Method for manufacturing adhesive sheet, and adhesive sheet

Abstract

To provide a method for producing an adhesive sheet having high adhesion between a base material and an adhesive layer in which the base material and the adhesive layer are not peeled off during use and to provide an adhesive sheet.SOLUTION: There is provided a method for producing an adhesive sheet which comprises: a step of applying g a coating liquid containing an organometallic compound onto a surface of a base material 10 to form an organometallic compound layer 21 having a thickness of 0.01 to 1 μm; a step of irradiating the organometallic compound layer 21 with energy to change at least a part of the organometallic compound in the organometallic compound layer 21 into a metal oxide to form a metal oxide layer 20, followed by hydrophilizing treatment; and a step of forming an adhesive layer 30 on the surface of the metal oxide layer 20.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a method for producing a pressure-sensitive adhesive sheet, and a pressure-sensitive adhesive sheet. [Background technology]

[0002] Adhesive sheets are made by forming an adhesive layer containing adhesives on a substrate, and are used for fixing parts in various industrial fields such as office equipment, home appliances, and automobiles.They are also used in a wide range of other applications, such as labels for displaying various types of information.

[0003] For example, Patent Document 1 discloses an adhesive sheet having an adhesive layer formed by irradiating an adhesive composition containing: a (meth)acrylic acid ester-based polymer (A) whose main component monomer is a (meth)acrylic acid alkyl ester having an alkyl group of 1 to 18 carbon atoms; an unsaturated group-containing phosphorus-based compound (B) having an unsaturated group in the molecule; and a photopolymerization initiator (C), with active energy rays.

[0004] Attempts have been made to control the adhesive properties of the adhesive sheet by subjecting it to various treatments.

[0005] For example, Patent Document 2 discloses a method in which a precursor containing an organic polyfunctional silane is supplied to a plasma flow, and the plasma flow enriched with the precursor is directed to a rolling surface, and the rolling surface is made of SiO x A method is disclosed for reducing the adhesiveness of the winding surface of an adhesive tape roll by covering it with a coating. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-229367 [Patent Document 2] Special table 2019-531360 publication Summary of the Invention [Problem to be solved by the invention]

[0007] It is desirable that the adhesive layer of the above-mentioned pressure-sensitive adhesive sheet adhere firmly to the substrate so that the adhesive layer does not peel off from the substrate during use, etc. However, Patent Documents 1 and 2 do not take this into consideration.

[0008] In order to ensure adhesion between the substrate and the adhesive layer, the combination of the substrate and the adhesive layer is important, and therefore there is a problem in that there are restrictions on the selection of materials for the substrate and the adhesive layer.

[0009] In this regard, attempts have been made to provide an intermediate layer between the substrate and the adhesive layer or to perform a surface treatment on the surface of the substrate, but there is still room for improvement in terms of improving the adhesion between the substrate and the adhesive layer.

[0010] The present invention has been made in consideration of the above-described circumstances, and aims to provide a method for manufacturing an adhesive sheet in which the adhesive layer has high adhesion between the substrate and the base material, and the adhesive layer does not peel off from the base material during use, and an adhesive sheet. [Means for solving the problem]

[0011] As a result of extensive research into achieving the above-mentioned object, the present inventors have discovered a method for producing a pressure-sensitive adhesive sheet, which includes the steps of: applying a coating liquid containing an organometallic compound onto the surface of a substrate to form an organometallic compound layer having a thickness of 0.01 to 1 μm; irradiating the organometallic compound layer with energy to convert at least a portion of the organometallic compound in the organometallic compound layer into a metal oxide to form a metal oxide layer, which is then hydrophilized; and forming an adhesive layer on the surface of the metal oxide layer, which has led to the completion of the present invention.

[0012] That is, the present invention is as follows.

[0013] (1) The method for producing a pressure-sensitive adhesive sheet includes the steps of: applying a coating liquid containing an organometallic compound onto the surface of a substrate to form an organometallic compound layer having a thickness of 0.01 to 1 μm; irradiating the organometallic compound layer with energy to convert at least a portion of the organometallic compound in the organometallic compound layer into a metal oxide to form a metal oxide layer, which is then further hydrophilized; and forming an adhesive layer on the surface of the metal oxide layer. (2) The method for producing a semiconductor device according to (1), wherein the energy irradiation is carried out in an air atmosphere. (3) The method according to (1) or (2), wherein the energy irradiation is carried out under atmospheric pressure. (4) The method for producing a metal oxide layer according to any one of (1) to (3), wherein the metal oxide layer has a surface water contact angle of 50° or less. (5) The method according to any one of (1) to (4), wherein the organometallic compound is at least one selected from the group consisting of organosilicon compounds, organoaluminum compounds, organotitanium compounds, organovanadium compounds, organozirconium compounds, organoniobium compounds, organomolybdenum compounds, organohafnium compounds, organotantalum compounds, organotungsten compounds, organocerium compounds, organonickel compounds, organochromium compounds, organocobalt compounds, organotin compounds, and organocopper compounds. (6) The pressure-sensitive adhesive sheet includes a substrate, a metal oxide layer formed on the surface of the substrate, and a pressure-sensitive adhesive layer formed on the surface of the metal oxide layer opposite the substrate, wherein the metal oxide layer is an organometallic compound layer having a thickness of 0.01 to 1 μm obtained by applying a coating liquid containing an organometallic compound, and the organometallic compound layer is subjected to a hydrophilization treatment by irradiating the organometallic compound layer with energy. [Effects of the Invention]

[0014] According to the present invention, it is possible to provide a method for producing a pressure-sensitive adhesive sheet in which the adhesive layer has high adhesion between the substrate and the substrate, and the adhesive layer does not peel off from the substrate during use, and a pressure-sensitive adhesive sheet. [Brief explanation of the drawings]

[0015] [Figure 1] FIG. 1 is a conceptual diagram illustrating an example of a manufacturing method according to this embodiment, in which FIG. 1(a) is a cross-sectional schematic diagram of a laminate produced by the manufacturing method according to this embodiment, FIG. 1(b) is a cross-sectional schematic diagram of a treated laminate obtained by subjecting the laminate of FIG. 1(a) to a hydrophilic treatment, and FIG. 1(c) is a cross-sectional schematic diagram of an example of a pressure-sensitive adhesive sheet obtained by the manufacturing method according to this embodiment. [Figure 2] FIG. 2 is a cross-sectional view of a pressure-sensitive adhesive sheet with a release substrate obtained by the production method according to this embodiment. DETAILED DESCRIPTION OF THE INVENTION

[0016] Hereinafter, a mode for carrying out the present invention (hereinafter simply referred to as "the present embodiment") will be described in detail. The following present embodiment is an example for explaining the present invention, and is not intended to limit the present invention to the following content. The present invention can be carried out by appropriately modifying it within the scope of its gist.

