Adhesive sheet

Abstract

The present invention relates to an adhesive sheet having a substrate layer and an adhesive layer provided on one side of the substrate layer, the adhesive sheet having a mass loss of 3% or less after being immersed in a 50 wt% NaOH solution at 125 DEG C for 180 minutes, the overall thickness reduction of the adhesive sheet being 3 [mu] m or less, and the shrinkage rate being within + / -5%. The bonding sheet has excellent bonding performance, alkali resistance and mechanical property.

Description

Technical Field The present invention relates to an adhesive sheet, and more particularly to an adhesive sheet having excellent adhesive properties, alkali resistance, and mechanical properties. Background Art When processing various articles, for the purpose of preventing damage (scratches, contamination, corrosion, etc.) to their surfaces, a technique of bonding a protective sheet (adhesive sheet) to the surface for protection is known. For example, when chemically treating glass or the like with a chemical solution (alkaline etching solution), the surface is protected by attaching an adhesive sheet to the surface of the object to be protected. However, in the above use, there are sometimes problems such as difficulty in achieving both adhesive properties, alkali resistance, and mechanical properties in the adhesive sheet. Summary of the Invention Problems to be Solved by the Invention The present invention has been made to solve the above-mentioned existing problems, and an object thereof is to provide an adhesive sheet having excellent adhesive properties, alkali resistance, and mechanical properties even after etching. Solutions for Solving the Problems The inventors of the present invention conducted in-depth research to solve the above problems, and as a result, found that by controlling the mass loss, the overall thickness reduction amount, and the shrinkage rate of the adhesive sheet within specific ranges after soaking the adhesive sheet in a 50 wt% NaOH solution at 125°C for 180 minutes, the above problems can be solved, and thus the present invention was completed. That is, the present invention is as follows.

[0001] An adhesive sheet having a base material layer and an adhesive layer provided on one side of the base material layer, wherein after the adhesive sheet is soaked in a 50 wt% NaOH solution at 125°C for 180 minutes, the mass loss is 3% or less, the overall thickness reduction amount of the adhesive sheet is 3 μm or less, and the shrinkage rate is within ±5%.

[0002] The adhesive sheet according to [1], wherein after the adhesive sheet is attached to glass and then soaked in a 50 wt% NaOH solution at 125°C for 180 minutes, the edge erosion rate is 2% or less or the edge erosion amount is 2 mm or less, and the peeling force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23°C is 12 N / 20 mm or less.

[0003] The adhesive sheet according to [1] or [2], wherein the peeling force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23°C is 0.5 N / 20 mm or more.

[0004] , The adhesive sheet according to [1] or [2], wherein the substrate layer is a single-layer film made of one or more polyolefins or fluorinated polyolefins, or a composite film made by combining two or more of the above single-layer films; the thickness of the substrate layer is 5 to 100 μm.

[0005] , The adhesive sheet according to [4], wherein the polyolefin is selected from at least one of high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP); the fluorinated polyolefin is selected from at least one of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

[0006] , The adhesive sheet according to [1] or [2], wherein the adhesive layer is formed from an adhesive composition, the adhesive composition comprising 100 parts by weight of a rubber elastomer, 5 to 50 parts by weight of a functional resin, 0.5 to 5 parts by weight of a crosslinking agent, and 0.2 to 2 parts by weight of a release aid; the thickness of the adhesive layer is 1 to 40 μm.

[0007] , The adhesive sheet according to [6], wherein the rubber elastomer is a saturated rubber elastomer selected from at least one of saturated ethylene-propylene rubber, silicone rubber, fluororubber, and thermoplastic styrene-butadiene rubber (SEBS); the Shore hardness of the rubber elastomer is 30 to 100.

[0008] , The adhesive sheet according to [6], wherein the functional resin is selected from at least one of epoxy resin, furan resin, silicone resin, polyurethane resin, terpene resin, and petroleum resin.

[0009] , The adhesive sheet according to [8], wherein the acid value of the functional resin is 5 mg KOH / g or less.

[0010] , The adhesive sheet according to [1] or [2], wherein the adhesive sheet further comprises a primer layer, the primer layer is disposed between the substrate layer and the adhesive layer, and the thickness of the primer layer is 0.05 to 1 μm.

[0011] , A glass etching method, comprising: using the adhesive sheet according to any one of [1] to

[10] to adhere to one or more main surfaces of glass, bringing the one or more main surfaces of the glass into contact with an etching solution, and then peeling off the adhesive sheet.

