Parts processing method

Abstract

The objective is to provide a versatile method for processing components temporarily fixed on a support plate, which allows alignment marks to be created at any position during any process. [Solution] The present invention provides a method for processing a member temporarily fixed on a support plate 21. The processing method of the present invention includes the following steps. A step of preparing an adhesive sheet 1B containing a color-changing component that can change color in response to external stimuli, The process of fixing the adhesive sheet 1B onto the support plate 21, The process involves applying an external stimulus to a predetermined position on the adhesive sheet 21 fixed to the support plate 21 to cause discoloration and form an alignment mark 23 on the adhesive sheet 1B, A step of temporarily fixing the component onto the adhesive sheet 1B which is fixed on the support plate 21.

Description

[Technical Field]

[0001] The present invention relates to a method for processing a component. More specifically, it relates to a method for processing a component that has been temporarily fixed on a support plate. [Background technology]

[0002] In the processing of electronic components, optical components, and other materials, materials are sometimes temporarily fixed onto a support plate to improve processing accuracy and handling, and to facilitate process control such as transportation between processes and shipping. For example, when performing various processes such as polishing, dicing, transfer, and mounting on a semiconductor wafer, a method is known in which the semiconductor wafer or semiconductor chip is temporarily fixed onto a support plate via an adhesive sheet before processing (for example, Patent Document 1).

[0003] When processing components by temporarily fixing them on a support plate, alignment marks may be provided on the support plate to serve as indicators for the position of the components on the support plate, the pitch between components when multiple components are temporarily fixed, the processing location, and the position when transferring the components to the next process (for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-082344 [Patent Document 2] WO2003 / 085714 publication [Overview of the project] [Problems that the invention aims to solve]

[0005] Such alignment marks need to be placed in different locations depending on the type and size of the workpiece being processed, as well as the processing location and method. Because they need to be custom-made, they have low versatility. Furthermore, since the support plates are often made from expensive materials such as glass, there is a problem of high costs.

[0006] The present invention has been made in view of the above problems, and an object thereof is to provide a highly versatile method for processing a member temporarily fixed on a support plate, which can form an alignment mark at an arbitrary position in an arbitrary process.

Means for Solving the Problems

[0007] As a result of intensive studies to achieve the above object, the present inventors have found that by temporarily fixing a member to a support plate via an adhesive sheet containing a discoloring component that can change color by an external stimulus, an alignment mark can be formed at an arbitrary position of the adhesive sheet in an arbitrary process, the versatility is extremely high, and the cost can be significantly reduced. The present invention has been completed based on these findings.

[0008] That is, a first aspect of the present invention provides a method for processing a member temporarily fixed on a support plate. In this specification, the method of the first aspect of the present invention may be referred to as "the member processing method of the present invention".

[0009] The member processing method of the present invention is a method of temporarily fixing a member to be processed on a support plate and processing the member. By temporarily fixing the member on the support plate, the processing accuracy and handling property can be improved, and process management such as conveyance between processes and shipping can be facilitated. When processing a member temporarily fixed on a support plate, in order to use as indices such as the position of the member on the support plate, the pitch between members when fixing a plurality of members, the position where processing is performed, and the position when transferring the member to the next process, an alignment mark may be provided on the support plate. Such alignment marks need to be provided at different positions according to the type and size of the member to be processed, the position of processing, the mode, etc., and need to be custom-made, so the versatility is low. Furthermore, since the support plate is often made of an expensive member such as glass, there is a problem that the cost becomes high.

[0010] The member processing method of the present invention includes the following steps. ·Preparing an adhesive sheet containing a discoloring component capable of changing color by an external stimulus (hereinafter sometimes referred to as the "adhesive sheet preparation step" in this specification) ·Fixing the adhesive sheet on the support plate (hereinafter sometimes referred to as the "adhesive sheet fixing step" in this specification) ·Applying the external stimulus to a predetermined position of the adhesive sheet fixed on the support plate to cause discoloration and forming an alignment mark on the adhesive sheet (hereinafter sometimes referred to as the "alignment mark forming step" in this specification) ·Temporarily fixing the member on the adhesive sheet fixed on the support plate (hereinafter sometimes referred to as the "member temporary fixing step" in this specification)

[0011] In the member processing method of the present invention, by the adhesive sheet preparation step, the adhesive sheet fixing step, and the member temporary fixing step, the member is temporarily fixed to the support plate via the adhesive sheet. In this specification, the adhesive sheet used in the member processing method of the present invention may sometimes be referred to as the "adhesive sheet of the present invention".

[0012] The adhesive sheet of the present invention contains a discoloring component capable of changing color by an external stimulus. In this specification, the discoloring component capable of changing color by the external stimulus may sometimes be referred to as the "discoloring component of the present invention".

[0013] The configuration of the adhesive sheet of the present invention, which contains the color-changing component of the present invention, allows the color-changing component at a predetermined location on the adhesive sheet to change color during the alignment mark formation process, thereby enabling the color-changing location to be used as an alignment mark. Since this alignment mark can be formed at any location on the adhesive sheet of the present invention in any process, it is highly versatile, dramatically improving production efficiency, and significantly reducing costs as there is no need to provide alignment marks on the support plate. Furthermore, since the alignment mark can be formed immediately before or during the process in which the alignment mark is used, it is possible to eliminate the need to replace the support plate with one having a different alignment mark, which is also advantageous as it dramatically improves manufacturing efficiency.

[0014] In one embodiment of the component processing method of the present invention, it is preferable to temporarily fix the component using the alignment marks formed on the adhesive sheet as indicators during the temporary component fixing step. By temporarily fixing the component using the alignment marks as indicators during the temporary component fixing step, the position of the component on the support plate, the pitch between components when multiple components are temporarily fixed, etc., can be accurately positioned, which is preferable.

[0015] Another embodiment of the component processing method of the present invention preferably further includes the following steps. - A step of performing processing other than the temporary fixing on the member that has been temporarily fixed onto the adhesive sheet (this may be referred to as the "member processing step" in this specification). In the aforementioned component processing step, it is preferable to perform the processing using the alignment marks formed on the adhesive sheet as an indicator. By processing the component temporarily fixed on the support plate using the alignment marks as an indicator, the processing accuracy and efficiency can be significantly improved, which is preferable.

[0016] Another embodiment of the component processing method of the present invention preferably further includes the following steps. - A step of peeling the member from the adhesive sheet (which may be referred to as the "member peeling step" in this specification). The configuration of the present invention's component processing method, which further includes the component peeling step, is preferable from the viewpoint of streamlining process management, such as transporting the processed component to the next processing step or shipping it out.

[0017] In another embodiment of the component processing method of the present invention, the component to be processed is preferably a semiconductor wafer or a semiconductor chip. In the manufacturing of semiconductor wafers or semiconductor chips, various processes such as polishing, dicing, transfer, and mounting require extremely high processing accuracy, and it is preferable that the component temporary fixing process and component processing process are performed using the alignment marks formed in the alignment mark formation process as indicators, thereby achieving such high processing accuracy.

[0018] In another embodiment of the component processing method of the present invention, the external stimulus is preferably irradiation with active energy rays. The configuration in which the external stimulus is irradiation with active energy rays is preferable because it is easy to form alignment marks by irradiating the adhesive sheet of the present invention with active energy rays at any position and in any step. [Effects of the Invention]

[0019] The present invention's component processing method allows for the creation of alignment marks at any position and in any process by applying an external stimulus to an adhesive sheet, which causes the color-changing component of the present invention to change color. Therefore, it is applicable to all processing techniques for temporarily fixing components on a support plate, offering high versatility and significantly improving production efficiency. Furthermore, since there is no need to create alignment marks on the support plate, costs can be drastically reduced. [Brief explanation of the drawing]

[0020] [Figure 1] This is a schematic cross-sectional view showing one embodiment of the adhesive sheet of the present invention. [Figure 2]This is a schematic cross-sectional view showing another embodiment of the adhesive sheet of the present invention. [Figure 3] Figure 2 is a schematic cross-sectional view showing one embodiment of the adhesive sheet fixing step in the component processing method of the present invention using the adhesive sheet shown. [Figure 4] Figure 2 is a schematic cross-sectional view showing one embodiment of the alignment mark formation process in the component processing method of the present invention using the adhesive sheet shown. [Figure 5] Figure 2 is a schematic cross-sectional view showing another embodiment of the alignment mark formation step in the component processing method of the present invention using the adhesive sheet shown. [Figure 6] Figure 2 is a schematic cross-sectional view showing one embodiment of the temporary fixing step of a component in the component processing method of the present invention using an adhesive sheet. [Figure 7] Figure 2 is a schematic cross-sectional view showing one embodiment of the component processing step in the component processing method of the present invention using the adhesive sheet shown. [Figure 8] Figure 2 is a schematic cross-sectional view showing one embodiment of the member peeling step in the member processing method of the present invention using the adhesive sheet shown. [Modes for carrying out the invention]

[0021] 1. Method for processing components according to the present invention The present invention relates to a method for processing a component that has been temporarily fixed on a support plate, and includes the following steps. • A step of preparing an adhesive sheet containing a color-changing component that can change color in response to external stimuli (adhesive sheet preparation step) - A step of fixing the adhesive sheet onto the support plate (adhesive sheet fixing step) - A step of forming alignment marks on the adhesive sheet fixed on the support plate by applying the external stimulus to a predetermined position on the adhesive sheet to cause discoloration (alignment mark formation step). - A step of temporarily fixing the member onto the adhesive sheet fixed on the support plate (member temporary fixing step)

[0022] In the component processing method of the present invention, the "component" to be processed is not particularly limited as long as it is a processable component (workpiece), and includes electronic components, optical components, etc. Examples of electronic components include semiconductor wafers or semiconductor chips such as semiconductors and optoelectronic semiconductors (LEDs), multilayer substrates, multilayer ceramics, and integrated encapsulation modules. Examples of optical components include lenses, diffractive optical elements, prisms, and polarizers. The component processing method of the present invention is suitable for processing semiconductor wafers or semiconductor chips that require high-precision processing.

[0023] In the component processing method of the present invention, "processing" is not particularly limited, but examples include polishing, dicing, fixing, transfer, mounting, cutting, grinding, laser processing, printing, and visual inspection. The process of temporarily fixing the component (component temporary fixing process) itself is also included as one embodiment of the "processing" of the component. The component processing method of the present invention is suitable for processing such as polishing, dicing, fixing, transfer, and mounting of semiconductor wafers or semiconductor chips that require high-precision processing.

[0024] In the component processing method of the present invention, the material of the support plate for temporarily fixing the component is not particularly limited as long as it can stably fix the component and process it, but examples include glass substrates, metal substrates, silicon substrates, sapphire substrates, plastic substrates, etc. From the viewpoint of ease of forming alliance marks and visibility of alliance marks, a highly transparent glass substrate is preferred.

[0025] In the component processing method of the present invention, "temporary fixing" of a component means temporarily fixing the component to a support plate during processing or transportation between processes, and then removing it. The removal of the component may be performed during processing such as transfer or mounting, or between processes.

[0026] In the component processing method of the present invention, the order of the above steps is not particularly limited unless otherwise specified. For example, the alignment mark formation step and the temporary component fixing step are not limited to the order described above, and the temporary component fixing step may be performed after the alignment mark formation step, or the alignment mark formation step may be performed after the temporary component fixing step. Furthermore, the alignment mark formation step may be performed simultaneously with the temporary component fixing step. Since it is preferable to temporarily fix the component using the alignment marks as an indicator, it is preferable to perform the temporary component fixing step after the alignment mark formation step.

[0027] In the component processing method of the present invention, the component is temporarily fixed to the support plate via the adhesive sheet of the present invention through the adhesive sheet preparation step, the adhesive sheet fixing step, and the component temporary fixing step.

[0028] Another embodiment of the component processing method of the present invention preferably further includes the following steps. - A step of performing processing other than the temporary fixing on the member that has been temporarily fixed onto the adhesive sheet (member processing step).

[0029] Another embodiment of the component processing method of the present invention preferably further includes the following steps. - A step of peeling the member from the adhesive sheet (member peeling step) The following explains each step.

[0030] 2. Adhesive sheet preparation process The adhesive sheet (adhesive sheet of the present invention) prepared in the adhesive sheet preparation step is not particularly limited in form, as long as it contains a discoloration component (discoloration component of the present invention) that can change color in response to external stimuli. For example, it may be a single-sided adhesive sheet with only one side being an adhesive surface, or a double-sided adhesive sheet with both sides being adhesive surfaces. From the viewpoint of attaching one side to a support plate and temporarily fixing a member to the other side, a double-sided adhesive sheet is preferred.

[0031] The adhesive sheet of the present invention may be a so-called "substrate-less type" adhesive sheet that does not have a base material (base layer), or it may be an adhesive sheet that has a base material. In this specification, a "substrate-less type" adhesive sheet may be referred to as a "substrate-less adhesive sheet," and an adhesive sheet that has a base material may be referred to as a "substrate-attached adhesive sheet." Examples of the above-mentioned substrate-less adhesive sheet include a double-sided adhesive sheet consisting of only a single adhesive layer, and a double-sided adhesive sheet consisting of two different adhesive layers. Examples of the above-mentioned substrate-attached adhesive sheet include a single-sided adhesive sheet having an adhesive layer on one side of the base material, and a double-sided adhesive sheet having adhesive layers on both sides of the base material. The above-mentioned "base material (base layer)" refers to the portion that is attached to the adherend (support plate or member) together with the adhesive layer when the adhesive sheet of the present invention is used (attached) to an adherend. The release liner that is peeled off when the adhesive sheet is used (attached) is not included in the above-mentioned base material.

[0032] One embodiment of the component processing method or adhesive sheet of the present invention may be described below with reference to the drawings, but the component processing method or adhesive sheet of the present invention is not limited to this embodiment.

[0033] Figure 1 is a schematic cross-sectional view showing one embodiment of the adhesive sheet of the present invention, where 1A is the adhesive sheet, 10 is the adhesive layer, and 110 and 120 are the release liners. As shown in Figure 1, the adhesive sheet 1A is a substrate-less double-sided adhesive sheet having a laminated structure in which a release liner 110, an adhesive layer 10, and a release liner 120 are laminated in this order. The adhesive surfaces of the release liners 110 and 120 are exposed when the adhesive layer 10 is peeled off when the support plate is fixed or when a member is temporarily fixed. One adhesive surface of the adhesive layer 10 is attached to and fixed to the support plate, and the member is temporarily fixed to the other adhesive surface.

[0034] Figure 2 is a schematic cross-sectional view showing another embodiment of the adhesive sheet of the present invention, where 1B is the adhesive sheet, 11 and 12 are the adhesive layers, S is the substrate, and 110 and 120 are the release liners. As shown in Figure 2, the adhesive sheet 1B is a double-sided adhesive sheet with a base material having a laminated structure in which a release liner 110, an adhesive layer 11, a base material S, an adhesive layer 12, and a release liner 120 are laminated in this order. The adhesive surfaces of the release liners 110 and 120 are exposed when the adhesive layers 11 and 12 are peeled off when the support plate is fixed or when a member is temporarily fixed. One of the adhesive layers 11 and 12 is attached to and fixed to the support plate, and the member is temporarily fixed to the other. The adhesive layers 11 and 12 may be composed of the same adhesive or may be composed of different adhesives.

[0035] [Color-changing components that can change color due to external stimuli] The adhesive sheet of the present invention contains a discoloration component (the discoloration component of the present invention) that can change color in response to external stimuli. The configuration of the adhesive sheet of the present invention, which contains the discoloration component of the present invention, allows the discolored area to be used as an alignment mark by applying the external stimuli to a predetermined position on the adhesive sheet during the alignment mark formation process, thereby causing the discoloration component at the location of the external stimuli to change color.