[0017] In the drawings, the same elements are given the same reference numerals, and redundant explanations will be omitted. Furthermore, unless otherwise specified, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings. Furthermore, the dimensional ratios of the drawings are not limited to the ratios shown in the drawings.

[0018] FIG. 1 is a conceptual diagram illustrating an example of a manufacturing method according to this embodiment, in which FIG. 1(a) is a cross-sectional schematic diagram of a laminate produced by the manufacturing method according to this embodiment, FIG. 1(b) is a cross-sectional schematic diagram of a treated laminate obtained by subjecting the laminate of FIG. 1(a) to a hydrophilic treatment, and FIG. 1(c) is a cross-sectional schematic diagram of an example of a pressure-sensitive adhesive sheet obtained by the manufacturing method according to this embodiment.

[0019] The method for producing the pressure-sensitive adhesive sheet 1 according to this embodiment includes the steps of: (1) a step of applying a coating liquid containing an organometallic compound onto the surface of a substrate 10 to form an organometallic compound layer 21 having a thickness of 0.01 to 1 μm; (2) a step of irradiating the organometallic compound layer 21 with energy to convert at least a part of the organometallic compound in the organometallic compound layer 21 into a metal oxide to form a metal oxide layer 20, and further making the layer hydrophilic; (3) forming an adhesive layer 30 on the surface of the metal oxide layer 20; The method for producing the pressure-sensitive adhesive sheet 1 includes the steps of: The pressure-sensitive adhesive sheet 1 obtained by the production method according to this embodiment includes at least a substrate 10, a metal oxide layer 20, and a pressure-sensitive adhesive layer 30 (see FIG. 1(c)).

[0020] According to the manufacturing method of this embodiment, by carrying out step (2), not only can the organometallic compound layer 21 be converted into the metal oxide layer 20, but also the surface thereof can be made hydrophilic. This allows the metal oxide layer 20 to function as an easy-adhesion layer, and also provides the metal oxide layer 20 with the function of inhibiting interlayer migration of low-molecular-weight substances.

[0021] Each step will be described below.

[0022] <Process (1)>

[0023] (1) First, a coating liquid containing an organometallic compound, which is a precursor of a metal oxide, is applied onto the surface of the substrate 10 to form an organometallic compound layer 21 having a thickness of 0.01 to 1 μm.

[0024] The material of the substrate 10 is not particularly limited, and can be any material that is used for a normal pressure-sensitive adhesive sheet 1. Specific examples of the substrate 10 include resin, paper, nonwoven fabric, metal, or composite sheets of these.

[0025] Resins that can be used for the substrate 10 include, for example, polyolefins such as polyethylene, polypropylene, and ethylene-propylene copolymers; polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate, and polyethylene naphthalate; acetate resins, acrylonitrile-butadiene-styrene copolymer (ABS) resins, polystyrene, and polyvinyl chloride. Among these, polyolefins and polyesters, which have low adhesion to the adhesive layer 30, are preferred, and polypropylene, polyethylene, and polyethylene terephthalate are more preferred, from the viewpoint of further demonstrating the effects of this embodiment. It is preferable that no easy-adhesion layer be interposed between the substrate 10 and the organometallic compound layer 21.

[0026] These may be used alone or in combination of two or more.

[0027] Examples of paper that can be used as the substrate 10 include kraft paper (acid paper or neutral paper), fine paper, medium-quality paper, lightly coated paper, coated paper, liner, semi-glassine paper, glassine paper, one-sided glazed paper, parchment paper, white paperboard, etc.

[0028] The substrate 10 may also contain additives such as colorants such as dyes and pigments, antioxidants such as anilides and phenols, ultraviolet absorbers such as benzophenones and benzotriazoles, light stabilizers, modifiers, rust inhibitors, fillers, surface lubricants, corrosion inhibitors, heat stabilizers, lubricants, antistatic agents, polymerization inhibitors, crosslinking agents, catalysts, plasticizers, leveling agents, thickeners, softeners, dispersants, and the like.

[0029] The substrate 10 may be a single layer or may be composed of two or more layers. When the substrate 10 is composed of two or more layers, two or more of the above-mentioned layers may be used in combination, or a known functional layer may be included in addition to the above-mentioned layers. When the substrate 10 is composed of two or more layers, it is preferable that the substrate 10 does not include an easy-adhesion layer.

[0030] The dimensions and shape of the substrate 10 are not particularly limited, and suitable dimensions and shapes can be adopted depending on the application. For example, the thickness of the substrate 10 is preferably 20 to 150 μm. The lower limit of this thickness is more preferably 25 μm or more, even more preferably 30 μm or more, and even more preferably 35 μm or more. The upper limit of this thickness is more preferably 80 μm or less, even more preferably 70 μm or less, and even more preferably 60 μm or less.

[0031] During the production of the pressure-sensitive adhesive sheet 1 according to this embodiment, the substrate 10 is preferably a long substrate, as this allows the substrate 10 to be continuously supplied, which is a great advantage in mass production. The longitudinal length of such a long substrate is usually 10 to 10,000 m, and preferably 100 to 3,000 m. The lateral length of the long substrate is usually 0.1 to 5 m, and preferably 0.2 to 2 m. In this specification, the term "long substrate" includes "a long substrate wound in a roll" and "a substrate unwound from a roll of long substrate."

[0032] The organometallic compound used may be any compound that changes into a metal oxide when irradiated with energy. It is preferable that the organometallic compound be soluble in a solvent and be solution-coatable. Because solution coating is a wet process coating that does not require a vacuum, it offers advantages over dry process coating in terms of film formation cost and film formation speed, improving mass productivity.