[0012] , The glass etching method according to

[11] , wherein the temperature of the etching solution is 100 to 130 °C, and the time for the one or more main surfaces of the glass to be in contact with the etching solution is 60 to 200 minutes. Advantages of the Invention When the adhesive sheet of the present invention is pasted on, for example, glass, it still has excellent adhesive properties, alkali resistance, and mechanical properties even after being etched with an alkaline etching solution. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 It is a cross-sectional view schematically showing the structure of the adhesive sheet according to an embodiment of the present invention. EXPLANATION OF REFERENCE NUMERALS 1 Adhesive sheet 10 Substrate layer 20 Adhesive layer DETAILED DESCRIPTION OF THE EMBODIMENTS Hereinafter, suitable embodiments of the present invention will be described. Matters required for implementing the present invention other than those specifically mentioned in this specification can be understood by those skilled in the art based on the teachings regarding the implementation of the invention described in this specification and the common general knowledge in the art at the time of filing. The present invention can be implemented based on the content disclosed in this specification and the common general knowledge in the art. In addition, in the following drawings, components or parts that perform the same function are sometimes denoted by the same reference numerals for description, and repeated descriptions are sometimes omitted or simplified. In addition, the embodiments described in the drawings are schematized for clearly explaining the present invention and do not necessarily accurately represent the dimensions and scales of the actually provided products. <Adhesive sheet> The adhesive sheet of the present invention has a substrate layer and an adhesive layer provided on one side of the substrate layer. Among them, after the adhesive sheet is immersed in a 50% by weight NaOH solution at 125°C for 180 minutes, the mass loss is 3% or less, the overall thickness reduction amount of the adhesive sheet is 3 μm or less, and the shrinkage rate is within ±5%. Figure 1 It is a cross-sectional view schematically showing the structure of the adhesive sheet according to an embodiment of the present invention. As Figure 1 shown, the adhesive sheet 1 includes a substrate layer 10 and an adhesive layer 20 provided on one side of the substrate layer 10. The adhesive layer 20 is preferably provided on the entire surface of the substrate layer 10. In addition, although not shown, the adhesive sheet of the present invention may be provided with a release liner on the outside of the adhesive layer for the purpose of protecting the adhesive surface before being put into use. In the concept of the adhesive sheet described in this specification, objects such as adhesive tapes, adhesive labels, and adhesive films can be included. It should be noted that the adhesive sheet disclosed here can be in a single sheet form or in a form of an adhesive sheet that has been further processed into various shapes. In some preferred embodiments, the adhesive sheet of the present invention can be provided in a long strip shape. The adhesive sheet of the present invention has the following characteristics: After the adhesive sheet is immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the mass loss is 3% or less, preferably 2% or less, more preferably 1% or less, still more preferably 0.5% or less, and the lower limit value is preferably 0.3%, more preferably 0.1%, still more preferably 0%. On the other hand, after the adhesive sheet is immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the reduction in the overall thickness of the adhesive sheet is 3 μm or less, preferably 2 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and the lower limit value is preferably 0.3 μm, more preferably 0.1 μm, still more preferably 0 μm. Moreover, after the adhesive sheet is immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the shrinkage rate is within ±5%. The shrinkage rate is preferably within ±3%, more preferably within ±2%, still more preferably within ±1%, and preferably within ±0.3%, more preferably within ±0.1%, still more preferably 0%. When the mass loss, the reduction in the overall thickness, and the shrinkage rate of the adhesive sheet fall within the above ranges respectively after the adhesive sheet is immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the adhesive sheet can have excellent adhesive properties, alkali resistance, and mechanical properties. The above mass loss, reduction in the overall thickness, and shrinkage rate can be measured, for example, by the methods described in the examples below. Preferably, in the present invention, after the adhesive sheet is attached to the glass and then immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the edge erosion rate is 2% or less or the edge erosion amount is 2 mm or less, and the peel force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23 °C is 12 N / 20 mm or less. The above edge erosion rate is preferably 0.8% or less, more preferably 0.5% or less, still more preferably 0.3% or less, and the lower limit value is preferably 0.2%, more preferably 0.1%, still more preferably 0%. The above edge erosion amount is preferably 1.5 mm or less, more preferably 1.0 mm or less, still more preferably 0.5 mm or less, and the lower limit value is preferably 0.3 mm, more preferably 0.1 mm, still more preferably 0 mm. The peel force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23 °C is preferably 11 N / 20 mm or less, more preferably 10 N / 20 mm or less, still more preferably 9 N / 20 mm or less, and the lower limit value is preferably 1.0 N / 20 mm, more preferably 0.5 N / 20 mm, still more preferably 0 N / 20 mm. When the adhesive sheet is adhered to the glass and the above-mentioned edge erosion rate, edge erosion amount, and peel strength fall within the