matrix, are added to an alcohol-based organic solvent and dispersed, and then a palladium-based catalyst precursor is added and dispersed. Subsequently, a reducing agent is added to chemically reduce the palladium-based catalyst precursor into metallic palladium nanoparticles, thereby preparing a sensitizing agent reaction solution.

[0134] Preparation step of moisture stabilizer dispersionA moisture stabilizer dispersion is prepared by adding hydrophobic silica aerogel to an organic solvent and high-speed dispersing it. The reason for preparing the solution in the form of a dispersion rather than directly adding the aerogel in powder form is to prevent the aggregation of aerogel particles with a nanoporous structure and to form a uniform gas permeation pathway within the silicon matrix.

[0135] Silicon composition precursor mixing step A siloxane base containing one or more vinyl groups, a siloxane adhesive, a hydrophobic silicone-based additive (surface-modified silica), a crosslinking agent, and the above-prepared moisture stabilizer dispersion and an activated sensitizer reaction solution are mixed. At this time, a viscosity modifier may be added to improve rheological properties in order to increase the precision of the coating process.

[0136] Application and curing steps : The completed composition is applied onto a substrate such as PET and cured at 100 to 150°C to form a film in which a sensitizer is anchored within a three-dimensional network structure. The substrate may be a polymer film such as PET (Polyethylene Terephthalate), PI (Polyimide), PEN (Polyethylene Naphthalate), PVC (Polyvinyl Chloride), and TPU (Thermoplastic Polyurethane). The silicone composition may be applied to the substrate with a uniform thickness using a doctor blade, an applicator, or a corresponding application means.

[0137] At this stage, the process may include preparing a dispersion by dispersing a silica-zirconium composite aerogel in an alcohol-based solvent, and then mixing it with a siloxane base. Additionally, the sensitizer may be introduced in the form of a reaction solution dispersed or dissolved in an organic solvent, thereby allowing the sensitizer to be more uniformly dispersed within the silicon matrix.

[0138] The applied silicone composition can be cured under heating conditions. The curing temperature may be, for example, in the range of about 100°C to 150°C, and within this range, the crosslinking reaction between the siloxane base and the crosslinking agent proceeds efficiently to form a film. The curing time can be appropriately controlled according to the composition of the composition, the application thickness, and the curing temperature.

[0139] The above manufacturing method may further include the step of irradiating ultraviolet light onto a solution in which a transition metal oxide and a metal-based catalyst precursor are mixed, or a silicon composition containing the same. The ultraviolet light source may function as an energy source to induce, for example, a synthesis (reduction) reaction of tungsten trioxide and palladium.

[0140] A UV lamp emitting ultraviolet light in the wavelength range of 200 nm to 400 nm can be used as the light source. The irradiation time and light intensity can be controlled according to the content of the sensitizer and the thickness of the film, thereby controlling the initial color of the final film and improving the hydrogen sensitization rate. Upon UV irradiation, palladium ions in the state of a catalyst precursor are photoreduced into metallic palladium nanoparticles, which are evenly loaded or bonded to the surface of tungsten trioxide particles. This photosynthetic process can activate the sensitizer components without the need for a separate strong chemical reducing agent, thereby improving the reaction sensitivity to hydrogen gas.

[0142] The hydrogen gas-sensitive silicone film manufactured in this manner exhibits a rapid and clear color change in response to hydrogen gas while stably attached to a substrate, and can maintain structural stability and color stability even during long-term use.

[0144] The present invention is capable of various modifications and may have various embodiments. Specific embodiments are illustrated in the drawings and described in detail in the detailed description below. However, this is not intended to limit the present invention to specific embodiments, and it should be understood that it includes all modifications, equivalents, and substitutions that fall within the spirit and scope of the present invention. In describing the present invention, detailed descriptions of related prior art are omitted if it is determined that such detailed descriptions may obscure the essence of the present invention.

[0146] [Example]

[0147] Example 1: Preparation of a hydrogen gas-sensitive silicone film

[0148] 1-1. Preparation of Sensitizer Reaction Solution

[0149] 3 g of tungsten trioxide (WO3, Thermo Scientific) powder, which is the discoloration matrix, and 0.1 g of polyvinylpyrrolidone (PVP, Sigma-Aldrich), which is a dispersant, were added to 400 ml of methanol solvent and dispersed using an ultrasonic disperser for 2 hours. Subsequently, 0.03 g of palladium chloride (PdCl2, Sigma-Aldrich), which is a catalyst precursor, was added and dispersed for an additional 40 minutes.