[0033] Suitable examples of organometallic compounds include at least one selected from the group consisting of organosilicon compounds, organoaluminum compounds, organotitanium compounds, organovanadium compounds, organozirconium compounds, organoniobium compounds, organomolybdenum compounds, organohafnium compounds, organotantalum compounds, organotungsten compounds, organocerium compounds, organonickel compounds, organochromium compounds, organocobalt compounds, organotin compounds, and organocopper compounds.

[0034] Among these organometallic compounds, organosilicon compounds and organotitanium compounds are more preferred.

[0035] Examples of the organosilicon compound include at least one selected from the group consisting of organopolysiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane; silicon alkoxides such as silicon tetramethoxide, silicon tetraethoxide, silicon tert-butoxide, silicon tetra-n-butoxide, and silicon tetraisopropoxide; and hydrolysis products thereof.

[0036] Examples of the organic titanium compound include at least one selected from the group consisting of titanium acetylacetone complexes such as titanium acetylacetonate, titanyl acetylacetonate, and titanium diisopropoxide; and titanium alkoxides such as titanium tetraethoxide, titanium tetra-n-butoxide, and titanium tetraisopropoxide.

[0037] These may be used alone or in combination of two or more.

[0038] Specific examples of the use of two or more compounds in combination include an organosilicon compound and an organotitanium compound; an organosilicon compound and an organocopper compound; an organotitanium compound and an organocopper compound; an organosilicon compound, an organotitanium compound and an organocopper compound; and the like.

[0039] The coating liquid containing the organometallic compound may contain at least the organometallic compound and a solvent. The solvent is not particularly limited, and a known solvent can be selected depending on the type of organometallic compound.

[0040] The solvent may be an organic solvent, such as alcohols, acetone, ethyl acetate, acetic acid, tetrahydrofuran (THF), diethyl ether (DME), methyl ethyl ketone (MEK), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), toluene, carbon tetrachloride, or n-hexane.

[0041] Examples of alcohols include monoalcohols such as methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, and phenethyl alcohol; diols such as ethylene glycol, propylene glycol, and butanediol; triols such as triethylene glycol; and polyols such as polyethylene glycol.

[0042] The concentration of the organometallic compound in the coating solution is not particularly limited, but is preferably 0.1 to 10% by mass. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the concentration of the organometallic compound within this range, the thickness of the organometallic compound layer 21 can be controlled more accurately, and defects in the appearance of the coating film, such as repelling and streaks, can be suppressed.

[0043] The coating solution containing the organometallic compound can be applied by a known method. For example, it can be formed by applying the solution to the surface of the substrate 10 using a coating machine such as a bar coater, die coater, gravure coater, roll coater, blade coater, air knife coater, or size press coater. Among these, the method using a bar coater, die coater, or gravure coater is preferred from the viewpoint of ease of forming a coating film.

[0044] After application, a further step such as heat drying may be carried out as necessary.

[0045] According to this embodiment, step (1) can be performed continuously in a roll-to-roll manner. Specifically, the substrate 10 (long substrate) wound around a core is unwound in the transport direction while being applied with an appropriate tension, and is passed through a coater to coat the surface of the substrate 10 with a coating liquid containing an organometallic compound. The substrate 10, which has passed through the coater and on which a coating film has been formed, is transported to a drying oven, where the coating film is dried to form an organometallic compound layer 21, and then the substrate 10 is wound around the core.

[0046] The thickness of the organometallic compound layer 21 thus formed is 0.01 to 1 μm. If the thickness is less than 0.01 μm, sufficient adhesion between the substrate and the adhesive layer cannot be obtained. Furthermore, if the thickness exceeds 1 μm, the organometallic compound layer may not be sufficiently converted to a metal oxide by the energy irradiation in step (2) (e.g., the surface of the organometallic compound layer 21 that contacts the substrate 10 may not be sufficiently modified), resulting in insufficient adhesion between the substrate 10 and the metal oxide layer 20. For example, if the thickness of the organometallic compound layer 21 exceeds 1 μm, even if the irradiated surface can be modified to some extent by energy irradiation, the opposite surface (back surface) may not be sufficiently modified, and a large amount of the organometallic compound may remain. Generally, organometallic compounds have low cohesion, and adhesion tends to decrease due to cohesive failure of the organometallic compound. Therefore, a thickness exceeding 1 μm does not provide sufficient effects (however, the function of this embodiment is not limited to this).

[0047] From this viewpoint, the lower limit of the thickness of organometallic compound layer 21 is preferably 0.03 μm or more, and more preferably 0.05 μm or more, and the upper limit of this thickness is preferably 0.5 μm or less, and more preferably 0.2 μm or less.

[0048] <Process (2)>

[0049] Next, (2) the organometallic compound layer 21 is irradiated with energy to convert at least a part of the organometallic compound in the organometallic compound layer 21 into a metal oxide to form a metal oxide layer 20, which is further made hydrophilic.

[0050] By performing step (2), a highly hydrophilic metal oxide layer 20 can be formed on the surface of the substrate 10. This makes the surface of the metal oxide layer 20 hydrophilic, thereby increasing adhesion to the adhesive layer 30. The reason why the metal oxide layer 20 becomes hydrophilic is unclear, but it is presumed to be for the following reason. First, by irradiating the organometallic compound layer 21 with energy, at least a portion of the organometallic compounds in the organometallic compound layer 21 changes to form the metal oxide layer 20. Then, water molecules present in the atmosphere or the like are added to the surface of the metal oxide layer 20. As a result, hydroxyl groups (-OH) are added to the surface of the metal oxide layer 20, making the surface of the metal oxide layer 20 hydrophilic, thereby firmly adhering the adhesive layer 30 and the metal oxide layer 20 together.

[0051] Furthermore, the presence of the metal oxide layer 20 between the substrate 10 and the adhesive layer 30 also provides a barrier function that prevents low molecular weight compounds (e.g., plasticizers, oils, etc.) contained in the substrate 10 and / or adhesive layer 30 from migrating to the adhesive layer 30 and / or substrate 10.

[0052] Furthermore, the presence of hydroxyl groups (-OH) on the surface of the metal oxide layer 20 allows it to actively bond with crosslinking agents (e.g., isocyanate-based crosslinking agents) or silane coupling agents contained in adhesives, etc., which is expected to also improve adhesion (however, the effects of this embodiment are not limited to these).

[0053] Methods for quantitatively evaluating the hydroxyl groups (-OH) on the surface of the metal oxide layer 20 include X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (TOF-SIMS), nuclear magnetic resonance (NMR), Fourier transform infrared spectroscopy (FT-IR), thermal desorption spectroscopy (TPD), and labeling agent method.