above ranges respectively, the adhesive sheet can have excellent adhesive properties, alkali resistance, and mechanical properties. The edge erosion amount or edge erosion rate refers to the depth of the etching solution infiltrated into the edge of the adhesive sheet or the percentage of this depth to the total thickness of the adhesive sheet measured after taking out the adhesive sheet together with the glass and soaking them in a 50 wt% NaOH solution at 125 °C for 180 minutes. The above-mentioned edge erosion rate, edge erosion amount, and peel strength can be measured, for example, by the methods described in the following examples. Preferably, when the adhesive sheet is adhered to the glass, the peel strength when peeling from the glass at a peeling speed of 300 mm / min in the 180° direction at 23 °C is 0.5 N / 20 mm or more. This peel strength is preferably 1.0 N / 20 mm or more, more preferably 1.5 N / 20 mm or more, further more preferably 2.0 N / 20 mm or more, and the upper limit value is preferably 8.0 N / 20 mm, more preferably 7.0 N / 20 mm, and further more preferably 6.0 N / 20 mm. [Adhesive layer] The adhesive layer of the present invention can be a layer formed from an adhesive composition. The adhesive composition contains 100 parts by weight of a rubber elastomer, 5 - 50 parts by weight of a functional resin, 0.5 - 5 parts by weight of a crosslinking agent, and 0.2 - 2 parts by weight of a peeling aid. The form of the adhesive composition is not particularly limited, and it can be, for example, various forms of adhesive compositions such as a water-dispersed type, a solvent type, a hot-melt type, and an active energy ray-curable type (such as a photo-curable type). Hereinafter, each component of the adhesive composition of the present invention will be described. (Rubber elastomer) In the present invention, the rubber elastomer is a saturated rubber elastomer selected from at least one of saturated ethylene-propylene rubber, silicone rubber, fluororubber, and thermoplastic styrene-butadiene rubber (SEBS). By using a saturated rubber elastomer in the present invention, the adhesive sheet can have excellent adhesive properties, alkali resistance, and mechanical properties. On the contrary, if an unsaturated rubber elastomer such as unsaturated styrene-isoprene-styrene rubber (SIS), styrene-butadiene rubber (SBR), natural rubber, and cis-1,4-polybutadiene rubber is used in the present invention, it is difficult for the adhesive sheet to have excellent adhesive properties, alkali resistance, and mechanical properties. The Shore hardness of the rubber elastomer is 30 - 100, preferably 35 - 80, and more preferably 40 - 50. The Shore hardness can be measured by using a Shore hardness tester and a known method. (Functional resin) The adhesive composition of the present invention contains a functional resin. As the functional resin, at least one of an epoxy resin, a furan resin, a silicone resin, a polyurethane resin, a terpene resin, and a petroleum resin can be mentioned. The epoxy resin is not particularly limited. For example, various epoxy resins such as triphenylmethane type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, modified bisphenol A type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, modified bisphenol F type epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, and phenoxy resin can be used. These epoxy resins can be used alone or in combination of two or more. From the viewpoint of ensuring the reactivity of the epoxy resin, an epoxy resin having an epoxy equivalent of 150 to 250 g / eq, a softening point or melting point of 50 to 130 °C, and being solid at normal temperature is preferred. Among them, from the viewpoint of reliability, triphenylmethane type epoxy resin, cresol novolac type epoxy resin, and biphenyl type epoxy resin are more preferred. In addition, bisphenol F type epoxy resin is preferred. Examples of the furan resin include furfuryl alcohol resin, furfural-acetone resin, and furfural-acetone-formaldehyde resin. Examples of the silicone resin include polymethyl silicone resin, polyethyl silicone resin, polyaryl silicone resin, and polyalkylaryl silicone resin. Examples of the polyurethane resin include flexible polyurethane foam, rigid polyurethane foam, thermoplastic polyurethane, and aqueous polyurethane dispersion. Examples of the terpene resin include α-pinene polymer, β-pinene polymer, dipentene polymer, etc., and modified terpene resins (for example, terpene phenol resin, styrene-modified terpene resin, aromatic-modified terpene resin, hydrogenated terpene resin) obtained by modifying these terpene resins (phenol modification, aromatic modification, hydrogenation modification, hydrocarbon modification, etc.). Examples of petroleum resins include aromatic petroleum resins, aliphatic petroleum resins, alicyclic petroleum resins (aliphatic cyclic petroleum resins), aliphatic aromatic petroleum resins, aliphatic alicyclic petroleum resins, hydrogenated petroleum resins, etc. Examples of aromatic petroleum resins include polymers using one or more vinyl group-containing aromatic hydrocarbons having 8 to 10 carbon atoms (styrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, α-methylstyrene, β-methylstyrene, indene, methylindene, etc.). As the aromatic petroleum resin, an aromatic petroleum resin (i.e., "C9 series petroleum resin") obtained from fractions such as vinyltoluene, indene, etc. (i.e., "C9 petroleum fraction") can be preferably used. Examples of aliphatic petroleum resins include polymers obtained by using one or more selected from olefins having 4 or 5 carbon atoms (e.g., butene-1, isobutene, pentene-1, etc.), dienes such as butadiene, piperylene, 1,3-pentadiene, isoprene, etc. In addition, as the aliphatic petroleum resin, an aliphatic petroleum resin (i.e., "C4 series petroleum resin", "C5 series petroleum resin", etc.) obtained from fractions such as butadiene, piperylene, and isoprene (i.e., "C4 petroleum fraction", "C5 petroleum fraction", etc.) can be preferably