[0036] The color-changing component of the present invention may be contained in any of the layers constituting the adhesive sheet of the present invention, and may be contained in one or more of the adhesive layer, the substrate, or other layers constituting the adhesive sheet. For example, in the case of adhesive sheet 1A, it may be contained in the adhesive layer 10. In the case of adhesive sheet 1B, it may be contained in one or more of the adhesive layers 11 and 12, or the substrate S. It is preferable that the color-changing component of the present invention be contained in the adhesive layer, as this makes it easy to prepare an adhesive sheet containing the color-changing component of the present invention and easy to adjust the content of the color-changing component.

[0037] Examples of the aforementioned external stimuli include irradiation with active energy rays such as electron beam irradiation, ultraviolet irradiation, and laser light irradiation, as well as heating. From the viewpoint of easily forming alignment marks at any position on the adhesive sheet of the present invention, irradiation with active energy rays is preferred, ultraviolet irradiation is more preferred, and ultraviolet laser light irradiation is even more preferred from the viewpoint of easily forming alignment marks at specific positions.

[0038] The term "discolorable" in response to external stimuli refers to the ability to change color due to external stimuli. From the perspective of using it as an alignment mark, "coloring," which changes from colorless (transparent) to colored, is preferable.

[0039] The color-changing component of the present invention is not particularly limited as long as it can change color in response to the external stimulus, but examples include a combination of a compound that changes color upon reaction with an acid and an acid generator, a combination of a compound that decolorizes upon reaction with a base and a base generator, and photochromic compounds.

[0040] [Compounds that change color upon reaction with acids] The compound that changes color upon reaction with an acid constituting the color-changing component of the present invention is preferably a compound that changes from colorless (transparent) to colored by an acid, such as a leuco dye. A leuco dye is an organic dye whose color tone changes reversibly with oxidation and reduction. It may also be one whose absorption wavelength changes with pH. More specifically, it refers to a reduced-type dye having one or more hydrogen atoms that forms a dye and develops color by adding or removing electrons. A leuco dye is colorless or has a weak color in a neutral or alkaline medium, but when reacted with an acidic substance or an electron-withdrawing substance, the lactone ring opens up as shown in the formula below and becomes colored. By selecting a leuco dye that is substantially colorless or has a weak color before electrons are removed, it is possible to make the change in color more pronounced and improve the visibility of the alignment marks.

[0041] [ka]

[0042] In the above formula, R 11 , and R 2 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Or, R 1 , and R 2 may together with the nitrogen atom to which they are attached form a 5- or 6-membered nitrogen-containing heterocyclic ring. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 may be the same or different and each represents a hydrogen atom, a halogen atom, a hydrocarbon group, or -NR 10 R 11 . R 10 , and R 11 may be the same or different and each represents a hydrogen atom or a hydrocarbon group. Or, R 10 , and R 11 may together with the nitrogen atom to which they are attached form a 5- or 6-membered nitrogen-containing heterocyclic ring. Or, R 6 and R 7 , R 7 and R 8 , R 8 and R 9 may combine to form an aromatic hydrocarbon ring such as a benzene ring together with the benzene ring to which they are attached.

[0043] ​​​​​​​​​​​​​​1-6 Alkoxy group, C 1-6 The compound may have substituents such as alkoxycarbonyl groups and tetrahydrofuryl groups. Examples of 5- or 6-membered nitrogen-containing heterocycles include pyrrolidine, piperidine, and morpholine.

[0044] The leuco dye is colored by the acid generated by irradiating the acid generator with active energy rays or by heating it.

[0045] Furthermore, leuco dyes can be decolorized by reacting them with a base after the lactone ring has opened and colored, causing the lactone ring to close. The base can be generated by irradiating a base generator (described later) with active energy rays or by heating it.

[0046] Examples of leuco dyes include leuco compounds such as phthalide dyes (indolinophthalide type, triphenylmethanephthalide type, etc.), fluorane dyes, triarylmethane dyes, diphenylmethane dyes, phenothiazine dyes, auramine dyes, spiropyran dyes, and rhodamine dyes.

[0047] From the viewpoint of excellent color development, the leuco dye is preferably at least one leuco dye selected from the group consisting of phthalide dyes and fluorane dyes. Leuco dyes may be used individually or in combination of two or more types.

[0048] Specific examples of leuco dyes include the following compounds: 2'-Anilino-6'-(N,N-dipentan-1-ylamino)-3'-methyl-3H-spiro[isobenzofuran-1,9'-xanthene]-3-one, 2-anilino-3-methyl-6-dibutylaminofluorane, 2-anilino-3-methyl-6-dipentylaminofluorane, 2-anilino-3-methyl-6-[ethyl(4-methylphenyl)amino]fluorane, 3,3-bis(p-dimethylaminophenyl)-phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide (also known as crystal violet) Lactone), 3,3-bis(p-dimethylaminophenyl)-6-diethylaminophthalide, 3,3-bis(p-dimethylaminophenyl)-6-chlorphthalide, 3,3-bis(p-dibutylaminophenyl)phthalide, 3-cyclohexylamino-6-chlorofluorane, 3-dimethylamino-5,7-dimethylfluorane, 3-(N-methyl-N-isobutyl)-6-methyl-7-anilinofluorane, 3-(N-ethyl-N-isoamyl)-6-methyl-7-anilinofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-chlorofluorane, 3-diethylamino-7-chlorofluorane Tylamino-7-methylfluorane, 3-diethylamino-7,8-benzfluorane, 3-diethylamino-6-methyl-7-chlorfluorane, 3-(Np-tolyl-N-ethylamino)-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 2-{N-(3'-trifluoromethylphenyl)amino}-6-diethylaminofluorane, 2-{3,6-bis(diethylamino)-9-(o-chloranilino)xanthyalbenzoate lactam}3-diethylamino-6-methyl-7-(m-trichloro (N,N-methylanilino)fluorane, 3-diethylamino-7-(o-chloranilino)fluorane, 3-dibutylamino-7-(o-chloranilino)fluorane, 3-(N-methyl-N-amylamino)-6-methyl-7-anilinofluorane, 3-(N-methyl-N-cyclohexylamino)-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-(2',4'-dimethylanilino)fluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, benzoylleucomethylene blue, 6'-chloro-8'-methoxy-benzoindlino-spiropyran, 6'-bromo-3'-methoxy-benzoindlino-spiropyran, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-chlorophenyl)phthalide, 3-(2'-hydroxy-4'-dimethylaminophenyl)-3-(2'-methoxy-5'-nitrophenyl)phthalide, 3 -(2'-hydroxy-4'-diethylaminophenyl)-3-(2'-methoxy-5'-methylphenyl)phthalide, 3-(2'-methoxy-4'-dimethylaminophenyl)-3-(2'-hydroxy-4'-chlor-5'-methylphenyl)phthalide, 3-morpholino-7-(N-propyl-trifluoromethylanilino)fluorane, 3-pyrrolidino-7-trifluoromethylanilinofluorane, 3-diethylamino-5-chloro-7-(N-bendi (Trifluoromethylanilino)fluorane, 3-pyrrolidino-7-(di-p-chlorophenyl)methylaminofluorane, 3-diethylamino-5-chlor-7-(α-phenylethylamino)fluorane, 3-(N-ethyl-p-toluidino)-7-(α-phenylethylamino)fluorane, 3-diethylamino-7-(o-methoxycarbonylphenylamino)fluorane, 3-diethylamino-5-methyl-7-(α-phenylethylamino)fluorane Oran, 3-diethylamino-7-piperidinofluorane, 2-chloro-3-(N-methyltoluidino)-7-(pn-butylanilino)fluorane, 3-(N-methyl-N-isopropylamino)-6-methyl-7-anilinofluorane, 3-dibutylamino-6-methyl-7-anilinofluorane, 3,6-bis(dimethylamino)fluorenspiro(9,3')-6'-dimethylaminophthalide, 3-(N-benzyl-N-cyclohexylamino)-5,6-Benzo-7-α-naphthylamino-4'-bromofluorane, 3-diethylamino-6-chlor-7-anilinofluorane, 3-{N-ethyl-N-(2-ethoxypropyl)amino}-6-methyl-7-anilinofluorane, 3-{N-ethyl-N-tetrahydrofurfurylamino}-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-mesitidino-4',5'-benzofluorane, 3-(p-dimethylaminophenyl)-3-{1,1-bis(p-dimethylaminophenyl) Nophenyl)ethylene-2-yl}phthalide, 3-(p-dimethylaminophenyl)-3-{1,1-bis(p-dimethylaminophenyl)ethylene-2-yl}-6-dimethylaminophthalide, 3-(p-dimethylaminophenyl)-3-(1-p-dimethylaminophenyl-1-phenylethylene-2-yl)phthalide, 3-(p-dimethylaminophenyl)-3-(1-p-dimethylaminophenyl-1-p-chlorophenylethylene-2-yl)-6-dimethylaminophthalide, 3-(4'- Dimethylamino-2'-methoxy)-3-(1"-p-dimethylaminophenyl-1"-p-chlorophenyl-1",3"-butadien-4"-yl)benzophthalide, 3-(4'-dimethylamino-2'-benzyloxy)-3-(1"-p-dimethylaminophenyl-1"-phenyl-1",3"-butadien-4"-yl)benzophthalide, 3-dimethylamino-6-dimethylamino-fluoren-9-spiro-3'(6'-dimethylamino)phthalide, 6-(diethylamino)-2-[(3 -Trifluoromethyl)anilino]xanthene-9-spiro-3'-phthalide, 3,3-bis{2-(p-dimethylaminophenyl)-2-(p-methoxyphenyl)ethenyl}-4,5,6,7-tetrachlorophthalide, 3-bis{1,1-bis(4-pyrrolidinophenyl)ethylene-2-yl}-5,6-dichloro-4,7-dibromophthalide, bis(p-dimethylaminostyryl)-1-naphthalenesulfonylmethane, bis(p-dimethylaminostyryl)-1-p-tolylsulfonylmethane.

[0049] Compounds that change color upon reaction with acid may be used individually or in mixtures of two or more types. The compound that changes color upon reaction with acid is preferably present in amounts of 0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, even more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight per 100 parts by weight of the adhesive sheet. Within these ranges, alignment marks can be efficiently formed by the color change caused by the compound that changes color upon reaction with acid.

[0050] [Acid Generator] The acid generator constituting the color-changing component of the present invention is a compound that generates acid (cation) when the aforementioned external stimulus is applied. The generated acid causes the compound that changes color through reaction with the acid to change color. When the external stimulus is irradiation with active energy rays, a photoacid generator is used, and when the external stimulus is heating, a thermoacid generator is used. From the viewpoint of easily creating alignment marks at any position on the adhesive sheet of the present invention by irradiation with active energy rays, a photoacid generator is preferred.

[0051] The photoacid generator is a compound that can generate acid (cations) by irradiation with active energy rays such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, and X-rays, not limited to light such as ultraviolet, visible, and infrared rays. By using the photoacid generator together with a compound that changes color upon reaction with the acid, the adhesive sheet of the present invention can be irradiated with active energy rays to cause discoloration at any location and at any time, thereby forming alignment marks.

[0052] The photoacid generator is not particularly limited as long as it is a compound that can generate acid (cation) by irradiation with active energy rays, and examples include sulfonium salt compounds, iodonium salt compounds, aromatic N-oxyimide sulfonates, sulfonic acid ester compounds, and halomethyl-substituted S-triazine derivatives.

[0053] From the viewpoint of having good compatibility with the adhesive that constitutes the adhesive sheet of the present invention (described later), the photoacid generator is preferably at least one compound selected from the group consisting of sulfonium salt compounds, iodonium salt compounds, and aromatic N-oxyimide sulfonates, and sulfonium salt compounds are particularly preferred.

[0054] Specific examples of sulfonium salt compounds include salts composed of cations such as dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8-dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl-4-phenylthiophenylsulfonium, and diphenyl-4-phenylthiophenylsulfonium, and anions such as chlorides, bromides, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and nonafluorobutanesulfonate.

[0055] Examples of iodonium salt compounds include salts composed of cations such as diphenyliodonium, bis(p-chlorophenyl)iodonium, ditolyliodonium, bis(p-tert-butylphenyl)iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis(m-nitrophenyl)iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis(p-methoxyphenyl)iodonium, p-octyloxyphenylphenyliodonium, and p-phenoxyphenylphenyliodonium, and anions such as chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, and nonafluorobutanesulfonate.

[0056] Examples of aromatic N-oxyimide sulfonates include N-(trifluoromethylsulfonyloxy)succinimide, N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)diphenylmaleimide, N-(trifluoromethylsulfonyloxy)bicyclohepto-5-ene-2,3-dicarboximide, and N-(trifluoromethylsulfonyloxy)naphthylimide.

[0057] Examples of sulfonic acid ester compounds include benzointosylate, α-methylolbenzointosylate, o-nitrobenzyl p-toluenesulfonate, and p-nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate. Specific examples of halomethyl-substituted S-triazine derivatives include 2,4,6-tris(trichloromethyl)-S-triazine, 2-methyl-4,6-bis(trichloromethyl)-S-triazine, 2-phenyl-4,6-bis(trichloromethyl)-S-triazine, and 2-methyl-4,6-bis(tribromomethyl)-S-triazine.

[0058] The thermal acid generator is a compound that can generate acid (cations) when heated. By using the thermal acid generator together with a compound that changes color upon reaction with the acid, the adhesive sheet of the present invention can be heated to cause discoloration or coloring at any location and at any time, thereby forming alignment marks.

[0059] Examples of thermal acid generators include aryl sulfonium salts, aryl iodonium salts, allene ion complexes, quaternary ammonium salts, aluminum chelates, and boron trifluoride amine complexes. Examples of anions include those similar to those used in photoacid generators, such as SbF6. - These may be antimony fluoride ions, such as those mentioned above.

[0060] These acid generators can be used individually or in combination of two or more. The acid generator is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, even more preferably 0.1 to 30 parts by weight, and still more preferably 0.1 to 20 parts by weight per 100 parts by weight of the adhesive sheet of the present invention. Within these ranges, acid can be efficiently generated by irradiation with active energy rays or heating, and alignment marks can be efficiently formed by discoloration caused by a compound that changes color upon reaction with the acid.

[0061] [Base Generator] The adhesive sheet of the present invention may contain a base-generating agent. The base-generating agent is a compound that generates a base when the external stimulus is applied. If the external stimulus is irradiation with active energy rays, a photobase-generating agent is used; if the external stimulus is heating, a thermobase-generating agent is used. From the viewpoint of efficiently removing alignment marks formed on the adhesive sheet of the present invention, a photobase-generating agent is preferred.

[0062] When the adhesive sheet of the present invention contains a photoacid generator, it is preferable to set the combination of the photoacid generator and the thermal base generator such that the base generator does not generate a base at the same time as the photoacid generator generates an acid upon irradiation with active energy rays. Furthermore, if the adhesive sheet of the present invention contains a thermoacid generator, it is preferable to set the combination of the thermoacid generator and the photobase generator such that the base generator does not generate a base at the same time as the thermoacid generator generates an acid due to heating.

[0063] A photobase generator is a compound that can generate bases (anions) by irradiation with active energy rays such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, and X-rays, not limited to light such as ultraviolet, visible, and infrared rays. By using a photobase generator together with a compound that changes color upon reaction with the acid, the alignment marks can be removed at any desired timing by irradiating the adhesive sheet of the present invention with active energy rays.

[0064] The photobase generator is not particularly limited as long as it is a compound that can generate a base (anion) by irradiation with active energy rays. Examples include transition metal complexes, compounds having a benzylcarbamate structure, compounds having an ortho-substituted nitrobenzene structure, oximes, imidazole derivatives, benzoin compounds, compounds having an N-formylated aromatic amino group, compounds having an N-acylated aromatic amino group, compounds having an alkoxybenzylcarbamate group, compounds having a 1,4-dihydropyridine skeleton, oxime esters, quaternary ammonium salts, and the like.