[0054] In this regard, when using a substrate 10 that has low adhesion to the adhesive layer 30 (e.g., a hydrophobic substrate 10), conventional attempts have been made to add functional groups to the treated surface by performing a surface treatment such as corona treatment, thereby hydrophilizing the surface and improving adhesion to the adhesive layer 30. However, such corona treatments only improve hydrophilicity by adding hydrophilic functional groups similar to those of surrounding gases (air, nitrogen, oxygen, carbon dioxide, etc.), and therefore have limitations in the improvement in hydrophilicity. For example, when a polypropylene substrate is subjected to corona treatment, the amount of hydrophilic functional groups added to the surface of the substrate is small, resulting in insufficient hydrophilization of the treated surface of the substrate.

[0055] The metal oxide is the same metal species as the organometallic compound described above. Specific examples of the transformation from an organometallic compound to a metal oxide include: If it is an organic silicon compound, it will change to silicon oxide (SiO2, etc.), In the case of organic aluminum compounds, they change to aluminum oxide (Al2O3, etc.), In the case of organic titanium compounds, they change into titanium oxide (TiO2, etc.), In the case of organic vanadium compounds, vanadium oxide (V2O5, VO2, V2O3, V6O 13 etc.), In the case of organic zirconium compounds, they change to zirconium oxide (ZrO2, etc.), In the case of organic niobium compounds, they change to niobium oxide (Nb2O5, NbO2, Nb2O3, etc.), In the case of organic molybdenum compounds, they change to molybdenum oxides (MoO2, MoO3, Mo2O5, etc.), In the case of organic hafnium compounds, they change to hafnium oxide (HfO2, etc.), In the case of organic tantalum compounds, they change to tantalum oxide (Ta2O5, etc.), If it is an organic tungsten compound, it will change to tungsten oxide (WO3, etc.), In the case of organic cerium compounds, they change to cerium oxide (Ce2O3, CeO2, etc.), In the case of organic nickel compounds, they change to nickel oxide (NiO, etc.), In the case of organic chromium compounds, they change to chromium oxides (CrO, Cr2O3, CrO3, etc.), In the case of organic cobalt compounds, they change to cobalt oxide (CoO, etc.), In the case of organic tin compounds, they change into tin oxide (SnO2, etc.), In the case of organic copper compounds, they change to copper oxide (Cu2O, CuO, etc.).

[0056] Among the metal oxides, silicon oxide, aluminum oxide, titanium oxide, nickel oxide, molybdenum oxide, chromium oxide, cobalt oxide, copper oxide, etc. are preferred. Among these, silicon oxide and titanium oxide are more preferred from the viewpoints of transparency and hydrophilicity.

[0057] The metal oxide contained in the metal oxide layer 20 may be a single type of metal oxide or a composite metal containing two or more types of metal oxide.

[0058] As an example, we will explain the case where an organometallic compound layer 21 is formed using polydialkylsiloxane (-OSiR2-; R represents an alkyl group) as the organosilicon compound, and then a silicon oxide metal oxide layer 20 is formed. First, when the organometallic compound layer 21 is irradiated with energy equivalent to the band gap energy (approximately 8.2 eV) of silicon oxide (O=Si=O), bonds such as Si-O, Si-C, and Si-H are broken, decomposing the polydialkylsiloxane. Furthermore, the polydialkylsiloxane is converted to silicon oxide (O=Si=O) by bonding (oxidizing) with oxygen in the air, forming the metal oxide layer 20. Furthermore, one of the oxygen atoms (O) in the silicon oxide reacts with trace amounts of water molecules (HO) or hydrogen radicals (·OH) present in the air, generating hydrophilic hydroxyl groups (-OH) on the surface of the metal oxide layer 20. For example, when energy is irradiated onto the surface of a silicon oxide layer (metal oxide layer 20), some of the bridging oxygen atoms are released, creating oxygen defects. The aforementioned water molecules and the like dissociate and adsorb to these oxygen defects, generating surface hydroxyl groups. It is believed that this mechanism results in the development or improvement of hydrophilicity in the silicon oxide layer, which is the metal oxide layer 20 (however, the effects of this embodiment are not limited to this).

[0059] As another example, a case will be described in which an organometallic compound layer 21 is formed using titanium alkoxide as the organotitanium compound, and then a metal oxide layer 20 of titanium oxide is formed. First, when titanium alkoxide is irradiated with energy equivalent to its band gap energy (approximately 3.2 eV), it is decomposed and oxidized, converting the titanium alkoxide to titanium oxide (O=Ti=O), forming the metal oxide layer 20. Furthermore, when the titanium oxide is irradiated with energy equivalent to its band gap energy (approximately 3.2 eV), one of the oxygen atoms (O) of the titanium oxide reacts with a trace amount of water molecules (HO) present outside, generating hydrophilic hydroxyl groups (-OH) on the surface of the titanium oxide. This is thought to result in the development or improvement of hydrophilicity (however, the effects of this embodiment are not limited to this).

[0060] As described above, when hydroxyl groups are formed on the surface of the metal oxide layer 20 (formation of surface hydroxyl groups), external water molecules are adsorbed thereto by hydrogen bonding or the like, thereby further improving hydrophilicity. In other words, not only chemically adsorbed water but also physically adsorbed water can contribute to hydrophilicity. As a result, a surface structure is formed in which hydrophilic and hydrophobic regions are mixed, and it becomes possible to control the water contact angle when water is dripped to a suitable angle (e.g., 50° or less) as described below, thereby further improving the adhesion between the substrate 10 and the adhesive layer 30. From this perspective, a preferred embodiment of this embodiment is one in which hydroxyl groups are present on the surface of the metal oxide layer 20.

[0061] In this embodiment, it is sufficient to provide energy to the organometallic compound layer 21 by irradiation to convert the organometallic compound into a metal oxide and then add a hydroxyl group. The energy irradiation is preferably performed by plasma treatment, excimer lamp treatment, low-mercury lamp treatment, electron beam treatment, gamma ray treatment, or the like, and more preferably by excimer lamp treatment. When performing excimer lamp treatment, it is preferable to use a xenon excimer lamp. Note that in this embodiment, it is preferable to irradiate the organometallic compound layer 21 with energy equivalent to the band gap energy of the metal oxide, and more preferably to irradiate the organometallic compound layer 21 with energy equal to or greater than the band gap energy of the metal oxide. By irradiating with this level of energy, the metal compound in the organometallic compound layer 21 can be efficiently converted (modified) into a metal oxide.