used. Examples of alicyclic petroleum resins include alicyclic hydrocarbon resins obtained by cyclization and dimerization of aliphatic petroleum resins (i.e., "C4 series petroleum resin", "C5 series petroleum resin", etc.) followed by polymerization, polymers of cyclic diene compounds (cyclopentadiene, dicyclopentadiene, ethylidene norbornane, dipentene, ethylidene dicycloheptene, vinylcycloheptene, tetrahydroindene, vinylcyclohexene, limonene, etc.) or their hydrogenated resins, alicyclic hydrocarbon resins obtained by hydrogenating the aromatic rings of the above aromatic hydrocarbon resins, the following aliphatic aromatic petroleum resins, etc. Examples of aliphatic aromatic petroleum resins include styrene-olefin copolymers, etc. In addition, as the aliphatic aromatic petroleum resin, so-called "C5 / C9 copolymer petroleum resin" can be used, etc. The acid value of the functional resin is 5 mg KOH / g or less, preferably 2 mg KOH / g or less, more preferably 0.5 mg KOH / g or less. By making the acid value of the functional resin within the above range, the adhesive sheet can have excellent adhesive properties, alkali resistance, and mechanical properties. In the adhesive composition, the amount of the functional resin used is 5 to 50 parts by weight, preferably 10 to 40 parts by weight, more preferably 20 to 30 parts by weight, based on 100 parts by weight of the rubber elastomer. (Crosslinking agent) In the present invention, the adhesive composition contains a crosslinking agent. As the crosslinking agent, commonly used crosslinking agents can be used, for example, epoxy-based crosslinking agents, isocyanate-based crosslinking agents, melamine-based crosslinking agents, aziridine-based crosslinking agents, metal chelate-based crosslinking agents, etc. These crosslinking agents can be used alone or in combination of two or more. As specific examples of the epoxy-based crosslinking agent, there is no particular limitation, and examples thereof may include: bisphenol A, an epoxy resin of the epichlorohydrin type, ethylene glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polyglycerol polyglycidyl ether, and the like. As the isocyanate-based crosslinking agent, examples thereof may include: 1,2-ethylene diisocyanate; 1,2-butylene diisocyanate, 1,3-butylene diisocyanate, 1,4-butylene diisocyanate and other butylene diisocyanates; 1,2-hexylene diisocyanate, 1,3-hexylene diisocyanate, 1,4-hexylene diisocyanate, 1,5-hexylene diisocyanate, 1,6-hexylene diisocyanate, 2,5-hexylene diisocyanate and other hexylene diisocyanates; 2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylene diisocyanate, lysine diisocyanate; isophorone diisocyanate; 1,2-cyclohexylene diisocyanate, 1,3-cyclohexylene diisocyanate, 1,4-cyclohexylene diisocyanate and other cyclohexylene diisocyanates; 1,2-cyclopentylene diisocyanate, 1,3-cyclopentylene diisocyanate and other cyclopentylene diisocyanates; hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated tetramethylxylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate; 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, 2,2'-diphenylmethane diisocyanate, 4,4'-diphenyl ether diisocyanate, 2-nitrobiphenyl-4,4'-diisocyanate, 2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyl diphenylmethane-4,4'-diisocyanate, 4,4'-diphenylpropane diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, naphthalene-1,4-diisocyanate, naphthalene-1,5-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, xylylene-1,4-diisocyanate, xylylene-1,3-diisocyanate, and the like. As examples of the melamine-based crosslinking agent, examples thereof may include: hexamethylol melamine, butylated melamine resin, and the like. As examples of the aziridine-based crosslinking agent, examples thereof may include: trimethylolpropane tris[3-(1-aziridinyl)propionate], trimethylolpropane tris[3-(1-(2-methyl)aziridinyl)propionate]. Examples of the metal chelate crosslinking agent include: aluminum chelate compounds, titanium chelate compounds, zinc chelate compounds, zirconium chelate compounds, iron chelate compounds, cobalt chelate compounds, nickel chelate compounds, tin chelate compounds, manganese chelate compounds, chromium chelate compounds, etc. In the adhesive composition, the amount of the crosslinking agent used is 0.5 to 5 parts by weight, preferably 1 to 4 parts by weight, more preferably 2 to 3 parts by weight, based on 100 parts by weight of the rubber elastomer. (Release aid) In the present invention, the adhesive composition contains a release aid. Examples of the release aid include polysiloxane release aids, paraffin release aids, polyethylene wax, acrylic polymers, etc. In the adhesive composition, the amount of the release aid used is 0.2 to 2 parts by weight, preferably 0.5 to 1.5 parts by weight, more preferably 0.8 to 1 part by weight, based on 100 parts by weight of the rubber elastomer. In addition to the above components, the adhesive composition of the present invention may contain various additives commonly used in the adhesive field, such as photoinitiators, plasticizers, softeners, anti-aging agents, antioxidants, etc., within the range that does not impair the effects of the present invention. Regarding such various additives, existing well-known additives can be used by conventional methods. Preferably, the adhesive composition of the present invention does not contain a plasticizer. (Preparation of the adhesive composition) In the present invention, the preparation of the adhesive composition can be completed by existing well-known methods. For example, the functional resin, crosslinking agent, release aid, and other optional additives can be dissolved in an organic solvent such as toluene or xylene and dispersed in the rubber elastomer. (Formation of the adhesive layer) The adhesive layer disclosed herein can be formed by existing well-known methods. For example, a method (direct method) of directly applying (typically coating) the adhesive composition onto the substrate layer and drying it to