[0065] A thermal base generator is a compound that can generate a base (anion) upon heating. By using a thermal base generator together with a compound that changes color upon reaction with the acid, the adhesive sheet of the present invention can be heated to make the alignment marks disappear at any desired time.

[0066] The thermal base generator is not particularly limited as long as it is a compound that can generate a base (anion) upon heating. Examples include carbamate derivatives such as 2-(4-biphenyl)-2-propyl carbamate and 1,1-dimethyl-2-cyanoethyl carbamate, urea derivatives such as urea and N,N,N'-trimethylurea, dihydropyridine derivatives such as 1,4-dihydronicotinamide, dicyandiamide, and salts consisting of acids and bases such as organic salts and inorganic salts.

[0067] These base-generating agents can be used individually or in combination of two or more. The amount of base generating agent is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, and even more preferably 0.1 to 20 parts by weight per 100 parts by weight of the adhesive sheet of the present invention. Within this range, bases can be efficiently generated by irradiation with active energy rays or heating, enabling the decolorization of alignment marks.

[0068] [Combination of a compound that decolorizes upon reaction with a base and a base generator] The compound that decolorizes upon reaction with a base constituting the color-changing component of the present invention is preferably a compound that changes from colored to colorless (transparent) upon contact with a base. For example, a compound obtained by the above-mentioned leuco dye changing color (coloring) upon reaction with an acid is an example. Compounds that decolorize upon reaction with a base can also be produced, for example, by the reaction of a leuco dye with an acid generated by heating the above-mentioned thermal acid generator.

[0069] The compound that decolorizes upon reaction with a base may be used individually or as a mixture of two or more types. The amount of the compound that decolorizes upon reaction with a base is the same as that of the compound that changes color upon reaction with an acid.

[0070] Examples of base generators used in combination with compounds that decolorize upon reaction with a base are the same as those mentioned above, and can be used in the same quantities.

[0071] A preferred embodiment of the combination of a compound that decolorizes upon reaction with a base and a base generator is to color the entire surface of an adhesive sheet with a compound that decolorizes upon reaction with a base generated by the reaction of a leuco dye with an acid generated by heating the above-mentioned thermal acid generator, and then decolorize the area by applying an external stimulus such as light to a predetermined location, thereby decolorizing the area with a base generated from the base generator, and using the decolorized area as an alignment mark.

[0072] [Photochromic compounds] The photochromic compound constituting the color-changing component of this invention is a compound whose molecular structure reversibly changes upon irradiation with light of a specific wavelength, resulting in a change in color. As an external stimulus, the area that has changed color upon irradiation with light of a specific wavelength can be used as an alignment mark.

[0073] There are no particular restrictions on the photochromic compound; any compound from the conventionally known compounds can be appropriately selected and used. For example, one or more compounds can be used from spiropyran compounds, spirooxazine compounds, fulgide compounds, naphthopyran compounds, bisimidazole compounds, etc., depending on the desired coloration.

[0074] The amount of the photochromic compound is preferably 0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, even more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight per 100 parts by weight of the adhesive sheet. Within this range, alignment marks can be efficiently formed by the color change caused by the photochromic compound.

[0075] [Adhesive layer] The adhesive layer constituting the adhesive sheet of the present invention is attached to the support plate in order to fix the adhesive sheet to the support plate. Furthermore, the adhesive layer constituting the adhesive sheet of the present invention also serves to temporarily fix the member. In the adhesive sheet of the present invention, the adhesive layer for temporarily fixing to a member is referred to as the "first adhesive layer," and the adhesive layer for fixing to a support plate is referred to as the "second adhesive layer." The first adhesive layer and the second adhesive layer may be composed of the same adhesive, or they may be composed of different adhesives.

[0076] If the adhesive sheet of this embodiment is a substrate-less adhesive sheet, the first adhesive layer and the second adhesive layer may be a single adhesive layer, or they may be laminated together. Furthermore, if the adhesive sheet of this embodiment is an adhesive sheet with a base material, the first adhesive layer and the second adhesive layer may be composed of the same adhesive layer, or they may be composed of different adhesives.

[0077] Furthermore, in the adhesive sheet of this embodiment, the discoloration component of the present invention may be contained in only one of the first adhesive layer and the second adhesive layer, or it may be contained in both the first adhesive layer and the second adhesive layer.

[0078] When processing using active energy ray irradiation, such as laser irradiation, is performed after the component has been temporarily fixed to the first adhesive layer, discoloration of the adhesive sheet due to the active energy ray irradiation is undesirable. Therefore, it is preferable that the first adhesive layer does not contain a discoloration component, and the second adhesive layer contains a discoloration component.

[0079] The compound that changes color upon reaction with acid is preferably present in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, even more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight, per 100 parts by weight of the adhesive layer (first adhesive layer or second adhesive layer). Within this range, alignment marks can be efficiently formed by the color change caused by the compound that changes color upon reaction with acid.

[0080] The acid generator is preferably present in an amount of 0.001 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, even more preferably 0.1 to 30 parts by weight, and still more preferably 0.1 to 20 parts by weight per 100 parts by weight of the adhesive layer (first adhesive layer or second adhesive layer). Within this range, acid can be efficiently generated by irradiation with active energy rays or heating, and alignment marks can be efficiently formed by discoloration caused by a compound that changes color upon reaction with the acid.

[0081] The amount of base generator is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, and even more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the adhesive layer (first adhesive layer or second adhesive layer). Within this range, bases can be efficiently generated by irradiation with active energy rays or heating, enabling the decolorization of alignment marks.

[0082] In the first and second embodiments, the content of the compound that decolorizes upon reaction with a base and the photochromic compound in the adhesive layer is the same as that of the compound that changes color upon reaction with an acid.

[0083] An embodiment of the first adhesive layer and the second adhesive layer of the adhesive sheet of the present invention will be described, but the first adhesive layer and the second adhesive layer are not clearly distinguished, and the first adhesive layer of this embodiment can be used as the second adhesive layer, and the second adhesive layer of this embodiment can be used as the first adhesive layer. Furthermore, if the adhesive sheet of the present invention is a substrate-less adhesive sheet having a single adhesive layer, it is also possible to use the first adhesive layer or the second adhesive layer as the single adhesive layer.

[0084] [First adhesive layer] The first adhesive layer is an adhesive layer for temporarily fixing the components. The thickness of the first adhesive layer is not particularly limited, but is preferably 1 μm or more, and more preferably 3 μm or more. A thickness above a certain level is preferable because it makes it easier for the first adhesive layer to temporarily fix the member with accuracy. Furthermore, the upper limit of the thickness of the first adhesive layer is not particularly limited, but is preferably 100 μm or less, and more preferably 75 μm or less. A thickness below a certain level is preferable because it makes it easier to peel off the member after processing.

[0085] In the adhesive sheet of this embodiment, the haze of the first adhesive layer (according to JIS K7136) is not particularly limited, but is preferably 10% or less, and more preferably 5.0% or less. A haze of 10% or less is preferable because it provides excellent transparency, improves the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment, and is therefore preferable. The haze can be measured, for example, by forming the first adhesive layer on a release liner, leaving it at normal conditions (23°C, 50%RH) for at least 24 hours, peeling off the release liner, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and a haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0086] In the adhesive sheet of this embodiment, the total light transmittance of the first adhesive layer in the visible light wavelength range (according to JIS K7361-1) is not particularly limited, but is preferably 85% or more, and more preferably 88% or more. A total light transmittance of 85% or more is preferable because it provides excellent transparency, improves the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment, and is therefore desirable. The total light transmittance can be measured, for example, by forming the first adhesive layer on a release liner, leaving it at normal conditions (23°C, 50%RH) for at least 24 hours, peeling off the release liner, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0087] The adhesive constituting the first adhesive layer described above is not particularly limited, but examples include silicone-based adhesives, urethane-based adhesives, acrylic-based adhesives, rubber-based adhesives, polyester-based adhesives, polyamide-based adhesives, epoxy-based adhesives, vinyl alkyl ether-based adhesives, and fluorine-based adhesives. Among these, from the viewpoint of being able to temporarily fix the members with high precision, and from the viewpoint of having high transparency and good visibility of alignment marks, silicone-based adhesives, urethane-based adhesives, and acrylic-based adhesives, which are easy to control to have low tack and transparency, are preferred, silicone-based adhesives and urethane-based adhesives are more preferred, and silicone-based adhesives are even more preferred.

[0088] [Silicone-based adhesive] The silicone adhesive is not particularly limited, and known or conventional silicone adhesives can be used, such as addition-type silicone adhesives, peroxide-curing type silicone adhesives, and condensation-type silicone adhesives. The silicone adhesive may be one-component or two-component. The silicone adhesive can be used alone or in combination of two or more types.

[0089] The aforementioned addition-type silicone adhesives are adhesives that produce a silicone polymer by an addition reaction (hydrosilylation reaction) between an organopolysiloxane having an alkenyl group such as a vinyl group on a silicon atom and an organopolysiloxane having a hydrosilyl group, using a platinum compound catalyst such as chloroplatinic acid. Peroxide-curing type silicone adhesives are adhesives that produce a silicone polymer by curing (crosslinking) an organopolysiloxane with a peroxide. Furthermore, condensation-type silicone adhesives are adhesives that produce a silicone polymer by a dehydration or dealcoholization reaction between polyorganosiloxanes having hydrolyzable silyl groups such as silanol groups or alkoxysilyl groups at their ends.

[0090] Examples of silicone-based adhesives include silicone-based adhesive compositions containing silicone rubber and silicone resin, due to their ease of controlling low tackiness.

[0091] The silicone rubber is not particularly limited as long as it is a silicone-based rubber component, but for example, organopolysiloxanes mainly composed of dimethylsiloxane, methylphenylsiloxane, etc. can be used. Depending on the type of reaction, silicone rubber having alkenyl groups bonded to silicon atoms (alkenyl group-containing organopolysiloxane; in the case of addition reaction), silicone rubber having at least methyl groups (in the case of peroxide curing), and silicone rubber having silanol groups or hydrolyzable alkoxysilyl groups at the ends (in the case of condensation) can be used. The weight-average molecular weight of organopolysiloxane in silicone rubber is usually 150,000 or more, but is preferably 280,000 to 1,000,000, and particularly preferably 500,000 to 900,000.

[0092] Furthermore, the silicone resin is not particularly limited as long as it is a silicone-based resin used in silicone-based adhesives, for example, the constituent unit "R3Si 1 / 2 The M unit consists of the constituent unit "SiO2", the Q unit consists of the constituent unit "RSiO2", and the constituent unit "RSiO 3 / 2Examples include silicone resins made of organopolysiloxanes, which are (co)polymers having at least one unit selected from the T units consisting of "" and the D units consisting of the constituent unit "R2SiO". In the constituent unit, R represents a hydrocarbon group or a hydroxyl group. Examples of the hydrocarbon group include aliphatic hydrocarbon groups (alkyl groups such as methyl and ethyl groups), alicyclic hydrocarbon groups (cycloalkyl groups such as cyclohexyl groups), and aromatic hydrocarbon groups (aryl groups such as phenyl and naphthyl groups). The ratio of the M unit to at least one unit selected from the Q, T, and D units is preferably about 0.3 / 1 to 1.5 / 1 (preferably 0.5 / 1 to 1.3 / 1). Various functional groups such as vinyl groups may be introduced into the organopolysiloxane in such silicone resins as needed. The introduced functional groups may be functional groups capable of crosslinking reactions. As the silicone resin, MQ resin consisting of M units and Q units is preferred. The weight-average molecular weight of the organopolysiloxane in the silicone resin is usually 1000 or more, but is preferably 1000 to 20000, and particularly preferably 1500 to 10000.

[0093] While there are no particular restrictions on the mixing ratio of silicone rubber to silicone resin, it is preferable, for example, that the ratio of silicone resin is 100 to 220 parts by weight (particularly 120 to 180 parts by weight) per 100 parts by weight of silicone rubber, as this makes it easier to control low tackiness.

[0094] In a silicone-based adhesive composition containing silicone rubber and silicone resin, the silicone rubber and silicone resin may simply be in a mixed state, or they may react with each other to form condensates (especially partial condensates), crosslinked products, addition reaction products, etc.

[0095] Furthermore, silicone-based adhesive compositions containing silicone rubber and silicone resin typically contain a crosslinking agent to create a crosslinked structure, as this makes it easier to control the tackiness. While there are no particular limitations on such crosslinking agents, siloxane-based crosslinking agents (silicone-based crosslinking agents) and peroxide-based crosslinking agents are suitably used. The crosslinking agent can be used alone or in combination of two or more types.

[0096] As the siloxane-based crosslinking agent, for example, a polyorganohydrogensiloxane having two or more hydrogen atoms bonded to silicon atoms in the molecule can be suitably used. In such a polyorganohydrogensiloxane, various organic groups other than hydrogen atoms may be bonded to the silicon atoms to which the hydrogen atoms are bonded. Examples of such organic groups include alkyl groups such as methyl groups and ethyl groups; aryl groups such as phenyl groups; and alkyl halides, but from the viewpoint of synthesis and handling, methyl groups are preferred. Furthermore, the skeletal structure of the polyorganohydrogensiloxane may be linear, branched, or cyclic, but a linear structure is preferred.

[0097] Examples of peroxide-based crosslinking agents include diacyl peroxide, alkyl peroxyester, peroxydicarbonate, monoperoxycarbonate, peroxyketal, dialkyl peroxide, hydroperoxide, and ketone peroxide. More specifically, examples include benzoyl peroxide, t-butyl peroxybenzoate, dicumyl peroxide, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di-t-butyl peroxyhexane, 2,4-dichlorobenzoyl peroxide, di-t-butyl peroxydiisopropylbenzene, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, and 2,5-dimethyl-2,5-di-t-butyl peroxyhexyn-3.

[0098] As addition-curing silicone adhesives, for example, the following are commercially available: product names "KR-3700", "KR-3701", "X-40-3237-1", "X-40-3240", "X-40-3291-1", and "X-40-3306" (all manufactured by Shin-Etsu Chemical Co., Ltd.). In addition, as peroxide-curing silicone adhesives, for example, product names "KR-100", "KR-101-10", and "KR-130" (all manufactured by Shin-Etsu Chemical Co., Ltd.) are commercially available.

[0099] The addition-type silicone adhesive composition preferably contains a curing catalyst such as a platinum catalyst. Examples of commercially available platinum catalysts include "CAT-PL-50T" (manufactured by Shin-Etsu Chemical Co., Ltd.), "DOWSIL NC-25 Catalyst," or "DOWSIL SRX212 Catalyst" (all manufactured by Dow Toray Corporation). From the viewpoint of balancing the tackiness, positional accuracy, and tack force of the first adhesive layer, the curing catalyst content is preferably about 0.1 to 10 parts by weight per 100 parts by weight of the silicone polymer (including silicone rubber, silicone resin, etc.) as the base polymer.

[0100] [Urethane-based adhesive] The urethane adhesive is not particularly limited, and known or conventional urethane adhesives can be used. However, a urethane adhesive composition containing a polyol, a polyfunctional isocyanate compound, and a catalyst is preferred because it is easy to control the tackiness.

[0101] As the polyol, any suitable polyol having two or more hydroxyl groups can be used. Examples of such polyols include polyols having two hydroxyl groups (diols), polyols having three hydroxyl groups (triols), polyols having four hydroxyl groups (tetraols), polyols having five hydroxyl groups (pentaols), and polyols having six hydroxyl groups (hexaols). The polyol may be just one type or two or more types.