[0062] In this embodiment, when performing excimer lamp treatment, it is preferable to irradiate the organometallic compound layer 21 with energy having a peak wavelength of 200 nm or less (a suitable example is vacuum ultraviolet light; VUV). The lower limit of the peak wavelength is preferably 100 nm or more, more preferably 120 nm or more, even more preferably 140 nm or more, and even more preferably 150 nm or more. The upper limit of the peak wavelength is more preferably 180 nm or less. In addition, the irradiation energy is 10 to 3000 mJ / cm. 2It is preferable to irradiate organometallic compound layer 21 with energy in the range of 1000 kJ / cm2 / s. Irradiating energy under such conditions makes it possible to efficiently impart energy equal to or greater than the band gap energy of the metal oxide in organometallic compound layer 21. As a result, the molecular bonds of the metal compound in organometallic compound layer 21 are broken and decomposed, and they are bonded (oxidized) with oxygen in the air, thereby efficiently forming metal oxide layer 20 as described above.

[0063] One of the conventional film formation techniques is a vapor deposition method such as chemical vapor deposition (CVD). In the vapor deposition method, for example, a vapor deposition material (precursor) is heated under reduced pressure or vacuum to generate a raw material gas, which is then deposited on a substrate to form a layer. Since this type of CVD method requires reduced pressure equipment, the equipment configuration becomes large and it is not a simple manufacturing method for adhesive sheets. It is also not practical from the viewpoint of manufacturing costs. Furthermore, since the film formation depends on the material of the substrate, there are restrictions on the combination of the substrate and the vapor deposition material (material selectivity).

[0064] In addition, in the field of conventional semiconductor manufacturing, atmospheric pressure MOCVD methods have also been attempted, in which CVD is performed using metal organic compounds (MOs) or metal organic complexes at atmospheric pressure. While atmospheric pressure MOCVD has the advantage of being able to be performed at atmospheric pressure, it requires precise control of the source gas and carrier gas to obtain a uniform film. Furthermore, the atmospheric pressure MOCVD method used in semiconductor manufacturing has limitations, such as the inability to simplify the reactor configuration due to the toxic source gases. Thus, atmospheric pressure MOCVD is not a simple method for producing pressure-sensitive adhesive sheets. Furthermore, as mentioned above, the difficulty in controlling the source gas and carrier gas can lead to uneven film formation and product problems, such as difficulty in obtaining a uniform hydrophilic surface.

[0065] However, the manufacturing method according to this embodiment forms an organometallic compound layer 21 on a substrate in advance, converts this into a metal oxide layer 20, and then makes this layer hydrophilic. Therefore, unlike conventional vapor deposition methods, this method has the advantage of not requiring manufacturing under vacuum and can be manufactured with a simple device configuration. Furthermore, it is possible to form a uniform metal oxide layer 20 and make it highly hydrophilic.

[0066] According to this embodiment, energy can be applied continuously in a roll-to-roll manner in step (2). Specifically, substrate 10 (long substrate) having organometallic compound layer 21 formed thereon obtained in step (1) is unwound in the conveying direction while being applied with an appropriate tension, and is transported to an energy applying device, where energy is applied to organometallic compound layer 21, and then substrate 10 is wound around a core.

[0067] As described above, according to this embodiment, step (2) does not necessarily have to be performed under reduced pressure, but can be performed under atmospheric pressure. Therefore, from the viewpoints of not restricting the device configuration and being superior in terms of production costs, it is preferable to perform energy irradiation under atmospheric pressure.

[0068] Furthermore, according to this embodiment, from the viewpoint of efficiently converting the organometallic compound to a metal oxide and further efficiently hydrophilizing the surface of the metal oxide layer 20, the energy irradiation is preferably performed in an oxygen-containing atmosphere. Taking into consideration the viewpoints of simplicity and cost, it is more preferable to perform the energy irradiation in an atmospheric atmosphere (air atmosphere). The oxygen-containing atmosphere may be any atmosphere containing oxygen, such as an atmosphere with an increased or decreased oxygen partial pressure of the atmospheric air. In any of these atmospheres, oxygen (O2) is present, allowing the introduction of these oxygen atoms into the organometallic compound, thereby efficiently converting it to a metal oxide. Furthermore, these oxygen atoms can be introduced into the surface of the metal oxide layer 20, allowing the introduction of hydroxyl groups (-OH) to the surface of the metal oxide layer 20. As a result, the hydrophilicity of the metal oxide layer 20 can be further improved, and the adhesion between the substrate 10 and the adhesive layer 30 can be further improved. Furthermore, since the process does not require an inert gas atmosphere such as nitrogen gas or a rare gas, it has the advantages of simplicity and low manufacturing costs. These advantages are particularly pronounced in an atmospheric atmosphere.

[0069] The energy irradiation conditions in step (2) are not particularly limited, but for example, in the case of excimer lamp treatment, the irradiation time is preferably 1 to 200 seconds, more preferably 5 to 100 seconds, and even more preferably 10 to 50 seconds. In addition, in the case of excimer lamp treatment, the irradiation distance from the irradiation target (substrate 10, etc.) is preferably 0.01 to 100 mm, more preferably 0.05 to 50 mm, and even more preferably 0.1 to 10 mm. By setting the irradiation time and irradiation distance as described above, it is possible to form a more uniform metal oxide layer 20 and to impart higher hydrophilicity.

[0070] The thickness of the metal oxide layer 20 is preferably 0.01 to 1 μm. The lower limit of this thickness is more preferably 0.03 μm or more, and even more preferably 0.05 μm or more. The upper limit of this thickness is more preferably 0.5 μm or less, and even more preferably 0.2 μm or less. By setting this lower limit of the thickness within this range, the hydrophilization effect in step (2) is further improved, and by setting this upper limit of the thickness within this range, the conversion from the organometallic compound to a metal oxide and the effect of modifying the surface of the metal oxide to hydrophilicity in step (2) are further improved, and the adhesion between the substrate 10 and the metal oxide layer 20 is further improved.