form the adhesive layer can be used. Additionally, a method (transfer method) of applying the adhesive composition onto a surface with peelability (release surface), drying it to form an adhesive layer on this surface, and transferring this adhesive layer onto the substrate layer can also be used. From the perspective of productivity, the transfer method is preferred. As the above release surface, the surface of a release liner, the back surface of a substrate layer subjected to a release treatment, etc. can be used. It should be noted that the adhesive layer disclosed herein is typically formed continuously, but is not limited to such a form, and can also be an adhesive layer formed in a regular or irregular pattern such as dots or stripes. Coating of the adhesive composition can be carried out, for example, using known coating machines such as gravure roll coaters, die coaters, rod coaters, etc. Alternatively, the adhesive composition can also be coated by impregnation or curtain coating methods. From the viewpoints of promoting the crosslinking reaction and improving the manufacturing efficiency, etc., drying of the adhesive composition is preferably carried out under heating. The drying temperature can be set, for example, to about 40 to 150 °C, and is usually preferably set to about 60 to 130 °C. After drying the adhesive composition, aging can be further carried out for the purposes of adjusting the component migration within the adhesive layer, proceeding the crosslinking reaction, relaxing the strain that may exist in the substrate film or the adhesive layer, etc. The thickness of the adhesive layer is not particularly limited. Considering the balance between the adhesiveness and cohesion to the adherend, the thickness of the adhesive layer is preferably 1 to 40 μm, more preferably 3 to 35 μm. By setting the thickness of the adhesive layer within the above range, good adhesiveness can be achieved. [Substrate layer] The substrate layer of the adhesive sheet of the present invention is a single-layer film made of one or more polyolefins or fluorinated polyolefins, or a composite film made by combining two or more of the above single-layer films. The polyolefin is selected from at least one of high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP); the fluorinated polyolefin is selected from at least one of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP). For the surface of the substrate layer of the present invention, in order to improve the adhesion and retention to the adjacent layer, etc., any surface treatment can be carried out. As the above surface treatment, for example, chemical or physical treatments such as chromic acid treatment, ozone exposure, flame exposure, high-voltage electric shock exposure, ionizing radiation treatment, etc., and coating treatment can be cited. The thickness of the substrate layer of the present invention is 5 to 100 μm, more preferably 30 to 60 μm. In one embodiment, the interior and / or surface of the substrate layer may also contain an antistatic agent. As the antistatic agent contained in the interior and / or surface of the substrate layer, any suitable antistatic agent can be used as long as the effects of the present invention can be obtained. For example, the antistatic agent described in the above adhesive layer can be used. As a method of making the substrate contain an antistatic material, there is no particular limitation as long as it is a method by which the above antistatic material can be uniformly mixed into the resin used for the substrate. For example, methods such as using a heating roll, Banbury mixer, pressure kneader, twin-screw kneader, etc. to make it contained in the substrate can be cited. [Primer layer] The adhesive sheet of the present invention may further include a primer layer provided between the substrate layer 10 and the adhesive layer 20. There is no particular limitation on the material for forming the undercoat, and one or more of polyurethane resins, epoxy resins, polyester resins, acrylic resins, polyamide resins, melamine resins, olefin resins, polystyrene resins, phenolic resins, isocyanurate resins, polyvinyl acetate resins, etc. can be used. In some preferred embodiments, the undercoat preferably includes at least one selected from the group consisting of thermosetting acrylic, polyurethane, and epoxy resin systems. Preferably, the undercoat is an acrylic matte resin or an epoxy resin. In some preferred embodiments, the undercoat preferably contains an antistatic agent. Thereby, the antistatic property of the adhesive sheet is improved, and the peeling static voltage can be sufficiently suppressed. The undercoat can be a single-layer structure or a multi-layer structure of two or more layers. In the method of disposing the multi-layer undercoat, it is preferred that at least one layer (typically at least one layer including the layer in contact with the substrate layer) is an undercoat containing an antistatic agent. As the antistatic agent, for example, the antistatic agents described in the above adhesive layer can be used. In addition, in some embodiments, the undercoat may further contain a crosslinking agent. As the crosslinking agent, crosslinking agents such as melamine-based, isocyanate-based, and epoxy-based crosslinking agents commonly used in the crosslinking of ordinary resins can be appropriately selected and used. Thereby, the anchoring property to the substrate layer can be preferably taken into account. In some preferred embodiments, the undercoat is preferably formed by a backside treatment agent. There is no particular limitation on the backside treatment agent that can be used for forming the undercoat, and known or conventional treatment agents such as silicone-based backside treatment agents, fluorine-based backside treatment agents, and long-chain alkyl-based backside treatment agents can be used according to the purpose and use. The backside treatment agent can be used alone or in combination of two or more. The thickness