[0102] The polyol preferably contains a polyol with a number-average molecular weight (Mn) of 400 to 20000. The content of the polyol with a number-average molecular weight (Mn) of 400 to 20000 in the total polyol is preferably 50 to 100% by weight, more preferably 70 to 100% by weight, even more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight, and most preferably substantially 100% by weight. By adjusting the content of the polyol with a number-average molecular weight (Mn) of 400 to 20000 in the polyol to within the above range, for example, a urethane-based adhesive with controlled low tack can be provided.

[0103] Examples of the aforementioned polyols include polyester polyols, polyether polyols, polycaprolactone polyols, polycarbonate polyols, and castor oil-based polyols.

[0104] The aforementioned polyester polyol can be obtained, for example, by an esterification reaction between a polyol component and an acid component.

[0105] Examples of the polyol component include ethylene glycol, diethylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethyl-1,3-propanediol, 2,4-diethyl-1,5-pentanediol, 1,2-hexanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,8-decanediol, octadecanediol, glycerin, trimethylolpropane, pentaerythritol, hexanetriol, and polypropylene glycol.

[0106] Examples of the aforementioned acidic components include succinic acid, methylsuccinic acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, 1,12-dodecanediic acid, 1,14-tetradecanediic acid, dimer acid, 2-methyl-1,4-cyclohexanedicarboxylic acid, 2-ethyl-1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and their acid anhydrides.

[0107] Examples of the aforementioned polyether polyols include polyether polyols obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, using water, low molecular weight polyols (propylene glycol, ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, etc.), bisphenols (bisphenol A, etc.), and dihydroxybenzene (catechol, resorcinol, hydroquinone, etc.) as initiators. Specifically, examples include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.

[0108] Examples of the polycaprolactone polyols include caprolactone-based polyester diols obtained by ring-opening polymerization of cyclic ester monomers such as ε-caprolactone and σ-valerolactone.

[0109] Examples of the polycarbonate polyols include: polycarbonate polyols obtained by polycondensation reaction of the polyol component with phosgene; polycarbonate polyols obtained by transesterification condensation of the polyol component with diesters such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, diisopropyl carbonate, dibutyl carbonate, ethylbutyl carbonate, ethylene carbonate, propylene carbonate, diphenyl carbonate, and dibenzyl carbonate; copolymerized polycarbonate polyols obtained by using two or more of the polyol components in combination; polycarbonate polyols obtained by esterification reaction of the various polycarbonate polyols with carboxyl group-containing compounds; and various Examples include: polycarbonate polyols obtained by etherification reaction of a polycarbonate polyol with a hydroxyl group-containing compound; polycarbonate polyols obtained by transesterification reaction of the aforementioned polycarbonate polyols with ester compounds; polycarbonate polyols obtained by transesterification reaction of the aforementioned polycarbonate polyols with hydroxyl group-containing compounds; polyester-based polycarbonate polyols obtained by polycondensation reaction of the aforementioned polycarbonate polyols with dicarboxylic acid compounds; copolymerized polyether-based polycarbonate polyols obtained by copolymerization of the aforementioned polycarbonate polyols with alkylene oxides; and the like.

[0110] Examples of the castor oil-based polyols include castor oil-based polyols obtained by reacting castor oil fatty acids with the polyol component. Specifically, examples include castor oil-based polyols obtained by reacting castor oil fatty acids with polypropylene glycol.

[0111] As the polyol, it is preferable to use a polyol (triol) having three hydroxyl groups as an essential component, from the viewpoint of low tackiness and wettability of the first adhesive layer to the material. The polyol (triol) having three hydroxyl groups is preferably present in an amount of 50 to 100% by weight, and more preferably 70 to 100% by weight, relative to the total amount of components constituting the polyol.

[0112] Examples of the aforementioned polyfunctional isocyanate compounds include aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic polyisocyanate compounds.

[0113] Examples of the aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0114] Examples of the alicyclic polyisocyanates include 1,3-cyclopentene diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated tetramethylxylylene diisocyanate.

[0115] Examples of the aromatic polyisocyanates include phenylenediisocyanate, 2,4-tolylenediisosoanate, 2,6-tolylenediisosoanate, 2,2'-diphenylmethanediisocyanate, 4,4'-diphenylmethanediisocyanate, 4,4'-toluidinediisocyanate, 4,4'-diphenyletherdiisocyanate, 4,4'-diphenyldiisocyanate, 1,5-naphthalenediisocyanate, xylylenediisocyanate, and the like.

[0116] Among these, aliphatic polyisocyanates and their modified forms are preferred. Compared to other isocyanate-based crosslinking agents, aliphatic polyisocyanates and their modified forms have a highly flexible crosslinking structure and are easy to control to low tack. Among aliphatic polyisocyanates and their modified forms, hexamethylene diisocyanates and their modified forms are particularly preferred.

[0117] From the viewpoint of adhesion to the material of the first adhesive layer, low tackiness, and wettability, the equivalent ratio (NCO / OH) of the isocyanate group of the polyfunctional isocyanate compound and the hydroxyl group of the polyol is preferably 1 to 5, more preferably 1.1 to 3, and even more preferably 1.2 to 2.

[0118] The urethane adhesive composition preferably contains a catalyst such as an iron-based compound and / or a tin-based compound. Specifically, tin-based catalysts such as dibutyltin dilaurate and dioctyltin dilaurate, tris(acetylacetonate) iron, tris(hexane-2,4-dionato) iron, tris(heptane-2,4-dionato) iron, tris(heptane-3,5-dionato) iron, tris(5-methylhexane-2,4-dionato) iron, tris(octane-2,4-dionato) iron, and tris(6-methylheptane-2 ,4-dionato) iron, tris(2,6-dimethylheptane-3,5-dionato) iron, tris(nonane-2,4-dionato) iron, tris(nonane-4,6-dionato) iron, tris(2,2,6,6-tetramethylheptane-3,5-dionato) iron, tris(tridecane-6,8-dionato) iron, tris(1-phenylbutane-1,3-dionato) iron, tris(hexafluoroacetylacetonate Examples of iron-based catalysts include iron, tris(acetate acetate)ferrous iron, tris(acetoacetate-n-propyl)ferrous iron, tris(acetoacetate-isopropyl)ferrous iron, tris(acetoacetate-n-butyl)ferrous iron, tris(acetoacetate-sec-butyl)ferrous iron, tris(acetoacetate-tert-butyl)ferrous iron, tris(propionylacetate-methyl)ferrous iron, tris(propionylacetate-n-propyl)ferrous iron, tris(propionylacetate-isopropyl)ferrous iron, tris(propionylacetate-n-butyl)ferrous iron, tris(propionylacetate-sec-butyl)ferrous iron, tris(propionylacetate-tert-butyl)ferrous iron, tris(acetoacetate benzyl)ferrous iron, tris(malonate dimethyl)ferrous iron, tris(malonate diethyl)ferrous iron, trimethoxyferrous iron, triethoxyferrous iron, triisopropoxyferrous iron, and ferric chloride.

[0119] The amount of catalyst contained in the urethane-based adhesive composition is preferably 0.002 to 0.5 parts by weight, more preferably 0.005 to 0.3 parts by weight, and even more preferably 0.01 to 0.1 parts by weight, per 100 parts by weight of polyol. Within this range, the crosslinking reaction rate is fast when the adhesive layer is formed, and the pot life of the adhesive composition is also extended, resulting in a desirable embodiment.

[0120] Furthermore, as a urethane-based adhesive, a urethane-based adhesive composition containing a urethane prepolymer is also preferred because it is easier to control its low tack properties.

[0121] Examples of urethane-based adhesive compositions containing a urethane prepolymer include adhesive compositions containing a polyurethane polyol as the urethane prepolymer and a polyfunctional isocyanate compound. The urethane prepolymer may be one type or two or more types. The polyfunctional isocyanate compound may be one type or two or more types.

[0122] The polyurethane polyol used as a urethane prepolymer is preferably obtained by reacting a polyester polyol and a polyether polyol with an organic polyisocyanate compound in the presence or absence of a catalyst.

[0123] Any suitable polyester polyol can be used as the polyester polyol. Examples of such polyester polyols include those obtained by reacting an acid component with a glycol component. Examples of acid components include terephthalic acid, adipic acid, azelaic acid, sebatic acid, phthalic anhydride, isophthalic acid, and trimellitic acid. Examples of glycol components include ethylene glycol, propylene glycol, diethylene glycol, butylene glycol, 1,6-hexane glycol, 3-methyl-1,5-pentanediol, 3,3'-dimethylolheptane, polyoxyethylene glycol, polyoxypropylene glycol, 1,4-butanediol, neopentyl glycol, and butylethylpentanediol. Examples of polyol components include glycerin, trimethylolpropane, and pentaerythritol. Other examples of polyester polyols include those obtained by ring-opening polymerization of lactones such as polycaprolactone, poly(β-methyl-γ-valerolactone), and polyvalerolactone.

[0124] Polyester polyols can be used with molecular weights ranging from low to high. Preferably, the number average molecular weight of the polyester polyol is 500 to 5000. If the number average molecular weight is less than 500, the reactivity may increase, potentially leading to gelation. If the number average molecular weight exceeds 5000, the reactivity may decrease, and furthermore, the cohesive force of the polyurethane polyol itself may weaken. The amount of polyester polyol used is preferably 10 to 90 mol% of the polyol constituting the polyurethane polyol.

[0125] Any suitable polyether polyol can be used as the polyether polyol. Examples of such polyether polyols include those obtained by polymerizing oxirane compounds such as ethylene oxide, propylene oxide, butylene oxide, and tetrahydrofuran using a low molecular weight polyol such as water, propylene glycol, ethylene glycol, glycerin, or trimethylolpropane as an initiator. Specifically, examples of such polyether polyols include polyether polyols with two or more functional groups, such as polypropylene glycol, polyethylene glycol, and polytetramethylene glycol.

[0126] Polyether polyols can be used with molecular weights ranging from low to high. Preferably, the number average molecular weight of the polyether polyol is between 1000 and 5000. If the number average molecular weight is less than 1000, the reactivity may increase, potentially leading to gelation. If the number average molecular weight exceeds 5000, the reactivity may decrease, and furthermore, the cohesive force of the polyurethane polyol itself may weaken. The amount of polyether polyol used is preferably 20 to 80 mol% of the polyol constituting the polyurethane polyol.

[0127] Polyether polyols can be used in combination with glycols such as ethylene glycol, 1,4-butanediol, neopentyl glycol, butylethylpentanediol, glycerin, trimethylolpropane, and pentaerythritol, or with polyhydric amines such as ethylenediamine, N-aminoethylethanolamine, isophoronediamine, and xylylenediamine, as needed.

[0128] As the polyether polyol, only difunctional polyether polyols may be used, or some or all of a polyether polyol having a number average molecular weight of 1000 to 5000 and at least three hydroxyl groups per molecule may be used. When some or all of a polyether polyol having an average molecular weight of 1000 to 5000 and at least three hydroxyl groups per molecule is used as the polyether polyol, a good balance between adhesiveness and re-peelability can be achieved. In such polyether polyols, if the number average molecular weight is less than 1000, the reactivity may increase, and gelation may become more likely. In such polyether polyols, if the number average molecular weight exceeds 5000, the reactivity may decrease, and furthermore, the cohesive force of the polyurethane polyol itself may decrease. The number average molecular weight of such polyether polyols is more preferably 2500 to 3500.

[0129] Any suitable organic polyisocyanate compound can be used as the organic polyisocyanate compound. Examples of such organic polyisocyanate compounds include aromatic polyisocyanates, aliphatic polyisocyanates, aromatic aliphatic polyisocyanates, and alicyclic polyisocyanates.

[0130] Examples of aromatic polyisocyanates include 1,3-phenylenediisocyanate, 4,4'-diphenyldiisocyanate, 1,4-phenylenediisocyanate, 4,4'-diphenylmethanediisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylenediisocyanate, 4,4'-toluidinediisocyanate, 2,4,6-triisocyanatetoluene, 1,3,5-triisocyanatebenzene, dianisidinediisocyanate, 4,4'-diphenyletherdiisocyanate, and 4,4',4"-triphenylmethanetriisocyanate.

[0131] Examples of aliphatic polyisocyanates include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

[0132] Examples of aromatic aliphatic polyisocyanates include ω,ω'-diisocyanate-1,3-dimethylbenzene, ω,ω'-diisocyanate-1,4-dimethylbenzene, ω,ω'-diisocyanate-1,4-diethylbenzene, 1,4-tetramethylxylylenediisocyanate, and 1,3-tetramethylxylylenediisocyanate.

[0133] Examples of alicyclic polyisocyanates include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4'-methylenebis(cyclohexyl isocyanate), 1,4-bis(isocyanate methyl)cyclohexane, and 1,4-bis(isocyanate methyl)cyclohexane.

[0134] Organic polyisocyanate compounds such as trimethylolpropane adducts, biuret compounds obtained by reaction with water, and trimers having an isocyanurate ring can also be used in combination.

[0135] Any suitable catalyst can be used to obtain polyurethane polyols. Examples of such catalysts include tertiary amine compounds and organometallic compounds.

[0136] Examples of tertiary amine compounds include triethylamine, triethylenediamine, and 1,8-diazabicyclo[5.4.0]-undecene-7(DBU).

[0137] Examples of organometallic compounds include tin compounds and non-tin compounds.

[0138] Examples of tin-based compounds include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, and tin 2-ethylhexanoate.

[0139] Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, and butoxytitanium trichloride; lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate; iron compounds such as iron 2-ethylhexanoate and iron acetylacetonate; cobalt compounds such as cobalt benzoate and cobalt 2-ethylhexanoate; zinc compounds such as zinc naphthenate and zinc 2-ethylhexanoate; and zirconium compounds such as zirconium naphthenate.

[0140] When using a catalyst to obtain polyurethane polyols, systems containing two types of polyols, polyester polyols and polyether polyols, tend to exhibit problems such as gelation and turbidity of the reaction solution due to their differing reactivity when using a single catalyst. Therefore, using two types of catalysts when obtaining polyurethane polyols makes it easier to control the reaction rate and catalyst selectivity, thereby resolving these issues. Examples of such two-catalyst combinations include tertiary amine / organometallic, tin / non-tin, and tin / tin. Preferably, it is tin / tin, and more preferably a combination of dibutyltin dilaurate and tin 2-ethylhexanoate. The weight ratio of tin 2-ethylhexanoate / dibutyltin dilaurate is preferably less than 1, and more preferably 0.2 to 0.6. A ratio of 1 or more may increase the likelihood of gelation due to the balance of catalytic activity.

[0141] When a catalyst is used to obtain polyurethane polyols, the amount of catalyst used is preferably 0.01 to 1.0% by weight relative to the total amount of polyester polyol, polyether polyol, and organic polyisocyanate compound.

[0142] When a catalyst is used to obtain polyurethane polyols, the reaction temperature is preferably less than 100°C, and more preferably 85°C to 95°C. Above 100°C, it may become difficult to control the reaction rate and crosslinking structure, potentially making it difficult to obtain polyurethane polyols with a predetermined molecular weight.

[0143] A catalyst may not be used to obtain polyurethane polyols. In that case, the reaction temperature is preferably 100°C or higher, and more preferably 110°C or higher. Furthermore, when obtaining polyurethane polyols without a catalyst, it is preferable to allow the reaction to proceed for 3 hours or more.

[0144] Methods for obtaining polyurethane polyols include, for example, 1) a method of charging polyester polyol, polyether polyol, catalyst, and organic polyisocyanate into a volumetric flask, and 2) a method of charging polyester polyol, polyether polyol, and catalyst into a flask and adding organic polyisocyanate dropwise. Method 2) is preferred for controlling the reaction when obtaining polyurethane polyols.