[0150] Subsequently, a WO3-Pd complex was prepared by chemically reducing PdCl2 to metallic palladium (Pd) by adding a 10 wt% L(+)-ascorbic acid (Daejeong Chemical) aqueous solution. After centrifugation (4,000 rpm, 30 min), the mixture was washed sequentially with distilled water and ethanol, and dried at 60 ℃ for 24 hours to obtain WO3-Pd powder.

[0151] The obtained WO3-Pd powder was added to methanol and ultrasonically dispersed to prepare a dispersion of WO3-Pd : methanol = 1 : 2 (weight ratio), which was used as a sensitizer reaction solution.

[0153] 1-2. Preparation of Silicon Composition Precursors

[0154] A silica-zirconium composite aerogel (Z2H1, Svenska Aerogel) was added to isopropyl alcohol (IPA) at a concentration of 2 wt% and ultrasonically dispersed to prepare an aerogel dispersion. Subsequently, the following components were mixed in sequence:

[0155] 5 g of vinyl-terminated polydimethylsiloxane (SL3358, KCC);

[0156] 3 g of silicone adhesive (SG6501, KCC);

[0157] 2 g of methylhydrogen polysiloxane crosslinking agent (SC1035, KCC);

[0158] 0.5 g of the above aerogel dispersion (0.01 g based on aerogel solid content); and

[0159] Silicone-based additive (AEROSIL® R 972, EVONIK) 0.2 g

[0160] 2 g of the sensitizer reaction solution prepared in 1-1 was additionally added to the above mixture and mixed for about 5 minutes to prepare a silicon composition precursor.

[0162] 1-3. Preparation of Hydrogen Gas Sensitive Silicon Film

[0163] 0.2 g of a platinum (Pt)-based catalyst (SK0010C, KCC) and 0.04 g of an additional silicon-based crosslinking agent (SC0016B, KCC) were added to the silicon composition precursor to promote the crosslinking reaction.

[0164] The mixed composition was applied twice repeatedly onto a PET film substrate using 300 μm and 400 μm applicators, and then heat-cured at 140 °C for 4 minutes to form a hydrogen gas-sensitive silicone film. After curing, the thickness of the formed silicone film was measured to be in the range of 180 to 230 μm.

[0166] Comparative Example 1

[0167] It was prepared in the same manner as in Example 1, except that the method of preparing the sensitizer reaction solution was changed as follows.

[0168] 3 g of WO3 (Thermo Scientific) powder and 0.06 g of PdCl2 (Sigma-Aldrich) were first added to 400 ml of methanol solvent, followed by the addition of 0.2 g of PVP (Sigma-Aldrich), and the mixture was dispersed using an ultrasonic disperser for 2 hours and 40 minutes. Subsequently, a WO3-Pd complex was prepared by chemically reducing PdCl2 by adding a 10 wt% L (+)-ascorbic acid aqueous solution.

[0170] Comparative Example 2

[0171] It was prepared in the same manner as in Example 1, except that the method of preparing the sensitizer reaction solution was changed as follows.

[0172] 3 g of WO3 (Thermo Scientific) powder and 0.03 g of PdCl2 (Sigma-Aldrich) were first added to 400 ml of methanol solvent, followed by the addition of 0.1 g of PVP (Sigma-Aldrich), and the mixture was dispersed using an ultrasonic disperser for 2 hours and 40 minutes. Subsequently, a WO3-Pd complex was prepared by chemically reducing PdCl2 by adding a 10 wt% L (+)-ascorbic acid aqueous solution.

[0174] Comparative Example 3

[0175] It was prepared in the same manner as in Example 1, except that the method of preparing the sensitizer reaction solution was changed as follows.

[0176] 3 g of self-synthesized WO3 and 0.1 g of PVP (Sigma-Aldrich) were added to 400 ml of methanol solvent and sonicated for 2 hours. Then, 0.03 g of PdCl2 (Sigma-Aldrich) was added and dispersed using an ultrasonic disperser for 40 minutes. Subsequently, a WO3-Pd complex was prepared by chemically reducing PdCl2 by adding a 10 wt% L (+)-ascorbic acid aqueous solution.

[0178] Comparative Example 4: Dispersion solvent - Acetone

[0179] It was prepared in the same manner as in Example 1, but acetone was used in the same volume as methanol as the dispersion solvent for the sensitizer reaction solution.