of the undercoat of the present invention is not particularly limited and can be 0.05 to 1 μm, preferably 0.1 to 0.5 μm. (Method for manufacturing an adhesive sheet) The adhesive sheet of the present invention can be manufactured by any suitable method. For example, methods such as a method of coating an adhesive composition on a substrate layer, or a method of transferring a coating layer formed by coating an adhesive composition on an arbitrary suitable substrate to the substrate layer can be cited. As a coating method of the above adhesive composition, any suitable coating method can be adopted. For example, each layer can be formed by drying after coating. As the coating method, for example, coating methods such as using a multiple coater, a die coater, a gravure coater, an applicator, a rod coater, an air knife coater, a reverse roll coater, a lip coater, an immersion coater, offset printing, flexographic printing, and screen printing can be cited. As the drying method, for example, natural drying, heat drying, etc. can be cited. The heating temperature in the case of heat drying can be set to any suitable temperature according to the characteristics of the substance to be dried. (Use) The adhesive sheet disclosed herein can be attached to various members or devices for uses such as protection. (Glass etching method) The present invention also relates to a glass etching method, which includes: using the adhesive sheet of the present invention to adhere to one or more main surfaces of glass, bringing the one or more main surfaces of the glass into contact with an etching solution, and then peeling off the adhesive sheet. In the present invention, the type of the etching solution is not particularly limited. The etching solution may contain one or more alkaline hydroxides in an amount of 20 to 60% by weight. The alkaline hydroxide is sodium hydroxide (NaOH), potassium hydroxide (KOH), or a combination of both sodium hydroxide and potassium hydroxide. The etching solution may further contain one or more of an alkali metal phosphate, an alkali metal carbonate, and a chelating agent. In one embodiment, the concentration of one or more of the alkali metal phosphate, the alkali metal carbonate, and the chelating agent in the etching solution is 0.1 to 20% by weight, preferably 0.5 to 15% by weight, more preferably 1 to 10% by weight. The alkali metal phosphate may be one or more of inorganic orthophosphates or pyrophosphates having sodium ions or potassium ions, including but not limited to sodium phosphates such as Na3PO4, Na4P2O7, potassium phosphates such as K3PO4 and K4P2O7. The alkali metal carbonate may be one or more of Na2CO3 and K2CO3. The chelating agent may be one or more of ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), citric acid, salicylic acid, glycine, oxalic acid, and disodium EDTA. The temperature of the etching solution is also not particularly limited, and is generally 100 to 130 °C, preferably 110 to 120 °C. The time for the one or more main surfaces of the glass to be in contact with the etching solution is also not particularly limited, and is generally 60 to 200 minutes, preferably 80 to 180 minutes, more preferably 100 to 120 minutes. By using the adhesive sheet of the present invention to paste on glass, it can still be well removed from the glass even when etched with an alkaline etching solution, and has excellent adhesive properties, alkali resistance, and mechanical properties. Examples Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited to these examples. The evaluation methods in the examples are as follows. For those without specific conditions indicated in the examples, they are carried out according to conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the materials or instruments used are all conventional products that can be obtained through commercial purchase. Example 1 Petroleum resin with an acid value of 0.1 mg KOH / g (20 parts by weight), (Bayer L75C, mainly composed of toluene diisocyanate) as a crosslinking agent (1 part by weight), and (Adeka PC-10, polyoxyethyl polyoxypropyl glycerol) as a peeling aid (0.5 part by weight) were dissolved in toluene, and then mixed with thermoplastic styrene-butadiene rubber (SEBS) (100 parts by weight) to obtain an adhesive composition. An acrylic matting resin solution was coated on one side of an HDPE film with a thickness of 50 μm (HD-PE002 from Shenzhen Hongda Technology Materials Company) as the substrate layer, and then dried in a suspension oven at 80 °C for 1 minute to form a bottom coating with a thickness of 0.2 μm. The above adhesive composition was coated on the side of the bottom coating opposite to the substrate layer, and then dried to obtain an adhesive layer with a thickness of 15 μm. The drying conditions were heating at 130 °C for 2 minutes. Finally, an adhesive sheet having a bottom coating between the substrate layer and the adhesive layer was obtained. After the adhesive sheet was adhered to the glass, it was immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes and then peeled off from the glass. The properties of the adhesive sheet were tested, and the results are shown in the following table. Examples 2 to 12 and Comparative Examples 1 to 7 Except for changing the types and amounts of the components of the adhesive composition, changing the types and thicknesses of the substrate layers, and not using the bottom coating as shown in the following table, adhesive sheets were obtained in the same manner as in Example 1. The evaluation results are shown in the following table. In the following table: HDPE: High-density polyethylene PET: Polyethylene terephthalate PP: Polypropylene PTFE: Polytetrafluoroethylene SEBS: Thermoplastic styrene-butadiene rubber SIS: Unsaturated styrene-isoprene-styrene rubber PVC: Polyvinyl chloride The parts are parts by weight, and "-" indicates not measured. Table 1 Table 2 Table 3 Table 4 Table 5 Table 6 <Evaluation test> (1) Peel strength after bonding to glass (before etching) (N / 