[0145] Any suitable solvent can be used to obtain polyurethane polyols. Examples of such solvents include methyl ethyl ketone, ethyl acetate, toluene, xylene, and acetone. Among these solvents, toluene is preferred.

[0146] As polyfunctional isocyanate compounds, those mentioned above can be used.

[0147] As a method for producing a polyurethane-based composition obtained from a composition containing a urethane prepolymer, any suitable manufacturing method can be adopted, as long as it is a method of producing a polyurethane-based resin composition using a so-called "urethane prepolymer" as a raw material.

[0148] [Acrylic adhesive] The acrylic adhesive is not particularly limited, and known or conventional acrylic adhesives can be used. For example, an acrylic adhesive composition containing an acrylic polymer as a base polymer is recommended because it is easy to control the tackiness.

[0149] The above-mentioned acrylic polymer is a polymer that contains structural units derived from acrylic monomers (monomer components having a (meth)acryloyl group in the molecule) as structural units of the polymer. Preferably, the above-mentioned acrylic polymer is a polymer that contains the largest mass percentage of structural units derived from (meth)acrylic acid ester. Note that only one type of acrylic polymer may be used, or two or more types may be used. In this specification, "(meth)acrylic" means "acrylic" and / or "methacrylic" (either one or both of "acrylic" and "methacrylic"), and the same applies to other terms.

[0150] Examples of the above (meth)acrylic acid esters include hydrocarbon group-containing (meth)acrylic acid esters. Examples of hydrocarbon group-containing (meth)acrylic acid esters include (meth)acrylic acid alkyl esters, (meth)acrylic acid cycloalkyl esters, and (meth)acrylic acid aryl esters. Examples of the above (meth)acrylic acid alkyl esters include (meth)acrylic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, butyl ester, isobutyl ester, s-butyl ester, t-butyl ester, pentyl ester, isopentyl ester, hexyl ester, heptyl ester, octyl ester, 2-ethylhexyl ester, isooctyl ester, nonyl ester, decyl ester, isodecyl ester, undecyl ester, dodecyl ester (lauryl ester), tridecyl ester, tetradecyl ester, hexadecyl ester, octadecyl ester, and eicosyl ester. Examples of the above (meth)acrylic acid cycloalkyl esters include (meth)acrylic acid cyclopentyl ester and cyclohexyl ester. Examples of the above-mentioned aryl (meth)acrylate esters include phenyl esters and benzyl esters of (meth)acrylic acid.

[0151] The hydrocarbon group-containing (meth)acrylic acid ester described above may be used by one type or by two or more types. In order to appropriately exhibit the basic properties such as tackiness due to the hydrocarbon group-containing (meth)acrylic acid ester in the first adhesive layer and to easily control low tackiness, the proportion of hydrocarbon group-containing (meth)acrylic acid ester in the total monomer components for forming the acrylic polymer is preferably 40% by mass or more, and more preferably 60% by mass or more.

[0152] The above acrylic polymer may contain constituent units derived from other monomer components copolymerizable with the hydrocarbon group-containing (meth)acrylic acid ester for the purpose of modifying properties such as cohesiveness, heat resistance, tackiness, etc. Examples of the above other monomer components include carboxyl group-containing monomers, acid anhydride monomers, hydroxyl group-containing monomers, glycidyl group-containing monomers, sulfonic acid group-containing monomers, phosphate group-containing monomers, acrylamide, acrylonitrile and other functional group-containing monomers, vinyl ester monomers, etc. Examples of the above carboxyl group-containing monomers include acrylic acid, methacrylic acid, carboxyethyl (meth)acrylate, carboxypentyl (meth)acrylate, itaconic acid, maleic acid, fumaric acid, crotonic acid, etc. Examples of the above acid anhydride monomers include maleic anhydride, itaconic anhydride, etc. Examples of the above hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, and (4-hydroxymethylcyclohexyl)methyl (meth)acrylate. Examples of the above glycidyl group-containing monomers include glycidyl (meth)acrylate and methylglycidyl (meth)acrylate. Examples of the above sulfonic acid group-containing monomers include styrene sulfonic acid, allyl sulfonic acid, 2-(meth)acrylamide-2-methylpropanesulfonic acid, (meth)acrylamidepropanesulfonic acid, sulfopropyl (meth)acrylate, and (meth)acryloyloxynaphthalenesulfonic acid. Examples of the above phosphate group-containing monomers include 2-hydroxyethyl acryloyl phosphate. Examples of the vinyl ester monomers mentioned above include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl pivalate, vinyl cyclohexanecarboxylate, and vinyl benzoate. The other monomer components may be used individually or in combination of two or more.To appropriately exhibit basic properties such as tackiness due to hydrocarbon group-containing (meth)acrylic acid esters in the first adhesive layer and to easily control low tackiness, the total proportion of the above-mentioned other monomer components in the total monomer components for forming the acrylic polymer is preferably 60% by mass or less, and more preferably 40% by mass or less.

[0153] The above-mentioned acrylic polymer may contain constituent units derived from polyfunctional monomers copolymerizable with monomer components that form the acrylic polymer, in order to form a crosslinked structure within its polymer backbone. Examples of the above-mentioned polyfunctional monomers include monomers having a (meth)acryloyl group and other reactive functional groups in the molecule, such as hexanediol di(meth)acrylate, (poly)ethylene glycol di(meth)acrylate, (poly)propylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, pentaerythritol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, epoxy(meth)acrylate (e.g., polyglycidyl(meth)acrylate), polyester(meth)acrylate, and urethane(meth)acrylate. Only one of the above-mentioned polyfunctional monomers may be used, or two or more may be used. To appropriately exhibit basic properties such as tackiness due to hydrocarbon group-containing (meth)acrylic acid esters in the first adhesive layer and to easily control low tackiness, the proportion of the above polyfunctional monomer in the total monomer components for forming the acrylic polymer is preferably 40% by mass or less, and more preferably 30% by mass or less.

[0154] Acrylic polymers are obtained by polymerizing one or more monomer components, including acrylic monomers. Polymerization methods include solution polymerization, emulsion polymerization, bulk polymerization, and suspension polymerization.

[0155] The mass-average molecular weight of the acrylic polymer is preferably 100,000 or more, and more preferably 200,000 to 3,000,000. When the mass-average molecular weight is 100,000 or more, there tends to be less low molecular weight material in the adhesive layer, which can further suppress contamination of components and other parts.

[0156] The acrylic adhesive composition forming the first adhesive layer may contain a crosslinking agent. For example, the acrylic polymer can be crosslinked to further reduce the amount of low molecular weight substances in the first adhesive layer. It can also increase the mass-average molecular weight of the acrylic polymer and control its tackiness. Examples of the crosslinking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (such as polyphenol compounds), aziridine compounds, and melamine compounds, with isocyanate-based crosslinking agents and / or epoxy-based crosslinking agents being preferred. When using a crosslinking agent, the amount used is preferably about 20 parts by weight or less, and more preferably 0.1 to 15 parts by weight, per 100 parts by weight of the acrylic polymer.

[0157] Examples of isocyanate crosslinking agents include aliphatic isocyanates, alicyclic isocyanates, and aromatic isocyanates. Examples of aliphatic isocyanates include trimethylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, and dimer acid diisocyanate. Examples of alicyclic isocyanates include cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane. Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and xylylene diisocyanate. Other examples of isocyanate-based crosslinking agents include the trimethylolpropane adduct of tolylene diisocyanate (product name "Coronate L", manufactured by Tosoh Corporation) and the isocyanurate derivative of hexamethylene diisocyanate (product name "Coronate HX", manufactured by Tosoh Corporation).

[0158] Examples of epoxy crosslinking agents (polyfunctional epoxy compounds) include N,N,N',N'-tetraglycidyl-m-xylenediamine, diglycidylaniline, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and sorbitol polyglycidyl ether. Examples include diglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylolpropane polyglycidyl ether, diglycidyl adipate ester, diglycidyl o-phthalate ester, triglycidyl-tris(2-hydroxyethyl) isocyanurate, resorcinol diglycidyl ether, and bisphenol-S-diglycidyl ether. Epoxy resins having two or more epoxy groups in their molecules are also included. A commercially available epoxy crosslinking agent is, for example, "Tetrad C" manufactured by Mitsubishi Gas Chemical Company, Inc.

[0159] By including a fatty acid ester in the adhesive composition constituting the first adhesive layer, low tack and wettability of the first adhesive layer to the material can be expected.

[0160] Examples of the aforementioned fatty acid esters include polyoxyethylene bisphenol A laurate, butyl stearate, 2-ethylhexyl palmitate, 2-ethylhexyl stearate, monoglyceride behenic acid, cetyl 2-ethylhexanoate, isopropyl myristate, isopropyl palmitate, cholesteryl isostearate, lauryl methacrylate, methyl coconut fatty acid, methyl laurate, methyl oleate, methyl stearate, myristyl myristate, octyldodecyl myristate, pentaerythritol monooleate, pentaerythritol monostearate, pentaerythritol tetrapalmitate, stearyl stearate, isotridecyl stearate, triglyceride 2-ethylhexanoate, butyl laurate, octyl oleate, and tridecyl isononanoate. The fatty acid ester may be one type or two or more types.

[0161] The amount of fatty acid ester contained in the urethane-based adhesive composition is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight, and even more preferably 3 to 30 parts by weight, per 100 parts by weight of polyol, from the viewpoint of low tackiness, wettability, and staining of the material of the first adhesive layer.

[0162] The first adhesive layer may contain an ultraviolet absorber. When the first adhesive layer contains an ultraviolet absorber, discoloration caused by irradiation with active energy rays can be suppressed. Therefore, when processing a member temporarily fixed to the first adhesive layer using irradiation with active energy rays such as laser light, discoloration of the adhesive sheet can be prevented.

[0163] The UV absorber is not particularly limited, but examples include triazine-based UV absorbers, benzotriazole-based UV absorbers, benzophenone-based UV absorbers, oxybenzophenone-based UV absorbers, salicylic acid ester-based UV absorbers, and cyanoacrylate-based UV absorbers, and these can be used individually or in combination of two or more. Among these, triazine-based UV absorbers and benzotriazole-based UV absorbers are preferred, and it is preferable that at least one UV absorber is selected from the group consisting of triazine-based UV absorbers having two or fewer hydroxyl groups in one molecule and benzotriazole-based UV absorbers having one benzotriazole skeleton in one molecule, because they have good solubility in monomers used to form acrylic adhesive compositions and have high UV absorption capacity around a wavelength of 380 nm.

[0164] Triazine-based UV absorbers having two or fewer hydroxyl groups in one molecule include, specifically, 2,4-bis-[{4-(4-ethylhexyloxy)-4-hydroxy}-phenyl]-6-(4-methoxyphenyl)-1,3,5-triazine (Tinosorb S, manufactured by BASF), 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine (TINUVIN 460, manufactured by BASF), and 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5-hydroxyphenyl and [(C 10 -C 16 (mainly C 12 -C 13Reaction product with alkyloxy)methyl]oxirane (TINUVIN400, BASF), 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol), reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis-(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester (TINUVIN405, BASF), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[(hexyl)oxy]-phenol (TINUVIN1577, BASF), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]-phenol (ADK STAB Examples include LA46 (manufactured by ADEKA) and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine (TINUVIN479, manufactured by BASF).

[0165] Furthermore, examples of benzotriazole-based UV absorbers having one benzotriazole skeleton in one molecule include 2-(2H-benzotriazole-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN 928, manufactured by BASF), 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole (TINUVIN PS, manufactured by BASF), benzenepropanoic acid, and 3-(2H-benzotriazole-2-yl)-5-(1,1-dimethylethyl)-4-hydroxy(C 7-9Ester compounds of side chains and linear alkyls (TINUVIN384-2, BASF), 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN900, BASF), 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN928, BASF), reaction product of methyl-3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 (TINUVIN1130, BASF), 2-(2H-benzotriazol-2-yl)-p-cresol (TINUVIN P (manufactured by BASF), 2(2H-benzotriazol-2-yl)-4-6-bis(1-methyl-1-phenylethyl)phenol (TINUVIN234, manufactured by BASF), 2-[5-chloro(2H)-benzotriazol-2-yl]-4-methyl-6-(tert-butyl)phenol (TINUVIN326, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4,6-di-tert-pentylphenol (TINUVIN328, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol (TINUVIN234, manufactured by BASF). Examples include N329 (manufactured by BASF), reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate and polyethylene glycol 300 (TINUVIN 213, manufactured by BASF), 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methylphenol (TINUVIN 571, manufactured by BASF), and 2-[2-hydroxy-3-(3,4,5,6-tetrahydrophthalimidomethyl)-5-methylphenyl]benzotriazole (Sumisorb 250, manufactured by Sumitomo Chemical Co., Ltd.).

[0166] Furthermore, examples of the benzophenone-based ultraviolet absorbers (benzophenone compounds) and oxybenzophenone-based ultraviolet absorbers (oxybenzophenone compounds) include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid (anhydrous and trihydrate), 2-hydroxy-4-octyloxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 4-benzyloxy-2-hydroxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2,2'-dihydroxy-4,4-dimethoxybenzophenone.

[0167] Examples of the salicylic acid ester-based ultraviolet absorbers (salicylic acid ester compounds) include phenyl-2-acryloyloxybenzoate, phenyl-2-acryloyloxy-3-methylbenzoate, phenyl-2-acryloyloxy-4-methylbenzoate, phenyl-2-acryloyloxy-5-methylbenzoate, phenyl-2-acryloyloxy-3-methoxybenzoate, phenyl-2-hydroxybenzoate, phenyl-2-hydroxy-3-methylbenzoate, phenyl-2-hydroxy-4-methylbenzoate, phenyl-2-hydroxy-5-methylbenzoate, phenyl-2-hydroxy-3-methoxybenzoate, and 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate (TINUVIN120, manufactured by BASF).

[0168] Examples of the cyanoacrylate-based ultraviolet absorbers (cyanoacrylate compounds) include alkyl-2-cyanoacrylate, cycloalkyl-2-cyanoacrylate, alkoxyalkyl-2-cyanoacrylate, alkenyl-2-cyanoacrylate, and alkynyl-2-cyanoacrylate.

[0169] The maximum absorption wavelength in the absorption spectrum of the UV absorber is preferably in the wavelength region of 300 to 400 nm, and more preferably in the wavelength region of 320 to 380 nm.

[0170] The UV absorber may be used alone or in a mixture of two or more types. From the viewpoint of preventing discoloration due to irradiation with active energy rays, the amount of UV absorber contained in the adhesive composition is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight per 100 parts by weight of the adhesive composition.

[0171] The first adhesive layer may contain an antioxidant. When the first adhesive layer contains an antioxidant, deterioration such as discoloration of the adhesive sheet of this embodiment during storage can be suppressed.

[0172] Examples of the aforementioned antioxidants include phenolic, phosphorus-based, sulfur-based, and amine-based antioxidants, and at least one selected from these is used. Among these, phenolic antioxidants are preferred, and hindered phenolic antioxidants are particularly preferred.