[0181] Comparative Example 5: Dispersion solvent - Tetrahydrofuran (THF)

[0182] It was prepared in the same manner as in Example 1, but tetrahydrofuran (THF) was used in the same volume as methanol as the dispersion solvent for the sensitizer reaction solution.

[0184] Comparative Example 6: Moisture stabilizer - Hydrophobic fumed silica (R972)

[0185] It was prepared in the same manner as in Example 1, but hydrophobic fumed silica (AEROSIL® R 972, EVONIK) was used as a moisture stabilizer instead of silica-zirconium composite aerogel (Z2H1) at the same solid content (an amount equivalent to 0.01 g based on the aerogel solid content).

[0187] Comparative Example 7: Moisture stabilizer - mold release agent

[0188] It was prepared in the same manner as in Example 1, but a silicone-based release agent (Uniadd-370, manufacturer's name) was used as the moisture stabilizer instead of silica-zirconium composite aerogel (Z2H1) with the same solid content.

[0190] Comparative Example 8: No moisture stabilizer added

[0191] It was prepared in the same manner as in Example 1, but without adding a moisture stabilizer (silica-zirconium composite aerogel, Z2H1).

[0193] Experimental Example 1. Confirmation of detection due to hydrogen gas exposure

[0194] A discoloration experiment was performed to confirm the hydrogen gas responsiveness of a transition metal oxide (WO3-Pd) film supported with a palladium-based catalyst according to the present invention.

[0195] The manufactured silicon film was placed in a chamber and exposed to hydrogen gas (H2) at a concentration of 4%, after which the color change of the surface was observed visually. As shown in Fig. 1, the film, which was pale yellowish-white before exposure to hydrogen gas, rapidly changed color to dark blue or bluish-gray immediately after exposure (within 10 seconds). This is because hydrogen atoms dissociated by the palladium-based catalyst diffused into the tungsten trioxide lattice, forming tungsten bronze (H x This is the result of forming WO3. It was confirmed that the above silicon film provides clear visual contrast even at low hydrogen concentrations, as the responsive component is evenly dispersed within the silicon matrix.

[0197] Experimental Example 2. WO 3 and WO 3 - Verification of structure / composition of Pd material

[0198] XRD, SEM, TEM, and EDX analyses were performed to prove that the sensitizer of the present invention is a composite of a tungsten trioxide matrix and a palladium nanocatalyst.

[0199] As a result of the X-ray diffraction pattern in Fig. 2(A), a crystal peak characteristic of tungsten trioxide was observed, confirming that the crystal structure of the matrix is ​​maintained stably. Electron microscopy observations in Figs. 2(B) and (C) confirmed that palladium particles of several nanometers (nm) in size were uniformly supported at high density on the surface of the tungsten trioxide particles. This indicates that the WO3-Pd composite synthesis process used in the present invention prevented the aggregation of catalyst particles and maximized the effective reaction area.

[0200] As a result of the elemental analysis in Fig. 2(D), the Pd component was clearly detected along with the W and O components, indicating that the catalyst component was strongly bonded to the transition metal oxide without any loss.

[0202] Experimental Example 3. WO 3 -Verification of the Pd chemical reduction reaction process

[0203] In the process of preparing the sensitizing agent reaction solution of Example 1, the change in the state of the reaction solution before and after the addition of the chemical reducing agent was observed visually.

[0204] As shown in Fig. 3(a), immediately after adding PdCl2 to the WO3 dispersion (before adding the reducing agent), the reaction solution is transparent pale yellow and the palladium precursor is in an ionic state (Pd 2+ It was in a dispersed state. Subsequently, as shown in Fig. 3(b), after adding a 10 wt% L(+)-ascorbic acid aqueous solution, a phenomenon was observed in which the turbidity of the reaction solution significantly increased and the color changed to a deeper intensity. This is because Pd is dispersed by ascorbic acid. 2+ Palladium metal (Pd 0 As the optical properties of the reaction solution changed as the WO3 particles were reduced to nanoparticles and evenly loaded onto the surface of the WO3 particles, it was visually confirmed that the chemical reduction reaction proceeded normally and a WO3-Pd complex was formed.

[0206] Experimental Example 4. Evaluation of stability according to the type of sensitizer dispersion solvent

[0207] To evaluate the effect of the type of dispersion solvent of the sensitizer reaction solution on the dispersion stability of WO3-Pd in ​​the silicon matrix, films according to Comparative Example 4 (acetone), Comparative Example 5 (THF), and Example 1 (methanol) were exposed to hydrogen gas (4%) under the same conditions to compare the uniformity of discoloration and the reaction rate.