20 mm, 23 °C, 180 °, 300 mm / 10 min) Cut test pieces with a width of 20 mm and a length of 150 mm from the adhesive sheets produced in each example and each comparative example. Use glass cleaned with toluene as the adherend. In a standard environment of 23 °C and 50% RH, let a 2 kg roller travel back and forth once to press the exposed adhesive surface against the adherend. After leaving the test pieces pressed against the adherend in the above standard environment for 30 minutes, according to JIS Z0237, use a universal material testing machine (manufactured by Shimadzu Corporation, product name "AG-Xplus electronic universal testing machine") to perform peeling at a tensile speed of 300 mm / min and a peeling angle of 180 °, and measure the force (N / 20 mm) required for this peeling. (2) Peel strength after bonding to glass and etching (N / 20 mm, 23 °C, 180 °, 300 mm / 10 min) Bond the adhesive sheets produced in each example and each comparative example to glass as described in (1) above. Then immerse the adhesive sheet together with the glass in a 50 wt% NaOH solution at 125 °C for 180 minutes and take it out. After leaving it in a standard environment of 23 °C and 50% RH for 30 minutes, according to JIS Z 0237, use a universal material testing machine (manufactured by Shimadzu Corporation, product name "AG-X plus electronic universal testing machine") to perform peeling at a tensile speed of 300 mm / min and a peeling angle of 180 °, and measure the force (N / 20 mm) required for this peeling. (3) Alkali resistance score The adhesive sheets produced in each example and each comparative example were cut into sheets of 100 mm * 100 mm and adhered to glass. Then, the adhesive sheet together with the glass was immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes and then taken out. Three points were randomly selected on the adhesive sheet and the corrosion depth was measured with a microscope. The scoring criteria are as follows. When the depth of the etching solution penetrating into the edge of the adhesive sheet is 1 mm or less or the seepage area accounts for 1% or less of the total area of the adhesive sheet, the score is 5. When the depth of the etching solution penetrating into the edge of the adhesive sheet is greater than 1 mm and 2 mm or less or the seepage area accounts for greater than 1% and 2% or less of the total area of the adhesive sheet, the score is 4. When the depth of the etching solution penetrating into the edge of the adhesive sheet is greater than 2 mm or the seepage area accounts for greater than 2% of the total area of the adhesive sheet, the score is 3 (NG: unqualified). When the adhesive sheet falls off but the adhesive sheet is not corroded, the score is 2 (NG: unqualified). When the adhesive sheet is corroded, the score is 1 (NG: unqualified). (4) Residual adhesive property The adhesive sheets produced in each example and each comparative example were adhered to glass. Then, the adhesive sheet together with the glass was immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes and then taken out. The test piece pressed against the adherend by such an operation was placed in a standard environment of 23 °C and 50% RH for 3 days, and after peeling at a tensile speed of 300 mm / min, it was visually inspected whether there was residual adhesive on the glass surface. Regarding no residual adhesive visually as "◎", regarding slight residual adhesive visually as "○", and regarding serious residual adhesive visually as "●". (5) Total thickness reduction The thickness of the adhesive sheets produced in each example and each comparative example was measured. Then, the adhesive sheet was immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, taken out, dried, and the thickness of the adhesive sheet was measured. The total thickness reduction of the adhesive sheet was obtained by subtracting the thickness after immersion from the thickness before immersion. When the total thickness reduction is 1 μm or less, it is judged as "◎". When the total thickness reduction is greater than 1 μm and 3 μm or less, it is judged as "○". When the total thickness reduction is greater than 3 μm, it is judged as "●". (6) Mass loss The weight of the adhesive sheets produced in each example and each comparative example was measured. Then, the adhesive sheet was immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, taken out, dried, and the weight of the adhesive sheet was measured. The weight reduction of the adhesive sheet was obtained by subtracting the weight after immersion from the weight before immersion. Based on the weight before immersion, the mass loss was calculated in %. When the mass loss is less than 1%, it is judged as "◎". When the mass loss is greater than 1% and less than or equal to 3%, it is judged as "○". When the mass loss is greater than 3%, it is judged as "●". (7)Shrinkage rate The adhesive sheets prepared in each of the examples and comparative examples are cut into sheets of 100 mm × 100 mm. Then, the adhesive sheets are taken out after being immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, and the TD / MD lengths of the adhesive sheets are measured. The shrinkage amount of the adhesive sheet is obtained by subtracting the TD / MD length after immersion from the TD / MD length before immersion (or vice versa). Based on the TD / MD length before or after immersion, the shrinkage rate is calculated in %. When the shrinkage rate is within ±3%, it is judged as "◎". When the shrinkage rate is greater than ±3% and less than or equal to ±5%, it is judged as "○". When the shrinkage rate exceeds ±5%, it is judged as "●". As shown in the above table, the adhesive sheets of Examples 1 to 15 have excellent adhesive properties, alkali resistance and mechanical properties, and can be easily peeled off after use without causing residual glue pollution. In contrast, the adhesive sheets of Comparative Examples 1 to 7 cannot balance the adhesive properties, alkali resistance and mechanical properties.