[0173] Specific examples of phenolic antioxidants include monocyclic phenol compounds such as 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-t-amyl-4-methylphenol, 2,6-di-t-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4-n-octylphenol, 2-isopropyl-4-methyl-6-t-butylphenol, 2-t-butyl-4-ethyl-6-t-octylphenol, 2-isobutyl-4-ethyl-6-t-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, styrene-mixed cresol, DL-α-tocopherol, and stearyl β-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, which are bicyclic phenolic compounds. Examples of phenolic compounds include 2,2'-methylenebis(4-methyl-6-t-butylphenol), 4,4'-butylidenebis(3-methyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol), 2,2'-thiobis(4-methyl-6-t-butylphenol), 4,4'-methylenebis(2,6-di-t-butylphenol), and 2,2'-methylenebis[6-(1-methylcyclohexyl )-p-cresol], 2,2'-ethylidenebis(4,6-di-t-butylphenol), 2,2'-butylidenebis(2-t-butyl-4-methylphenol), 3,6-dioxaoctamethylenebis[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionate], triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol Bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,2'-thiodiethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], etc., as tri-ring phenol compounds, 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-t-butylbenzyl)isocyanurate, 1,3,5-tris[(3,Examples of tetracyclic phenolic compounds include 5-di-t-butyl-4-hydroxyphenyl)propionyloxyethyl isocyanurate, tris(4-t-butyl-2,6-dimethyl-3-hydroxybenzyl)isocyanurate, and 1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene; tetracyclic phenolic compounds include tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane; and phosphorus-containing phenolic compounds include bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)calcium and bis(3,5-di-t-butyl-4-hydroxybenzylphosphonate ethyl)nickel.

[0174] The antioxidant may be used alone or in a mixture of two or more. From the viewpoint of suppressing deterioration such as discoloration during storage and the processability of the adhesive sheet, the amount of antioxidant contained in the adhesive composition is preferably 0.01 to 10 parts by weight, more preferably 0.03 to 5 parts by weight, and even more preferably 0.1 to 3 parts by weight per 100 parts by weight of the adhesive composition.

[0175] The adhesive composition constituting the first adhesive layer may contain any other suitable components as long as they do not impair the effects of the present invention. Examples of such other components include tackifiers, inorganic fillers, organic fillers, metal powders, pigments, foils, softeners, plasticizers, conductive agents, surface lubricants, leveling agents, heat stabilizers, polymerization inhibitors, lubricants, solvents, and the like.

[0176] [Second adhesive layer] The second adhesive layer is an adhesive layer for fixing to the support plate, and it is preferable that it consists of a release adhesive layer. The configuration in which the second adhesive layer consists of a release adhesive layer is preferable because it allows the second adhesive layer to be peeled off from the support plate without contamination such as adhesive residue, thereby improving reworkability. The second adhesive layer can be made into a release adhesive layer by adjusting its tackiness through the type and composition of the adhesive, the degree of crosslinking, etc., or by reducing its tackiness through physical stimuli such as heat, ultraviolet rays, or other electromagnetic waves.

[0177] The 180° peel-off adhesive strength of the second adhesive layer to the glass plate at 25°C is not particularly limited, but it is preferably 5000mN / 25mm or less, more preferably 3000mN / 25mm or less, and even more preferably 1000mN / 25mm or less, from the viewpoint of being able to peel it off from the support plate without contamination such as adhesive residue, and from the viewpoint of improving reworkability. Furthermore, from the viewpoint of adhesion of the support plate to the second adhesive layer, the 180° peel-off adhesive strength of the second adhesive layer to the glass plate at 25°C is preferably 1mN / 25mm or more, and more preferably 5mN / 25mm or more.

[0178] The adhesive strength of the second adhesive layer can be adjusted by adjusting the type and composition of the adhesive, the degree of crosslinking, etc., or by forming a Weak Boundary Layer (WBL) by incorporating a plasticizer.

[0179] The thickness of the second adhesive layer is not particularly limited, but is preferably 1 μm or more, and more preferably 3 μm or more. A thickness above a certain level is preferable because it makes it easier for the second adhesive layer to be stably fixed to the support plate. Furthermore, the upper limit of the thickness of the second adhesive layer is not particularly limited, but is preferably 30 μm or less, and more preferably 20 μm or less. A thickness below a certain level makes it easier to peel the second adhesive layer from the support plate, improving reworkability, which is preferable.

[0180] The haze of the second adhesive layer (according to JIS K7136) is not particularly limited, but is preferably 10% or less, and more preferably 5% or less. A haze of 10% or less is preferable because it provides excellent transparency, for example, improving the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment. The haze can be measured, for example, by forming the second adhesive layer on a release liner, leaving it at normal conditions (23°C, 50%RH) for at least 24 hours, peeling off the release liner, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and a haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0181] In the adhesive sheet of this embodiment, the total light transmittance of the second adhesive layer in the visible light wavelength range (according to JIS K7361-1) is not particularly limited, but is preferably 85% or more, and more preferably 88% or more. A total light transmittance of 85% or more is preferable because it provides excellent transparency, for example, improving the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment. The total light transmittance can be measured, for example, by forming the second adhesive layer on a release liner, leaving it at normal conditions (23°C, 50%RH) for at least 24 hours, peeling off the release liner, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0182] The adhesive constituting the second adhesive layer described above is not particularly limited, but examples include silicone-based adhesives, urethane-based adhesives, acrylic-based adhesives, rubber-based adhesives, polyester-based adhesives, polyamide-based adhesives, epoxy-based adhesives, vinyl alkyl ether-based adhesives, and fluorine-based adhesives, which are used in the first adhesive layer described above. Among these, silicone-based adhesives, urethane-based adhesives, and acrylic-based adhesives are preferred from the viewpoint of being able to be peeled off from the support plate without contamination such as adhesive residue, improving reworkability, and having high transparency and good visibility of alignment marks, with urethane-based adhesives and acrylic-based adhesives being more preferred, and acrylic-based adhesives being even more preferred.

[0183] The second adhesive layer may be an adhesive layer that can be intentionally reduced by external forces during the use of the adhesive sheet of this embodiment (adhesive force reduction type adhesive layer), or it may be an adhesive layer that does not have its adhesive force reduced by external forces during the use of the adhesive sheet (adhesive force non-reduction type adhesive layer), and can be appropriately selected depending on the method and conditions for processing the component using the adhesive sheet of this embodiment.

[0184] If the second adhesive layer is a type of adhesive layer whose adhesive strength can be reduced, it becomes possible to switch between a state in which the second adhesive layer exhibits relatively high adhesive strength and a state in which it exhibits relatively low adhesive strength during the manufacturing and usage processes of the adhesive sheet of this embodiment. For example, in the process of the first adhesive layer receiving a component during the usage process of the adhesive sheet of this embodiment, it is possible to suppress and prevent the adhesive sheet from lifting off the support plate by utilizing the state in which the second adhesive layer exhibits relatively high adhesive strength. On the other hand, in the subsequent process of peeling the adhesive sheet of this embodiment from the support plate, the reworkability can be improved by reducing the adhesive strength of the second adhesive layer.

[0185] Examples of adhesives that form such a tack-reducing adhesive layer include radiation-curable adhesives and heat-foaming adhesives. One type of adhesive may be used to form the tack-reducing adhesive layer, or two or more types of adhesives may be used.

[0186] As the above-mentioned radiation-curable adhesive, for example, an adhesive that hardens upon irradiation with electron beams, ultraviolet rays, alpha rays, beta rays, gamma rays, or X-rays can be used, and an adhesive that hardens upon irradiation with ultraviolet rays (ultraviolet-curable adhesive) can be used in particular preference.

[0187] Examples of the above-mentioned radiation-curable adhesives include additive-type radiation-curable adhesives containing a base polymer such as an acrylic polymer and radiation-polymerizable monomer components or oligomer components having radiation-polymerizable functional groups such as carbon-carbon double bonds.

[0188] As the base polymer, an acrylic polymer similar to that used in the first adhesive layer can be used. To appropriately express the basic properties such as tackiness due to hydrocarbon group-containing (meth)acrylic acid ester in the second adhesive layer, and to easily control tackiness and peelability, the proportion of hydrocarbon group-containing (meth)acrylic acid ester in the total monomer components for forming the acrylic polymer is preferably 40% by mass or more, and more preferably 60% by mass or more.

[0189] The above-mentioned acrylic polymer may contain a hydroxyl group-containing monomer. When the acrylic polymer in the second adhesive layer contains a hydroxyl group-containing monomer, an appropriate cohesive force is easily obtained in the second adhesive layer. From the viewpoint of achieving appropriate adhesion and cohesive force in the second adhesive layer, the proportion of the hydroxyl group-containing monomer in the above-mentioned acrylic polymer is, for example, 0.1 to 30% by mass, and preferably 0.5 to 20% by mass.

[0190] The above-mentioned acrylic polymer may contain a carboxyl group-containing monomer. When the acrylic polymer in the second adhesive layer contains a carboxyl group-containing monomer, it is easier to obtain adequate adhesive reliability in the second adhesive layer. From the viewpoint of achieving adequate adhesive reliability in the second adhesive layer, the proportion of the carboxyl group-containing monomer in the above-mentioned acrylic polymer is, for example, 0.1 to 30% by mass, and preferably 0.5 to 20% by mass.

[0191] The above-mentioned acrylic polymer may also contain a vinyl ester monomer. When the acrylic polymer in the second adhesive layer contains a vinyl ester monomer, an appropriate cohesive force is easily obtained in the second adhesive layer. From the viewpoint of achieving an appropriate cohesive force in the second adhesive layer, the proportion of the vinyl ester monomer in the above-mentioned acrylic polymer is, for example, 0.1 to 60% by mass, and preferably 0.5 to 50% by mass.

[0192] The acrylic adhesive composition forming the second adhesive layer may contain a crosslinking agent. For example, the acrylic polymer can be crosslinked to further reduce the amount of low molecular weight substances in the second adhesive layer. It can also increase the mass-average molecular weight of the acrylic polymer and control its release properties. Examples of the crosslinking agent include polyisocyanate compounds, epoxy compounds, polyol compounds (such as polyphenol compounds), aziridine compounds, and melamine compounds. When using an isocyanate-based crosslinking agent and / or an epoxy-based crosslinking agent, the amount used is preferably about 10 parts by weight or less, and more preferably 0.1 to 10 parts by weight, per 100 parts by weight of the acrylic polymer.

[0193] The acrylic adhesive composition forming the second adhesive layer may contain a crosslinking accelerator. The type of crosslinking accelerator can be appropriately selected depending on the type of crosslinking agent used. In this specification, a crosslinking accelerator refers to a catalyst that increases the rate of the crosslinking reaction by the crosslinking agent. Examples of such crosslinking accelerators include tin (Sn)-containing compounds such as dioctyl tin dilaurate, dibutyl tin dilaurate, dibutyl tin diacetate, dibutyl tin diacetylacetonate, tetra-n-butyl tin, and trimethyl tin hydroxide; amines such as N,N,N',N'-tetramethylhexanediamine and triethylamine; and N-containing compounds such as imidazoles. Among these, Sn-containing compounds are preferred. The use of these crosslinking accelerators is particularly effective when a hydroxyl group-containing monomer is used as the sub-monomer and an isocyanate-based crosslinking agent is used as the crosslinking agent. The amount of crosslinking accelerator contained in the above adhesive composition can be, for example, about 0.001 to 0.5 parts by weight (preferably about 0.001 to 0.1 parts by weight) per 100 parts by weight of the acrylic polymer.

[0194] Examples of the above radiation-polymerizable monomer components include urethane (meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and 1,4-butanediol di(meth)acrylate. Examples of the above radiation-polymerizable oligomer components include various oligomers such as urethane-based, polyether-based, polyester-based, polycarbonate-based, and polybutadiene-based oligomers, with a molecular weight of approximately 100 to 30,000 being preferred. The content of the above radiation-curable monomer components and oligomer components in the radiation-curable adhesive forming the second adhesive layer is, for example, 5 to 500 parts by weight, preferably 40 to 150 parts by weight, per 100 parts by weight of the base polymer. Furthermore, as an additive-type radiation-curable adhesive, for example, the one disclosed in Japanese Patent Publication No. 60-196956 may be used.

[0195] The above-mentioned radiation-curable adhesives also include intrinsically charged radiation-curable adhesives containing a base polymer having radiation-polymerizable functional groups such as carbon-carbon double bonds in the polymer side chains, polymer main chain, or polymer main chain ends. Using such intrinsically charged radiation-curable adhesives tends to suppress unintended changes in adhesive properties over time caused by the movement of low molecular weight components within the formed second adhesive layer.

[0196] As the base polymer contained in the above-mentioned intrinsically charged radiation-curable adhesive, an acrylic polymer is preferred. As a method for introducing a radiation-polymerizable carbon-carbon double bond into an acrylic polymer, for example, an acrylic polymer is obtained by polymerizing (copolymerizing) a raw material monomer containing a monomer component having a first functional group, and then a compound having a second functional group that can react with the first functional group and a radiation-polymerizable carbon-carbon double bond is subjected to a condensation or addition reaction with the acrylic polymer while maintaining the radiation polymerizability of the carbon-carbon double bond.

[0197] Examples of combinations of the first functional group and the second functional group include carboxyl group and epoxy group, epoxy group and carboxyl group, carboxyl group and aziridyl group, aziridyl group and carboxyl group, hydroxyl group and isocyanate group, and isocyanate group and hydroxyl group. Among these, from the viewpoint of ease of reaction tracking, combinations of hydroxyl group and isocyanate group, and combinations of isocyanate group and hydroxyl group are preferred. In particular, producing polymers having highly reactive isocyanate groups is technically difficult, while from the viewpoint of ease of production and acquisition of acrylic polymers having hydroxyl groups, a combination in which the first functional group is a hydroxyl group and the second functional group is an isocyanate group is preferred. Examples of compounds having an isocyanate group and a radioactively polymerizable carbon-carbon double bond, i.e., radioactively polymerizable unsaturated functional group-containing isocyanate compounds, include methacryloyl isocyanate, 2-methacryloyloxyethyl isocyanate, and m-isopropenyl-α,α-dimethylbenzyl isocyanate. Furthermore, examples of acrylic polymers having hydroxyl groups include those containing the above-mentioned hydroxyl group-containing monomers, as well as constituent units derived from ether compounds such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether.

[0198] The above radiation-curable adhesive preferably contains a photopolymerization initiator. Examples of the above photopolymerization initiator include α-ketol compounds, acetophenone compounds, benzoin ether compounds, ketal compounds, aromatic sulfonyl chloride compounds, photoactive oxime compounds, benzophenone compounds, thioxanthone compounds, camphorquinone, halogenated ketones, acylphosphinoxides, and acylphosphonates. Examples of the above α-ketol compounds include 4-(2-hydroxyethoxy)phenyl(2-hydroxy-2-propyl)ketone, α-hydroxy-α,α'-dimethylacetophenone, 2-methyl-2-hydroxypropiophenone, and 1-hydroxycyclohexylphenyl ketone. Examples of the above acetophenone compounds include methoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, and 2-methyl-1-[4-(methylthio)-phenyl]-2-morpholinopropane-1. Examples of the above benzoin ether compounds include benzoin ethyl ether, benzoin isopropyl ether, and anisoin methyl ether. Examples of the above ketal compounds include benzyldimethyl ketal. Examples of the above aromatic sulfonyl chloride compounds include 2-naphthalenesulfonyl chloride. Examples of the above photoactive oxime compounds include 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime. Examples of the above benzophenone compounds include benzophenone, benzoylbenzoic acid, and 3,3'-dimethyl-4-methoxybenzophenone. Examples of the thioxanthone compounds mentioned above include thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone, and 2,4-diisopropylthioxanthone. The content of the photopolymerization initiator in the radiation-curable adhesive is, for example, 0.05 to 20 parts by weight per 100 parts by weight of the base polymer.