[0071] The surface of the metal oxide layer 20 preferably has a water contact angle of 50° or less, more preferably 30° or less, and even more preferably 10° or less. In particular, it is preferable that the surface on the adhesive layer 30 side has the water contact angle described above. By setting the upper limit of the water contact angle within this range as a degree of hydrophilization, restrictions on the type of adhesive used in the adhesive layer 30 can be relaxed. In other words, it is possible to improve adhesion to the substrate 10 with a wide variety of adhesives. Furthermore, it is possible to more effectively prevent quality defects such as adhesive residue.

[0072] <Process (3)>

[0073] Next, (3) an adhesive layer 30 is formed on the surface of the metal oxide layer 20. According to the present embodiment, the surface of the metal oxide layer 20 is hydrophilized to impart high hydrophilicity (a suitable example is a state in which the water contact angle of the metal oxide layer 20 is 50° or less), and then the adhesive layer 30 is formed, thereby achieving high adhesion between the substrate 10 and the adhesive layer 30.

[0074] Examples of methods for forming the adhesive layer 30 include a method of forming a layer by applying an adhesive composition to become the adhesive layer 30 onto the surface of the metal oxide layer 20 using a coating machine such as a bar coater, die coater, gravure coater, roll coater, blade coater, air knife coater, or size press coater. Among these, methods using a bar coater, die coater, or gravure coater are preferred from the viewpoint of ease of layer formation.

[0075] As the adhesive of the adhesive composition, for example, known acrylic adhesives, rubber adhesives, silicone adhesives, epoxy adhesives, ester adhesives, etc. can be used.

[0076] The adhesive composition may further contain additives such as colorants (e.g., dyes, pigments), antioxidants (e.g., anilides, phenols), UV absorbers (e.g., benzophenones, benzotriazoles), light stabilizers, modifiers, rust inhibitors, fillers, surface lubricants, corrosion inhibitors, heat stabilizers, lubricants, antistatic agents, polymerization inhibitors, crosslinkers, and solvents. That is, the adhesive layer 30 may contain these additives as needed. As described below, the metal oxide layer 20 can effectively inhibit the migration of low-molecular-weight compounds to other layers, and thus can also inhibit the migration of low-molecular-weight additives to other layers.

[0077] According to this embodiment, step (3) can be performed continuously in a roll-to-roll manner. Specifically, the substrate 10 (long substrate) wound around a core is unwound in the conveying direction while being applied with an appropriate tension, and is passed through a coater to coat a coating liquid containing a pressure-sensitive adhesive composition on the surface of the metal oxide layer 20. The substrate 10, which has passed through the coater and on which a coating film has been formed, is conveyed to a drying oven, where the coating film is dried to form a pressure-sensitive adhesive layer 30, and then the substrate 10 is wound around the core.

[0078] According to this embodiment, the pressure-sensitive adhesive sheet 1 can be produced by carrying out the above-mentioned steps (1) to (3). The above-mentioned steps (1) to (3) may be carried out using continuous in-line equipment, or each of steps (1) to (3) may be carried out using offline equipment. The pressure-sensitive adhesive sheet 1 can also be used as a pressure-sensitive adhesive sheet with a release substrate, which further comprises a release substrate. The pressure-sensitive adhesive sheet with a release substrate can be produced, for example, by the following method.

[0079] FIG. 2 is a cross-sectional view of a pressure-sensitive adhesive sheet with a release substrate obtained by the production method according to this embodiment.

[0080] The adhesive sheet 4 with a release substrate is obtained by laminating a release substrate 40 on the surface of the adhesive layer 30 of the adhesive sheet 1 shown in Fig. 1. This adhesive sheet 4 with a release substrate can be obtained, for example, by the following manufacturing method.

[0081] First, the above-described steps (1) and (2) are carried out to prepare a treated laminate 3 (see FIG. 1(b)) having a substrate 10 and a metal oxide layer 20.

[0082] Then, a pressure-sensitive adhesive composition that will become the adhesive layer 30 is prepared and applied to the surface of the release substrate 40 by the method described in step (3) to form the adhesive layer 30. In this way, a release substrate 40 (release substrate 5 with adhesive layer) on which the adhesive layer 30 has been formed is prepared.

[0083] Next, the treated laminate 3 and the release substrate 5 with an adhesive layer are bonded together so that the metal oxide layer 20 of the treated laminate 3 comes into contact with the adhesive layer 30 of the release substrate 5 with an adhesive layer, thereby obtaining an adhesive sheet 4 with a release substrate (see Figure 2).

[0084] The release substrate 40 is not particularly limited, and any known material can be used.

[0085] As described above, the manufacturing method according to this embodiment makes it possible to obtain a highly adhesive pressure-sensitive adhesive sheet 1 without peeling between the substrate 10 and the pressure-sensitive adhesive layer 30. Furthermore, it is also possible to impart to the metal oxide layer 20 a function of inhibiting migration of low-molecular-weight substances to other layers.

[0086] A suitable example of the pressure-sensitive adhesive sheet 1 includes a substrate 10, a metal oxide layer 20 formed on the surface of the substrate 10, and a pressure-sensitive adhesive layer 30 formed on the surface of the metal oxide layer 20 opposite the substrate 10, wherein the metal oxide layer 20 is a metal oxide layer that has been hydrophilized by irradiating an organometallic compound layer having a thickness of 0.01 to 1 μm obtained by applying a coating liquid containing an organometallic compound with energy. For example, when the organometallic compound is an organosilicon compound, the pressure-sensitive adhesive sheet 1 contains silicon oxide (metal oxide) that has been hydrophilized by irradiating the organosilicon compound with energy, and is confirmed to have peaks derived from hydroxyl group-containing compounds such as silanol by labeling analysis using an XPS apparatus.

[0087] The pressure-sensitive adhesive sheet 1 thus obtained can be suitably used as a sheet for general labels, a sheet for processing electronic parts, a sheet for displays, a sheet for automobiles, a sheet for windows, and the like. [Example]

[0088] The present invention will be described in more detail with reference to the following examples and comparative examples, but the present invention is not limited to these examples. Note that percentages and parts are by weight unless otherwise specified.