[0208] As shown in Fig. 4, when acetone (Comparative Example 4) and THF (Comparative Example 5) were used as dispersion solvents, non-uniform color change or reduced reaction rate was observed on the film surface. On the other hand, the film of Example 1, in which methanol was used as a dispersion solvent, exhibited rapid and uniform blue discoloration immediately upon exposure to hydrogen gas. This indicates that methanol is the most superior solvent compared to acetone and THF in terms of WO3-Pd dispersion stability and distribution within the silicon matrix.

[0210] Experimental Example 5. WO 3 - Comparison of reactivity according to Pd synthesis conditions (composition and order of addition)

[0211] In order to evaluate the effect of synthesis conditions of WO3-Pd composites (palladium content, type of WO3 raw material, and order of component addition) on the hydrogen sensitivity of the film, silicon films containing sensitizers prepared according to Comparative Examples 1 to 3 and Example 1 were each compared under the same hydrogen gas (4%) exposure conditions.

[0212] As shown in Fig. 5, the appearance of films prepared as Comparative Example 1, Comparative Example 2, and Comparative Example 3 (indicated as 1, 2, and 3 in Fig. 5, respectively) and the film prepared as Example 1 (indicated as 4 in Fig. 5) before and after hydrogen exposure was compared.

[0213] As a result, in the case of films prepared by adding a dispersant (PVP) and performing batch dispersion treatment after first adding a palladium precursor with tungsten trioxide (WO3) as in Comparative Examples 1 and 2, a color change due to chemical reduction was observed; however, since the transition metal oxide surface coating by the dispersant (PVP) did not occur prior to the addition of the palladium precursor, the uniformity of loading palladium nanoparticles onto the WO3 surface was reduced, and the uniformity of discoloration was lower compared to Example 1. In addition, in the case of Comparative Example 1, even though the palladium precursor content (PdCl2 0.06 g) and dispersant content (PVP 0.2 g) were twice that of Example 1 (PdCl2 0.03 g, PVP 0.1 g), the uniformity of discoloration was reduced, confirming that the order of component addition has a greater influence on loading uniformity than the content.

[0214] Meanwhile, in the case of Comparative Example 3, a sequential addition method was used in which the dispersant (PVP) was added first, just like in Example 1, but self-synthesized WO3 was used instead of a commercial product (Thermo Scientific) as the WO3 raw material. As a result, a relatively good discoloration reaction was observed compared to Comparative Examples 1 and 2, but the performance was degraded compared to Example 1. This is believed to be due to differences in the crystallinity or particle size distribution of the self-synthesized WO3.

[0215] On the other hand, the film of Example 1, in which a dispersant (PVP) was added first to sufficiently coat the surface of the transition metal oxide, followed by the sequential addition of a palladium precursor and reduction with a chemical reducing agent, exhibited a rapid and uniform color change upon exposure to hydrogen gas. From this, it was confirmed that the PVP pre-addition sequential addition chemical reduction method is the most superior synthesis condition in terms of the WO3 surface loading efficiency and catalytic activity of palladium nanoparticles.

[0217] Experimental Example 6. Confirmation of the effect of inhibiting responder dissolution according to the type of moisture stabilizer

[0218] In order to evaluate the effect of the type of moisture stabilizer on the dissolution inhibition performance of the responsive agent, films according to Comparative Example 6 (R972 silica), Comparative Example 7 (release agent), Comparative Example 8 (no addition), and Example 1 (Z2H1 aerogel) were immersed in distilled water for 24 hours (1 day), and then the dissolution of the responsive component and changes in hydrogen responsive performance were observed.

[0219] As shown in Fig. 6, when R972 silica (Comparative Example 6) was used, the immersion solution was colored after immersion, and the discoloration reaction upon hydrogen exposure was weakened. Similarly, partial leaching of the responsive component was observed when a release agent (Comparative Example 7) was used. In the case of Comparative Example 8, which did not have a moisture stabilizer added, the degree of leaching was the most severe, and the color change reaction to hydrogen exposure after immersion was significantly reduced.

[0220] On the other hand, the film of Example 1, in which silica-zirconium composite aerogel (Z2H1) was applied as a moisture stabilizer, maintained a transparent state in the immersion solution under the same conditions, and the discoloration reaction to hydrogen gas was maintained normally even after immersion. From this, it was confirmed that the physical capture and anchoring effects due to the nanoporous structure of the silica-zirconium composite aerogel play a key role in stably maintaining the sensitizer in a moist environment.