[0199] The above-mentioned heat-foaming adhesive is an adhesive containing components (foaming agents, thermally expandable microspheres, etc.) that foam or expand upon heating. Examples of the foaming agents include various inorganic and organic foaming agents. Examples of the inorganic foaming agents include ammonium carbonate, ammonium bicarbonate, sodium bicarbonate, ammonium nitrite, sodium borohydride, and azides. Examples of the above-mentioned organic blowing agents include salt fluoride alkanes such as trichloromonofluoromethane and dichloromonofluoromethane; azo compounds such as azobisisobutyronitrile, azodicarbonamide, and barium azodicarboxylate; hydrazine compounds such as p-toluenesulfonyl hydrazide, diphenylsulfon-3,3'-disulfonyl hydrazide, 4,4'-oxybis(benzenesulfonyl hydrazide), and allylbis(sulfonyl hydrazide); semicarbazide compounds such as p-toluenesulfonyl semicarbazide and 4,4'-oxybis(benzenesulfonyl semicarbazide); triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole; and N-nitroso compounds such as N,N'-dinitrosopentamethylenetetramine and N,N'-dimethyl-N,N'-dinitrosotelephthalamide. Examples of the above-mentioned thermally expandable microspheres include microspheres in which a substance that readily gasifies and expands upon heating is enclosed within the shell. Examples of substances that readily gasifies and expand upon heating include isobutane, propane, and pentane. Thermally expandable microspheres can be produced by enclosing a substance that readily gasifies and expands upon heating within a shell-forming material using methods such as coacervation or interfacial polymerization. As the shell-forming material, substances that exhibit thermal fusion or substances that can rupture due to the thermal expansion of the enclosed material can be used. Examples of such substances include vinylidene chloride-acrylonitrile copolymer, polyvinyl alcohol, polyvinyl butyral, polymethyl methacrylate, polyacrylonitrile, polyvinylidene chloride, and polysulfone.

[0200] Examples of the non-reducing adhesive layer mentioned above include a pressure-sensitive adhesive layer. The pressure-sensitive adhesive layer includes an adhesive layer formed from the radiation-curable adhesive described above, which is pre-cured by radiation irradiation while maintaining a certain level of adhesion. The adhesive forming the non-reducing adhesive layer may be one type of adhesive or two or more types of adhesives. Furthermore, the entire second adhesive layer may be a non-reducing adhesive layer, or only a portion of it may be a non-reducing adhesive layer. For example, if the second adhesive layer has a single-layer structure, the entire second adhesive layer may be a non-reducing adhesive layer, or a specific portion of the second adhesive layer may be a non-reducing adhesive layer while other portions are adhesive layers with reduced adhesion. Also, if the second adhesive layer has a laminated structure, all adhesive layers in the laminated structure may be non-reducing adhesive layers, or some adhesive layers in the laminated structure may be non-reducing adhesive layers.

[0201] An adhesive layer formed from a radiation-curable adhesive (a radiation-curable adhesive layer that has not been irradiated) and then cured in advance by radiation (a radiation-irradiated radiation-curable adhesive layer) exhibits tackiness due to the polymer components it contains, even if its tackiness is reduced by radiation, and is capable of exhibiting the minimum tackiness required for the adhesive sheet of this embodiment. When using a radiation-irradiated radiation-curable adhesive layer, the entire second adhesive layer may be a radiation-irradiated radiation-curable adhesive layer in the direction of surface expansion of the second adhesive layer, or a part of the second adhesive layer may be a radiation-irradiated radiation-curable adhesive layer and the other part may be an unirradiated radiation-curable adhesive layer. In this specification, "radiation-curable adhesive layer" refers to an adhesive layer formed from a radiation-curable adhesive, and includes both a radiation-curable unirradiated radiation-curable adhesive layer and a radiation-cured radiation-curable adhesive layer after the adhesive layer has been cured by radiation.

[0202] As the adhesive forming the pressure-sensitive adhesive layer described above, known or conventional pressure-sensitive adhesives can be used, and acrylic adhesives with an acrylic polymer as the base polymer are preferably used. When the second adhesive layer contains an acrylic polymer as a pressure-sensitive adhesive, it is preferable that the acrylic polymer is a polymer in which the constituent units derived from (meth)acrylic acid ester are the most abundant by mass. As the acrylic polymer described above, for example, an acrylic polymer that can be included in the additive-type radiation-curable adhesive described above can be used.

[0203] [Base material] In this embodiment, when the adhesive sheet is an adhesive sheet with a substrate, the substrate is an element that functions as a support. Examples of substrates include plastic substrates (particularly plastic films). The substrate may be a single layer or a laminate of the same or different types of substrates.

[0204] Examples of resins constituting the above-mentioned plastic substrates include polyolefin resins such as low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, ultra-low-density polyethylene, random copolymer polypropylene, block copolymer polypropylene, homopolypropylene, polybutene, polymethylpentene, ethylene-vinyl acetate copolymer (EVA), ionomer, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester (random, alternating) copolymer, ethylene-butene copolymer, and ethylene-hexene copolymer; polyurethane; polyesters such as polyethylene terephthalate (PET), polyethylene naphthalate, and polybutylene terephthalate (PBT); polycarbonate; polyimide; polyether ether ketone; polyetherimide; polyamides such as aramid and fully aromatic polyamide; polyphenyl sulfide; fluororesin; polyvinyl chloride; polyvinylidene chloride; cellulose resin; silicone resin; and cellulose triacetate (TAC). When the adhesive sheet of this embodiment is subjected to processing involving heating, such as thermocompression (e.g., 150°C) to transfer and mount the received component onto a mounting substrate, the substrate preferably contains a heat-resistant resin such as polyimide (PI), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyamide (PA), or polyetheretherketone (PEEK) as its main component, and more preferably contains polyimide as its main component. Furthermore, when processing a member temporarily fixed on the adhesive sheet of this embodiment using active energy ray irradiation such as laser light irradiation, polyimide (PI), polyethylene terephthalate (PET), cellulose triacetate (TAC), etc., which exhibit ultraviolet absorption properties, are also preferable from the viewpoint of preventing discoloration of the adhesive sheet. Furthermore, the main component of the base material is defined as the component that accounts for the largest mass proportion among the constituent components. The above resin may be used by one type only, or by two or more types.

[0205] When the base material is a plastic film, the plastic film may be unoriented or oriented in at least one direction (uniaxial direction, biaxial direction, etc.), but unoriented is preferred because it is less likely to exhibit thermal shrinkage.

[0206] The surface of the substrate facing the first adhesive layer and / or the second adhesive layer may be subjected to surface treatments such as physical treatments like corona discharge treatment, plasma treatment, sandblasting, ozone exposure treatment, flame exposure treatment, high-voltage electric shock exposure treatment, and ionization radiation treatment; chemical treatments like chromic acid treatment; coating agents (primers); and easy-adhesion treatments using silicone primers, in order to improve adhesion and retention with the adhesive layer. In addition, to impart antistatic properties, a conductive vapor-deposited layer containing metals, alloys, or oxides thereof may be provided on the substrate surface, or a conductive polymer such as PEDOT-PSS may be coated. It is preferable that the surface treatment to improve adhesion is applied to the entire surface of the substrate facing the adhesive layer.

[0207] From the viewpoint of ensuring sufficient strength for the substrate to function as a support in the adhesive sheet of this embodiment, the thickness of the substrate is preferably 5 μm or more, more preferably 10 μm or more, even more preferably 15 μm or more, and particularly preferably 20 μm or more. Furthermore, from the viewpoint of achieving appropriate flexibility in the adhesive sheet of this embodiment, the thickness of the substrate is preferably 200 μm or less, more preferably 180 μm or less, and even more preferably 150 μm or less.

[0208] In the adhesive sheet of this embodiment, the haze of the substrate (according to JIS K7136) is not particularly limited, but is preferably 10% or less, and more preferably 5.0% or less. When the haze is 10% or less, excellent transparency is obtained, and for example, the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment is improved, which is preferable. The above haze can be measured using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0209] In the adhesive sheet of this embodiment, the total light transmittance of the substrate in the visible light wavelength range (according to JIS K7361-1) is not particularly limited, but is preferably 85% or higher, and more preferably 88% or higher. A total light transmittance of 85% or higher is preferable because it provides excellent transparency, for example, improving the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment. The total light transmittance can be measured using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0210] In the adhesive sheet of this embodiment, the substrate may contain the color-changing component of the present invention. That is, the substrate may contain a compound that changes color upon reaction with an acid, an acid generator, and optionally a base generator, and may change color upon external stimuli to form alignment marks. Alternatively, the substrate may contain a compound that decolorizes upon reaction with a base, and a base generator, or a photochromic compound, and may change color upon external stimuli to form alignment marks.

[0211] The compound that changes color upon reaction with acid is preferably in an amount of 0.01 to 30 parts by weight, more preferably 0.1 to 30 parts by weight, even more preferably 0.1 to 20 parts by weight, and still more preferably 1 to 10 parts by weight per 100 parts by weight of the substrate. Within this range, alignment marks can be efficiently formed by the color change caused by the compound that changes color upon reaction with acid.

[0212] The acid generator is preferably in an amount of 0.001 to 30 parts by weight per 100 parts by weight of the base material, more preferably 0.01 to 25 parts by weight, even more preferably 0.1 to 30 parts by weight, and still more preferably 0.1 to 20 parts by weight. Within these ranges, acid can be efficiently generated by irradiation with active energy rays or heating, and alignment marks can be efficiently formed by discoloration caused by a compound that changes color upon reaction with the acid.

[0213] The amount of base generating agent is preferably 0.001 to 30 parts by weight, more preferably 0.01 to 25 parts by weight, and even more preferably 0.1 to 20 parts by weight per 100 parts by weight of the substrate. Within this range, bases can be efficiently generated by active energy ray irradiation or heating, enabling the decolorization of alignment marks.

[0214] The amount of photochromic compounds that decolorize upon reaction with a base in the substrate is the same as that of the compounds that change color upon reaction with an acid.

[0215] [Removable Liner] The adhesive layer surface of the adhesive sheet of the present invention (the adhesive surface of the first adhesive layer and / or the second adhesive layer) may be protected by a release liner until use. The release liner is used as a protective material for the adhesive layer and is peeled off when the adhesive sheet is attached to the substrate. Note that the release liner is not necessarily required.

[0216] As the above-mentioned release liner, conventional release paper can be used. Specifically, for example, in addition to a substrate having a release treatment layer with a release treatment agent on at least one surface, low-adhesion substrates made of fluorine-based polymers (e.g., polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinyl fluoride, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropropylene copolymer, chlorofluoroethylene-vinylidene fluoride copolymer, etc.) or low-adhesion substrates made of non-polar polymers (e.g., polyethylene, polypropylene, and other olefin resins) can be used.

[0217] As the above-mentioned peel-off liner, for example, a peel-off liner having a release treatment layer formed on at least one surface of the peel-off liner substrate can be suitably used. Examples of such peel-off liner substrates include plastic substrate films (synthetic resin films) such as polyester film (polyethylene terephthalate film, etc.), olefin resin film (polyethylene film, polypropylene film, etc.), polyvinyl chloride film, polyimide film, polyamide film (nylon film), and rayon film, as well as paper (high-quality paper, Japanese paper, kraft paper, glassine paper, synthetic paper, topcoat paper, etc.), and composites of these made by laminating or co-extrusion (2-3 layer composites).

[0218] The release agent constituting the above-mentioned release layer is not particularly limited, but for example, silicone-based release agents, fluorine-based release agents, long-chain alkyl-based release agents, etc., can be used. The release agent can be used alone or in combination of two or more types.

[0219] To prevent adverse effects on the component, the above-mentioned peel-off liner may have an antistatic layer formed on at least one surface of the peel-off liner substrate. The antistatic layer may be formed on one surface of the peel-off liner (the peel-off treated surface or the untreated surface), or on both surfaces of the peel-off liner (the peel-off treated surface and the untreated surface).

[0220] Examples of antistatic agents contained in the antistatic resin forming the antistatic layer include cationic antistatic agents having cationic functional groups such as quaternary ammonium salts, pyridinium salts, and primary, secondary, and tertiary amino groups; anionic antistatic agents having anionic functional groups such as sulfonates, sulfate esters, phosphonates, and phosphate esters; amphoteric antistatic agents such as alkyl betaines and their derivatives, imidazolines and their derivatives, and alanine and its derivatives; nonionic antistatic agents such as amino alcohols and their derivatives, glycerin and its derivatives, and polyethylene glycol and its derivatives; and ion-conductive polymers obtained by polymerizing or copolymerizing monomers having the above-mentioned cationic, anionic, and amphoteric ion-conductive groups. These compounds may be used individually or in combination of two or more.

[0221] The thickness of the release liner is not particularly limited and can be appropriately selected from the range of 5 to 100 μm.

[0222] The method for preparing (manufacturing) the adhesive sheet of this embodiment varies depending on the composition of the adhesive composition, etc., and is not particularly limited; known forming methods can be used, but examples include the following methods (1) to (4). (1) A method for manufacturing an adhesive sheet by applying (coating) the above adhesive composition onto a substrate to form a composition layer, and curing the composition layer (for example, by heat curing or curing by irradiation with active energy rays such as ultraviolet light) to form an adhesive layer. (2) A method for producing an adhesive sheet by applying the above adhesive composition onto a release liner to form a composition layer, curing the composition layer (for example, by heat curing or curing by irradiation with active energy rays such as ultraviolet light) to form an adhesive layer, and then transferring the adhesive layer onto a substrate. (3) A method for producing an adhesive sheet by applying the above adhesive composition onto a substrate, drying it to form an adhesive layer. (4) A method for producing an adhesive sheet by applying the above adhesive composition onto a release liner, drying it to form an adhesive layer, and then transferring the adhesive layer onto a substrate.

[0223] Of the curing methods described in (1) to (4) above, a heat curing method is preferred because it offers excellent productivity and allows for the formation of a homogeneous and smooth-surfaced adhesive layer.

[0224] The method for applying (coating) the above adhesive composition onto a predetermined surface can be any known coating method, and is not particularly limited. Examples include roll coating, kiss roll coating, gravure coating, reverse coating, roll brushing, spray coating, dip roll coating, bar coating, knife coating, air knife coating, curtain coating, lip coating, and extrusion coating methods using a die coater.

[0225] The thickness (total thickness) of the adhesive sheet in this embodiment is not particularly limited, but is preferably 10 μm or more, and more preferably 15 μm or more. A thickness above a certain level is preferable because it makes it easier to stably temporarily fix the member to the first adhesive layer. Furthermore, the upper limit of the thickness (total thickness) of the adhesive sheet in this embodiment is not particularly limited, but is preferably 500 μm or less, and more preferably 300 μm or less. A thickness below a certain level is preferable because it makes it easier to accurately temporarily fix the member to the first adhesive layer. Note that the thickness of the adhesive sheet in this embodiment does not include the thickness of the release liner.

[0226] The haze of the adhesive sheet of this embodiment (according to JIS K7136) is not particularly limited, but is preferably 10% or less, and more preferably 5.0% or less. A haze of 10% or less is preferable because it provides excellent transparency, for example, improving the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment. The haze can be measured, for example, by leaving the adhesive sheet at room temperature (23°C, 50%RH) for at least 24 hours, peeling off the release liner if present, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and a haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0227] The total light transmittance (according to JIS K7361-1) of the adhesive sheet of this embodiment in the visible light wavelength range is not particularly limited, but is preferably 85% or higher, and more preferably 88% or higher. A total light transmittance of 85% or higher is preferable because it provides excellent transparency, for example, improving the visibility of alignment marks formed by applying external stimuli to the adhesive sheet of this embodiment. The total light transmittance can be measured, for example, by leaving the adhesive sheet at room temperature (23°C, 50%RH) for at least 24 hours, peeling off the release liner if one is present, and attaching the sample to a glass slide (for example, one with a total light transmittance of 91.8% and haze of 0.4%), using a haze meter (manufactured by Murakami Color Technology Laboratory Co., Ltd., product name "HM-150").

[0228] 3. Adhesive sheet fixing process In the adhesive sheet fixing process of this embodiment, the adhesive sheet of the present invention is fixed onto a support plate. "Fixing" the adhesive sheet of the present invention onto the support plate means that the adhesive sheet is fixed to the extent that it does not peel off the support plate during temporary fixing, processing, or peeling of the member. Therefore, after processing and peeling the member, the adhesive sheet may be peeled off the support plate. The adhesive sheet can be reused by fixing another adhesive sheet of the present invention to the support plate again after the adhesive sheet has been peeled off.