[0089] Example 1

[0090] (Formation of organometallic compound layer)

[0091] 100 parts by mass of an addition reaction curing polyorganosiloxane (manufactured by Shin-Etsu Chemical Co., Ltd., product name: KS835, addition reaction curing PDMS) was diluted with toluene to prepare a 10% by mass solution, to which 2 parts by mass of a platinum catalyst (manufactured by Shin-Etsu Chemical Co., Ltd., product name: PL-50T) was added to prepare a coating liquid of an organometallic compound.

[0092] Next, the coating solution of the organometallic compound was applied to the surface of a substrate 10 (polypropylene (PP), manufactured by Oji F-Tex Co., Ltd., product name: Alphan PK-002, thickness 40 μm). Then, by heating and drying at 90°C for 1 minute, an organometallic compound layer 21 having a thickness of 0.05 μm after drying was formed on the substrate 10. In this way, a laminate 2 (substrate 10 / organometallic compound layer 21, see FIG. 1(a)) was obtained.

[0093] (Formation of Metal Oxide Layer 20 and Hydrophilization Treatment)

[0094] The surface of the organometallic compound layer 21 of the obtained laminate 2 (substrate 10 / organometallic compound layer 21) was irradiated with ultraviolet light having a peak wavelength of 172 nm for 30 seconds using a xenon excimer lamp (manufactured by Hamamatsu Photonics KK, product name: FLAT EXCIMER EX-mini, L12530-01) in an air atmosphere and under atmospheric pressure, with the distance between the light irradiation window and the laminate being 1 mm, to achieve an irradiation energy of 10 to 3000 mJ / cm. 2 By applying energy in the range of 1000 to 10000 times, the organometallic compound was converted into metal oxide (SiO2), thereby producing a post-treatment laminate 3 (substrate 10 / metal oxide layer 20, see FIG. 1(b)). The energy applied to the organometallic compound by the excimer lamp treatment was equal to or greater than the band gap energy of metal oxide (SiO2).

[0095] The change from the organometallic compound layer 21 to the metal oxide layer 20 was confirmed by XPS analysis. 3+ Chemical shifts due to Si 4+ A chemical shift due to the change from PDMS to SiO2 was observed. The presence of hydroxyl groups (-OH) on the surface of the metal oxide layer 20 was confirmed by labeling analysis using an X-ray photoelectron spectrometer (XPS device; manufactured by ULVAC-PHI, Inc., product name: Quantum2000). The water contact angle on the surface of the metal oxide layer 20 obtained in this manner was measured.

[0096] The change from the organometallic compound layer 21 to the metal oxide layer 20 was confirmed by measuring peaks derived from C1s, O1s, and Si2p using an XPS device and by observing the elemental composition, it was confirmed that PDMS had changed to SiO2.

[0097] In addition, the hydroxyl groups (-OH) on the surface of the metal oxide layer 20 were labeled with a labeling reagent, and then measured by X-ray photoelectron spectroscopy (XPS) to confirm the presence of hydroxyl groups on the surface of the metal oxide layer 20 (labeling analysis).

[0098] (Formation of adhesive layer 30)

[0099] An acrylic acid ester copolymer (weight average molecular weight: 600,000) was prepared by copolymerizing 80 parts by mass of 2-ethylhexyl acrylate and 20 parts by mass of 2-hydroxyethyl acrylate. 2 parts by mass of trimethylolpropane-modified tolylene diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: Coronate L) as a crosslinking agent was mixed with the obtained acrylic acid ester copolymer, thoroughly stirred, and diluted with methyl ethyl ketone to obtain a coating solution of an adhesive composition with a solids concentration of 25% by mass.

[0100] The obtained adhesive composition coating solution was applied using a knife coater to the release-treated surface of a release substrate 40 (manufactured by Lintec Corporation, product name: SP-PET382150, adhesive sheet with a thickness of 38 μm, see Figure 2), one side of which had been release-treated with a silicone-based release agent, so that the thickness after drying would be 25 μm, and then the adhesive layer 30 was formed by heating it at 100°C for 1 minute.

[0101] Next, the release substrate 40 on which the adhesive layer 30 was formed was attached to the treated laminate 3 (substrate 10 / metal oxide layer 20, see FIG. 1(b)) so that the metal oxide layer 20 of the treated laminate 3 was in contact with the adhesive layer 30. Then, by curing for 7 days under conditions of 23°C and 50% RH, an adhesive sheet 4 with a release substrate (substrate 10 / metal oxide layer 20 / adhesive layer 30 / release substrate 40, see FIGS. 2 and 1(c)) was produced.

[0102] <Example 2>

[0103] Except for the fact that the thickness of the organometallic compound layer 21 and the thickness of the metal oxide layer 20 were 0.1 μm, an adhesive sheet 4 with a release substrate was produced in the same manner as in Example 1. The energy imparted to the organometallic compound by the excimer lamp treatment was equal to or greater than the band gap energy of the metal oxide (SiO2).

[0104] As a result of analysis in the same manner as in Example 1, it was confirmed that the organometallic compound layer 21 had changed into a metal oxide layer 20 made of SiO2, and that hydroxyl groups (-OH) were present on the surface.

[0105] Example 3

[0106] A release substrate-attached pressure-sensitive adhesive sheet 4 was produced in the same manner as in Example 1, except that 100 parts by mass of titanium oligomer (manufactured by Matsumoto Fine Chemical Co., Ltd., trade name: Orgatix PC-250; organic titanium compound) was diluted with ethanol to prepare a 2 mass% organometallic compound solution. The energy imparted to the organometallic compound by excimer lamp treatment was equal to or greater than the band gap energy of the metal oxide (TiO2).

[0107] As a result of analysis in the same manner as in Example 1, it was confirmed that the organometallic compound layer 21 had changed into a metal oxide layer 20 made of TiO2, and that hydroxyl groups (-OH) were present on the surface.

[0108] Example 4

[0109] Except for the fact that the thickness of the organometallic compound layer 21 and the thickness of the metal oxide layer 20 were set to 0.1 μm, an adhesive sheet 4 with a release substrate was produced in the same manner as in Example 3. The energy imparted to the organometallic compound by the excimer lamp treatment was equal to or greater than the band gap energy of the metal oxide (TiO).

[0110] As a result of analysis in the same manner as in Example 1, it was confirmed that the organometallic compound layer 21 had changed into a metal oxide layer 20 made of TiO2, and that hydroxyl groups (-OH) were present on the surface.