[0222] Experimental Example 7. WO 3 - Comparison of hydrogen sensitivity according to reduction method during Pd synthesis

[0223] To compare the effect of the reduction method of the palladium precursor (PdCl2) on the hydrogen sensitivity performance of the WO3-Pd composite, films containing samples prepared separately by chemical reduction and UV photoreduction were exposed to hydrogen gas (4%) under the same conditions to compare the discoloration performance.

[0224] As shown in Fig. 7a, in the case of WO3-Pd prepared by the chemical reduction method (Example 1), a blue discoloration reaction occurred throughout the film upon exposure to hydrogen gas. However, as shown in Fig. 7b, in the case of WO3-Pd prepared by the UV photoreduction method, the loading efficiency of palladium nanoparticles on the WO3 surface was lower compared to the chemical reduction method, so the reaction rate was significantly reduced upon exposure to hydrogen.

[0225] From this, it was confirmed that the reduction method using a chemical reducing agent exhibits superior hydrogen responsiveness compared to the UV photoreduction method in terms of WO3 surface loading efficiency and catalytic activity of palladium nanoparticles.

[0228] The foregoing description of the present invention is for illustrative purposes only, and those skilled in the art will understand that other specific forms can be easily modified without altering the technical spirit or essential features of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive.

Claims

Claim 1 A hydrogen gas-sensitive silicone composition comprising: a siloxane base comprising a polysiloxane containing one or more vinyl groups; an adhesive comprising a siloxane; a crosslinking agent comprising a Si-H bond that reacts with the siloxane base; a sensitizer comprising a transition metal oxide and a palladium-based catalyst; and a moisture stabilizer for suppressing the leaching or deterioration of the sensitizer by moisture, wherein the moisture stabilizer comprises a silica-metal composite aerogel, and the metal element of the silica-metal composite aerogel is one or more selected from the group consisting of zirconium (Zr), aluminum (Al), titanium (Ti), and magnesium (Mg). Claim 2 In claim 1, one or more hydrogen atoms bonded to a carbon atom included in the polysiloxane are deuterium, a C1 to C8 alkyl group, a C1 to C8 alkenyl group, a C1 to C8 alkynyl group, or a C3 to C 12 A hydrogen gas-sensitive silicon composition substituted with a cycloalkyl group or a combination thereof. Claim 3 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the siloxane base comprises vinyl-terminated polydimethylsiloxane. Claim 4 In claim 1, the adhesive is a hydrogen gas-sensitive silicone composition comprising a silicone adhesive composition containing MQ resin. Claim 5 A hydrogen gas-sensitive silicone composition according to claim 4, wherein the MQ resin is included in an amount of 10 to 60 parts by weight per 100 parts by weight of adhesive. Claim 6 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the crosslinking agent comprises methyl hydrogen polysiloxane, ethyl hydrogen polysiloxane, a polysiloxane containing Si-H bonds, or a combination thereof. Claim 7 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the crosslinking agent comprises a solvent-free polysiloxane having a viscosity of 10 to 100 cSt. Claim 8 A hydrogen gas-sensitive silicon composition according to claim 1, wherein the transition metal of the transition metal oxide comprises one or more metals selected from the group consisting of W, Ti, Sn, Zn, Mo, V, Cr, and Mn. Claim 9 A hydrogen gas-sensitive silicone composition according to claim 1, comprising, with respect to 100 parts by weight of the composition, 20 to 50 parts by weight of a siloxane base, 10 to 40 parts by weight of an adhesive, 5 to 30 parts by weight of a crosslinking agent, and 1 to 20 parts by weight of a sensitizing agent. Claim 10 A hydrogen gas-sensitive silicon composition according to claim 1, wherein the composition further comprises a platinum (Pt)-based catalyst to promote the crosslinking reaction between the siloxane base and the crosslinking agent. Claim 11 In claim 1, the palladium-based catalyst is metallic palladium (Pd) supported on the surface of a transition metal oxide. 0 A hydrogen gas-sensitive silicon composition comprising ) nanoparticles. Claim 12 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the sensitizer further comprises one or more dispersants selected from the group consisting of polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyethylene glycol (PEG), and polyethyleneimine (PEI). Claim 13 A hydrogen gas-sensitive silicon composition according to claim 1, wherein the weight ratio of the transition metal oxide to the palladium-based catalyst is 1:0.001 to 1:0.