Claims

1. An adhesive sheet having a substrate layer and an adhesive layer provided on one side of the substrate layer, characterized in that, After the adhesive sheet is immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the mass loss is 3% or less, the overall thickness reduction of the adhesive sheet is 3 μm or less, and the shrinkage rate is within ±5%.

2. The adhesive sheet according to claim 1, wherein, After the adhesive sheet is adhered to glass and then immersed in a 50 wt% NaOH solution at 125 °C for 180 minutes, the edge erosion rate is 2% or less or the edge erosion amount is 2 mm or less, and the peel force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23 °C is 12 N / 20 mm or less.

3. The adhesive sheet according to claim 1 or 2, wherein After the adhesive sheet is adhered to glass, the peel force when the adhesive sheet is peeled from the glass at a peeling speed of 300 mm / min in the 180° direction at 23 °C is 0.5 N / 20 mm or more.

4. The adhesive sheet according to claim 1 or 2, wherein The base material layer is a single-layer film made of one or more polyolefins or fluorinated polyolefins, or a composite film made by combining two or more of the above single-layer films; the thickness of the base material layer is 5 to 100 μm.

5. The adhesive sheet according to claim 4, wherein The polyolefin is selected from at least one of high-density polyethylene (HDPE), low-density polyethylene (LDPE), and polypropylene (PP); the fluorinated polyolefin is selected from at least one of polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), and tetrafluoroethylene-hexafluoropropylene copolymer (FEP).

6. The adhesive sheet according to claim 1 or 2, characterized in that, The adhesive layer is formed from an adhesive composition comprising 100 parts by weight of a rubber elastomer, 5 to 50 parts by weight of a functional resin, 0.5 to 5 parts by weight of a crosslinking agent, and 0.2 to 2 parts by weight of a peeling aid; the thickness of the adhesive layer is 1 to 40 μm.

7. The adhesive sheet according to claim 6, wherein, The rubber elastomer is a saturated rubber elastomer selected from at least one of saturated ethylene-propylene rubber, silicone rubber, fluororubber, and thermoplastic styrene-butadiene rubber (SEBS); the Shore hardness of the rubber elastomer is 30 to 100.

8. The adhesive sheet according to claim 6, wherein, The functional resin is selected from at least one of epoxy resin, furan resin, silicone resin, polyurethane resin, terpene resin, and petroleum resin.

9. The adhesive sheet according to claim 8, wherein, The acid value of the functional resin is 5 mg KOH / g or less.

10. The adhesive sheet according to claim 1 or 2, wherein The adhesive sheet further includes a primer layer provided between the base material layer and the adhesive layer, and the thickness of the primer layer is 0.05 to 1 μm.

11. A glass etching method, comprising: Use the adhesive sheet according to any one of claims 1 to 10 to adhere to one or more main surfaces of glass, bring one or more main surfaces of the glass into contact with an etching solution, and then peel off the adhesive sheet.

12. The glass etching method according to claim 11, wherein, The temperature of the etching solution is 100 to 130 °C, and the time for one or more main surfaces of the glass to be in contact with the etching solution is 60 to 200 minutes.

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