[0111] <Comparative Example 1>

[0112] A pressure-sensitive adhesive sheet with a release substrate was produced in the same manner as in Example 1, except that the metal oxide layer 20 was not formed on the surface of the substrate 10 .

[0113] <Comparative Example 2>

[0114] A pressure-sensitive adhesive sheet with a release substrate was produced in the same manner as in Example 1, except that the thickness of organometallic compound layer 21 and the thickness of metal oxide layer 20 were set to 0.003 μm.

[0115] As a result of analysis in the same manner as in Example 1, it was confirmed that the organometallic compound layer 21 had changed into a metal oxide layer 20 made of SiO2, and that hydroxyl groups (-OH) were present on the surface.

[0116] <Comparative Example 3>

[0117] A pressure-sensitive adhesive sheet with a release substrate was produced in the same manner as in Example 3, except that the thickness of the organometallic compound layer 21 and the thickness of the metal oxide layer 20 were set to 3.0 μm.

[0118] As a result of analysis in the same manner as in Example 1, it was confirmed that the organometallic compound layer 21 had changed into a metal oxide layer 20 made of SiO2, and that hydroxyl groups (-OH) were present on the surface.

[0119] <Evaluation method>

[0120] The physical properties were evaluated according to the following methods. The pressure-sensitive adhesive sheet 1 (see FIG. 1) to be measured was prepared by removing the release substrate 40 from a pressure-sensitive adhesive sheet 4 with a release substrate (see FIG. 2).

[0121] (Surface analysis)

[0122] As described above, the surface analysis of the organometallic compound layer 21 and the metal oxide layer 20 was carried out in accordance with the following method. The change from the organometallic compound layer 21 to the metal oxide layer 20 was confirmed by XPS analysis to see whether or not there was a change from the organometallic compound to a metal oxide before and after the treatment. Then, the surface of the metal oxide layer 20 was subjected to labeling analysis using an XPS device to confirm whether or not hydroxyl groups (—OH) were present.

[0123] (Thickness measurement)

[0124] The thickness of the organometallic compound layer 21 and the thickness of the metal oxide layer 20 were measured under the following conditions using a reflective film thickness meter (Filmetrics, product name: F20) and a spectroscopic ellipsometer (JA Woollam Japan, product name: M-2000). Measurement range: 0.001 to 0.5 μm: Spectroscopic ellipsometer Measurement range: 0.5 to 10 μm: Reflection type film thickness meter

[0125] (Water contact angle measurement)

[0126] In accordance with JIS R 3257, the contact angle of the surface of the metal oxide layer 20 with respect to 2 μL of water was measured using a fully automatic contact angle measuring device (manufactured by Kyowa Interface Science Co., Ltd., product name: DM-701).

[0127] (Adhesion test)

[0128] The adhesiveness of the adhesive sheet was evaluated by a rub-off test, in which the surface of the adhesive layer was rubbed strongly with a fingertip five times over a distance of 3 cm, and then visually inspected to see if any adhesive had come off from the surface of the adhesive layer. ◯: No peeling of the adhesive from the surface of the adhesive layer was visually confirmed. ×: Peeling off of the adhesive from the surface of the adhesive layer was visually confirmed.

[0129] (Mineral oil migration inhibition test)

[0130] Furthermore, a mineral oil migration inhibition test was conducted on the PSA sheets 1 of Examples 1 to 4 (see FIG. 1(c)), and the effect of inhibiting migration of low molecular weight compounds was also verified. Specifically, mineral oil (component: hydrogen-treated heavy naphthenic oil) was applied to the surface of the metal oxide layer 20 of the treated laminate 3 at the stage of FIG. 1(b) using a bar coater, and the sheet was left to stand at room temperature for 7 days. The state after 7 days was then observed. As a result, it was visually confirmed that the mineral oil had not penetrated into the substrate 10 in any of Examples 1 to 4.

[0131] Tables 1 and 2 show the manufacturing conditions and evaluation results for each of the examples and comparative examples.

[0132] [Table 1]

[0133] [Table 2]

[0134] From the above, it was at least confirmed that this example makes it possible to produce an adhesive sheet in which the metal oxide layer is highly hydrophilic, the adhesive layer has high adhesion to the substrate, the substrate and the adhesive layer do not peel off during use, and the migration of low molecular weight compounds can also be suppressed. [Explanation of symbols]

[0135] 1: Adhesive sheet 2: Laminate 3: Laminate after treatment 4: Adhesive sheet with release backing 5: Release substrate with adhesive layer 10: Base material 20: Metal oxide layer 21: Organometallic compound layer 30: Adhesive layer 40: Release substrate

Claims

1. a step of directly applying a coating liquid containing an organometallic compound onto the surface of a substrate to form an organometallic compound layer having a thickness of 0.01 to 1 μm; a step of irradiating the organometallic compound layer with energy to convert at least a part of the organometallic compound in the organometallic compound layer into a metal oxide to form a metal oxide layer, and further making the metal oxide layer hydrophilic; forming an adhesive layer directly on the surface of the metal oxide layer; Including, the metal oxide layer is a single layer, The energy is irradiated by an excimer lamp treatment. A method for manufacturing an adhesive sheet.

2. The energy irradiation is carried out in an atmospheric environment. The method of claim 1.

3. The energy irradiation is carried out under atmospheric pressure. The method according to claim 1 or 2.

4. the metal oxide layer has a surface water contact angle of 50° or less; The method according to any one of claims 1 to 3.

5. the organometallic compound is at least one selected from the group consisting of organosilicon compounds, organoaluminum compounds, organotitanium compounds, organovanadium compounds, organozirconium compounds, organoniobium compounds, organomolybdenum compounds, organohafnium compounds, organotantalum compounds, organotungsten compounds, organocerium compounds, organonickel compounds, organochromium compounds, organocobalt compounds, organotin compounds, and organocopper compounds; The method according to any one of claims 1 to 4.

6. A substrate; a metal oxide layer formed directly on the surface of the substrate; an adhesive layer formed directly on the surface of the metal oxide layer opposite to the substrate; Including, the metal oxide layer is a metal oxide layer obtained by applying a coating liquid containing an organometallic compound to an organometallic compound layer having a thickness of 0.01 to 1 μm, and then subjecting the organometallic compound layer to a hydrophilic treatment by irradiating the organometallic compound layer with energy; the metal oxide layer is a single layer, The energy is irradiated by an excimer lamp treatment. Adhesive sheet.

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