1. Claim 14 A hydrogen gas-sensitive silicon composition according to claim 1, wherein the composition further comprises a silicon-based additive comprising surface-modified silica, selected from one or more of a silane-based compound, a silazane-based compound, a siloxane-based compound, a titanate-based coupling agent, a zirconate-based coupling agent, an aluminum-based coupling agent, a higher fatty acid having a hydrophobic functional group, and a fluorine-based organic compound. Claim 15 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the composition further comprises a viscosity modifier comprising one or more organic solvents selected from the group consisting of toluene, xylene, ethylbenzene, hexane, heptane, naphtha, methyl ethyl ketone (MEK), and ethyl acetate (EA). Claim 16 A hydrogen gas-sensitive silicone composition according to claim 1, wherein the silica-metal composite aerogel has a surface substituted with hydrophobic functional groups. Claim 17 In claim 1, the composite aerogel has a three-dimensional nanoporous structure with an average pore size of 5 to 15 nm and a specific surface area (BET) of 120 to 220 m² 2 / g, hydrogen gas-sensitive silicon composition. Claim 18 A method for manufacturing a hydrogen gas-sensitive silicone film, comprising the steps of: preparing a silicone composition by mixing a siloxane base comprising a polysiloxane comprising one or more vinyl groups, an adhesive comprising a siloxane, a crosslinking agent comprising a Si-H bond that reacts with the siloxane base, a sensitizing agent comprising a transition metal oxide and a palladium-based catalyst, and a moisture stabilizer; applying the silicone composition onto a substrate; and forming a hydrogen gas-sensitive silicone film by curing the silicone composition, wherein the moisture stabilizer comprises a silica-metal composite aerogel, and the metal element of the silica-metal composite aerogel is one or more selected from the group consisting of zirconium (Zr), aluminum (Al), titanium (Ti), and magnesium (Mg). Claim 19 A method for manufacturing a hydrogen gas-sensitive silicone film according to claim 18, wherein the above description is selected from the group consisting of PET (Polyethylene Terephthalate), PI (Polyimide), PEN (Polyethylene Naphthalate), PVC (Polyvinyl Chloride), and TPU (Thermoplastic Polyurethane). Claim 20 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 18, wherein the silicon composition comprises one or more selected from silane-based compounds, silazane-based compounds, siloxane-based compounds, titanate-based coupling agents, zirconate-based coupling agents, aluminum-based coupling agents, higher fatty acids having hydrophobic functional groups, and fluorine-based organic compounds, and further comprises a hydrophobic silicon-based additive including surface-modified silica. Claim 21 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 18, wherein the silica-metal composite aerogel has a surface substituted with hydrophobic functional groups and is included in the composition in the form of a dispersion dispersed in an organic solvent. Claim 22 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 18, wherein the step of preparing the silicon composition comprises the step of photoreducing the palladium-based catalyst by irradiating ultraviolet (UV) light onto a mixture containing a transition metal oxide and a palladium-based catalyst precursor. Claim 23 A method for manufacturing a hydrogen gas-sensitive silicon film, wherein, in paragraph 18, the sensitizer is in the form of a reaction solution dispersed in an organic solvent. Claim 24 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 18, further comprising the step of adding a platinum (Pt)-based catalyst to the silicon composition. Claim 25 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 18, wherein the step of preparing the silicon composition comprises adding a reducing agent to a mixture containing a transition metal oxide and a palladium-based catalyst precursor to chemically reduce the palladium-based catalyst. Claim 26 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 25, wherein the reducing agent is one or more selected from the group consisting of ascorbic acid, sodium borohydride (NaBH₄), citric acid, and tannic acid. Claim 27 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 25, wherein the step of preparing the silicon composition comprises: a step of preparing a first dispersion by mixing a transition metal oxide and a dispersant in an organic solvent; a step of adding and dispersing a palladium-based catalyst precursor to the first dispersion; and a step of chemically reducing the palladium-based catalyst by adding a reducing agent to the dispersion in which the palladium-based catalyst precursor is dispersed. Claim 28 A method for manufacturing a hydrogen gas-sensitive silicon film according to claim 27, wherein the step of preparing the first dispersion is a step of introducing a transition metal oxide and a dispersant into an organic solvent and then performing ultrasonic dispersion treatment for 30 minutes to 5 hours to adsorb the dispersant onto the surface of the transition metal oxide particles, and the step of chemically reducing the palladium-based catalyst is a step of introducing the palladium-based catalyst precursor into the first dispersion and then performing ultrasonic dispersion treatment for 10 minutes to 2 hours.

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