[0229] In the adhesive sheet fixing process of this embodiment, the adhesive sheet of the present invention may be fixed to the entire surface of the support plate or to a part of the support plate, as long as it is sufficient to temporarily fix the member to the support plate.

[0230] Figure 3 is a schematic cross-sectional view showing one embodiment of the adhesive sheet fixing process in the component processing method of the present invention using the adhesive sheet 1B shown in Figure 2. In the adhesive sheet 1B of this embodiment, the adhesive layer 11 is a first adhesive layer for temporarily fixing the component, and the adhesive layer 12 is a second adhesive layer for fixing to the support plate. In this embodiment, the adhesive sheet 1B can be fixed to the support plate 21 by peeling off the release liner 120 protecting the adhesive layer 12 from the adhesive sheet 1B (see Figure 3(a)) and adhering the adhesive surface of the exposed adhesive 12 to the support plate 21 (see Figure 3(b)) (see Figure 3(c)). Similarly, when using the adhesive sheet 1A shown in Figure 1, the adhesive sheet 1A can be fixed to the support plate 21 by peeling off the release liner 120 and attaching the adhesive surface 10 to the support plate 21 (not shown).

[0231] 4. Alignment mark formation process In the alignment mark formation process of this embodiment, the external stimulus is applied to a predetermined position on an adhesive sheet fixed on a support plate to cause discoloration and form an alignment mark on the adhesive sheet.

[0232] In this invention, "alignment mark" refers to a mark that serves as an indicator for positioning when processing a component. In this invention, the alignment mark can be formed at any position on the adhesive sheet of the present invention at any process, making it highly versatile and significantly improving production efficiency. Furthermore, since there is no need to provide alignment marks on the support plate, costs can be significantly reduced. Moreover, since the alignment mark can be formed immediately before or during the process in which the alignment mark is used, it is possible to eliminate the need to replace the support plate with one having a different alignment mark, which is also advantageous as it significantly improves manufacturing efficiency.

[0233] In the alignment mark formation process of this embodiment, the "predetermined position" refers to the position where the alignment mark is formed on the adhesive sheet fixed to the support plate. For example, the alignment mark serves as an indicator of the temporary fixing position of the member on the support plate, the pitch between members when multiple members are temporarily fixed, and the position of processing within the member. Note that the alignment mark only needs to serve as the above indicator and does not necessarily have to be placed at the temporary fixing or processing positions.

[0234] In the alignment mark formation process of this embodiment, "external stimulus" refers to a stimulus applied to the adhesive sheet of the present invention that causes the discoloration component contained in the adhesive sheet to change color, thereby forming an alignment mark. Examples include irradiation with active energy rays such as electron beam irradiation, ultraviolet irradiation, and laser light irradiation, as well as heating. From the viewpoint of easily forming alignment marks at any position on the adhesive sheet of the present invention, irradiation with active energy rays is preferred, ultraviolet irradiation is more preferred, and ultraviolet laser light irradiation is even more preferred from the viewpoint of easily forming alignment marks at specific positions.

[0235] When the external stimulus is irradiation with active energy rays, the irradiation of the active energy rays to the predetermined location includes, for example, a method of irradiating the location with active energy rays through a photomask having an opening at a location corresponding to the predetermined location, or a method of locally irradiating the location with laser light.

[0236] The aforementioned "discoloration" due to external stimuli refers to a change in color caused by external stimuli. From the viewpoint of visibility as an alignment mark, "coloring," which is a change from colorless (transparent) to colored, is preferable.

[0237] Figure 4 is a schematic cross-sectional view showing one embodiment of the alignment mark formation process in the component processing method of the present invention using the adhesive sheet 1B shown in Figure 2. In this embodiment, the adhesive sheet 1B is attached to the support plate 21 by the adhesive surface of the adhesive layer 12. In this embodiment, the adhesive layer 12 of the adhesive sheet 1B contains the color-changing component of the present invention, while the adhesive layer 11 does not contain the color-changing component of the present invention. In this embodiment, the color-changing component contained in the adhesive layer 12 of the adhesive sheet 1B includes a compound that changes color upon reaction with an acid, and a photoacid generator. In this embodiment, the support plate 21 is a highly transparent glass substrate.

[0238] In Figure 4(a), a photomask 22 is placed on the side of the support plate 21 that is not attached to the adhesive layer 12. In this embodiment, the openings in the photomask 22 correspond to the positions where the member 31, described later, is placed on the adhesive layer 11.

[0239] In Figure 4(b), the active energy ray U is irradiated onto the photomask 22. The active energy ray U passes through the opening of the photomask 22 and the highly transparent support plate 21, reaching the adhesive layer 12. The photoacid generator decomposes to generate acid, and the compound that changes color upon reaction with the acid changes color (becomes colored), forming an alignment mark 23 at the position corresponding to the opening of the photomask 22. In this embodiment, the adhesive layer 11 does not contain the color-changing component of the present invention, so no alignment mark is formed.

[0240] The active energy rays include light such as ultraviolet light, visible light, and infrared light, as well as radiation such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, and X-rays, with electron beams and ultraviolet light being preferred, and ultraviolet light being more preferred. After the alignment marks 23 are formed, the photomask 22 may be peeled off and removed from the support plate 21 (see Figure 4(c)).

[0241] Figure 5 is a schematic cross-sectional view showing another embodiment of the alignment mark formation process in the component processing method of the present invention using the adhesive sheet 1B shown in Figure 2. In this embodiment, the adhesive sheet 1B is attached to the support plate 21 by the adhesive surface of the adhesive layer 12. In this embodiment, the adhesive sheet 1B contains the color-changing component of the present invention, while the adhesive layer 11 does not contain the color-changing component of the present invention. In this embodiment, the color-changing component contained in the adhesive layer 12 of the adhesive sheet 1B includes a compound that changes color upon reaction with an acid, and a photoacid generator. In this embodiment, the support plate 21 is a highly transparent glass substrate.

[0242] In Figure 5(a), laser light L is irradiated from the support plate 21 side, passes through the highly transparent support plate 21, reaches the adhesive layer 12, the photoacid generator decomposes and generates acid, and the compound that changes color upon reaction with the acid changes color (colors), forming the alignment mark 23. In this embodiment, the laser light L is irradiated locally onto the adhesive layer 12, and the alignment mark 23 is formed only at the irradiated location. In this embodiment, the position on the adhesive layer 12 where the laser light L is irradiated and the alignment mark 23 is formed corresponds to the position where the member 31, described later, is placed on the adhesive layer 11. In this embodiment, since the adhesive layer 11 does not contain the color-changing component of the present invention, no alignment mark is formed.

[0243] The laser light includes ultraviolet light, visible light, infrared light, and radiation lasers such as alpha rays, beta rays, gamma rays, electron beams, neutron beams, and X-rays, with ultraviolet laser light being more preferred.

[0244] In Figure 5(b), the laser beam L is irradiated at a different position than in Figure 5(a), and alignment marks 23 are formed at a different position on the adhesive layer 12. In Figure 5(c), the laser beam is irradiated from the support plate 21 side, sequentially irradiating at different positions, and alignment marks 23 are formed at the same position as in Figure 4(c). Alternatively, the laser beam may be irradiated all at once to form all alignment marks 23 simultaneously.

[0245] 5. Temporary fixing process for components In the temporary fixing step of this embodiment, the member is temporarily fixed onto an adhesive sheet fixed on the support plate. In the temporary fixing step of this embodiment, the member is temporarily fixed using the alignment marks formed on the adhesive sheet as an indicator. In the temporary fixing step of this embodiment, by temporarily fixing the member using the alignment marks as an indicator, the position of the member on the support plate, the pitch between members when multiple members are temporarily fixed, etc., can be accurately positioned.

[0246] Figure 6 is a schematic cross-sectional view showing one embodiment of the temporary fixing step of a component in the component processing method of the present invention using the adhesive sheet 1B shown in Figure 2. In the temporary fixing step of this embodiment, in Figure 6(a), the release liner 110 is peeled off from the adhesive sheet 1B, and then, in Figure 6(b), multiple members 31 are attached to the temporary fixing material 30 and are positioned spaced apart opposite the adhesive surface of the adhesive layer 11 on the upper part of the adhesive surface of the exposed adhesive layer 11.

[0247] In this embodiment, the size of the member 31 is not particularly limited, but thin and fine members can be used. For example, the major axis may be 500 μm or less, or 100 μm or less; the minor axis may be 400 μm or less, or 50 μm or less. The lower limits of the major axis and minor axis are not particularly limited, but they should be 5 μm or more. Furthermore, the thickness of member 31 is not particularly limited, but may be 100 μm or less, or 50 μm or less. The lower limit of the thickness of member 31 is also not particularly limited, but may be 5 μm or more.

[0248] In Figure 6(b), one of the members 31 is peeled off from the temporary fixing material 30, and in Figure 6(c), it is placed on the adhesive layer 11 and temporarily fixed. The position where member 31 is temporarily fixed on the adhesive layer 11 is aligned to the corresponding position using the alignment mark 23 as an indicator.

[0249] In this embodiment, the method for peeling the member 31 from the temporary fixing material 30 is not particularly limited. For example, the member 31 is pushed from the surface of the temporary fixing material 30 where the member 31 is not adhered, using a pin member or the like, so that the member 31 is brought close to the adhesive surface of the adhesive layer 11, and the adhesive surface of the adhesive layer 11 receives it. At that time, the member 31 may be brought into contact with the adhesive surface of the adhesive layer 11, or the member 31 may be peeled from the temporary fixing material 30 non - contact and dropped onto the adhesive layer 11. Alternatively, an adsorption member such as a collet may be used to individually peel the member 31 from the temporary fixing material 30 and place it on the adhesive layer 11 for temporary fixing (not shown in the figure).

[0250] As another preferred embodiment, laser light may be irradiated from the surface of the temporary fixing material 30 where the member 31 is not adhered to peel the member 31 from the temporary fixing material 30 and drop it onto the adhesive layer 11. When the member 31 is peeled from the temporary fixing material 30 by irradiating laser light, it is preferable that the adhesive layer 11 contains an ultraviolet absorber. Since the laser light is absorbed by the adhesive layer 11 when the adhesive layer 11 contains an ultraviolet absorber, discoloration of the adhesive layer 12 can be suppressed.

[0251] FIG. 6(d) shows an embodiment in which all the members 31 are temporarily fixed on the adhesive layer 11, and the members 31 are aligned at corresponding positions using the alignment marks 23 as an index. The temporary fixing of the member 31 to the adhesive layer 11 may be performed individually or a plurality of them may be performed collectively.

[0252] 6. Member processing step In the member processing step of this embodiment, processing other than the temporary fixing is performed on the member temporarily fixed on the adhesive sheet. In the member temporary fixing step of this embodiment, it is preferable to perform the processing using the alignment marks formed on the adhesive sheet as an index. By processing the member temporarily fixed on the support plate using the alignment marks as an index, the processing accuracy and efficiency can be significantly improved, which is preferable. [[ID=十六]]

[0253] [[ID=十七]] FIG. 7 is a schematic cross-sectional view showing an embodiment of a member processing step in the member processing method of the present invention using the adhesive sheet 1B shown in FIG. 2. In the present embodiment, in FIG. 7(a), processing P is being performed on one of the members 31 temporarily fixed on the adhesive 11. The processing P is carried out using the alignment mark 23 as an index. For example, the processing P can be performed at a specific position of the member 31 with reference to the alignment mark 23 that positions the member 31.

[0254] The "processing" in the present embodiment is processing other than the temporary fixing of the member 31 onto the adhesive 11, and includes, for example, polishing, dicing, cutting, grinding, laser processing, printing, appearance inspection, etc. In the present embodiment, when the processing P is laser processing, it is preferable that the adhesive layer 11 contains an ultraviolet absorber. Since the laser light of the laser processing is absorbed by the adhesive layer 11 when the adhesive layer 11 contains an ultraviolet absorber, discoloration of the adhesive layer 12 can be suppressed.

[0255] In the present embodiment, in FIG. 7(b), 32 is the member after processing. In the present embodiment, processing P is being performed on one of the other members 31 temporarily fixed on the adhesive 11. The processing P may be sequentially performed on the members 31, or may be performed on all the members 31 at once. FIG. 7(c) is a schematic cross-sectional view showing an embodiment in which all the members 31 have been processed.

[0256] 7. Member peeling step In the member peeling step of the present embodiment, the member is peeled from the adhesive sheet. The configuration in which the member processing method of the present invention further includes the member peeling step is preferable from the viewpoint of improving the efficiency of process management such as transporting the processed member to the next process or shipping.

[0257] In the member peeling step of the present embodiment, the peeling of the member may be the peeling of the member after processing, the peeling between the processing steps, or the processing itself may involve the peeling of the member. For example, when the processing is transfer to another substrate, mounting, etc., the transfer and mounting involve the peeling of the member from the adhesive sheet of the present invention.

[0258] Figure 8 is a schematic cross-sectional view showing one embodiment of the member peeling step in the member processing method of the present invention using the adhesive sheet 1B shown in Figure 2. In this embodiment, Figure 8(a) is a schematic cross-sectional view showing an embodiment in which the processed member 32 is temporarily fixed to the adhesive layer 11. Figure 8(b) is a schematic cross-sectional view showing an embodiment in which one of the members 32 has been peeled off from the adhesive layer 11, and Figure 8(c) is a schematic cross-sectional view showing an embodiment in which all of the members 32 have been peeled off from the adhesive layer 11.

[0259] The members 32 may be peeled off from the adhesive layer 11 individually using, for example, an adsorption member such as a collet, or all members 32 may be peeled off and transferred at once by pressing another substrate onto them.

[0260] The adhesive sheet, from which all components 32 have been removed, may be peeled off the support plate 21 (see Figure 8(d)). The support plate 21 from which the adhesive sheet has been removed can be reused by fixing another adhesive sheet of the present invention to it.

[0261] If the adhesive sheet of the present invention is a substrate-less adhesive sheet, the component processing method of the present invention can be carried out in the same manner using the adhesive sheet 1A shown in Figure 1 instead of adhesive sheet 1B. [Examples]

[0262] The present invention will be described in more detail below with reference to examples, but the present invention is not limited in any way by these examples.

[0263] [Manufacturing Example 1]: Manufacturing of acrylic copolymer (1) In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, 95 parts by weight of butyl acrylate (manufactured by Nippon Shokubai Co., Ltd.), 5 parts by weight of acrylic acid (manufactured by Toagosei Co., Ltd.), 0.2 parts by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 156 parts by weight of ethyl acetate were charged. Nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for 10 hours while maintaining the liquid temperature in the flask at around 63°C to prepare a solution (solid content: 40% by weight) of an acrylic copolymer (1) with a weight-average molecular weight of 700,000.

[0264] [Manufacturing Example 2]: Manufacturing of acrylic copolymer (2) In a four-necked flask equipped with a stirring blade, thermometer, nitrogen gas inlet tube, and condenser, 100 parts by weight of 2-ethylhexyl acrylate (2EHA) (manufactured by Nippon Shokubai Co., Ltd.), 4 parts by weight of 2-hydroxyethyl acrylate (HEA) (manufactured by Toagosei Co., Ltd.), 0.02 parts by weight of 2,2'-azobisisobutyronitrile (manufactured by Wako Pure Chemical Industries, Ltd.) as a polymerization initiator, and 180 parts by weight of ethyl acetate were charged. Nitrogen gas was introduced while gently stirring, and the polymerization reaction was carried out for 6 hours while maintaining the liquid temperature in the flask at around 65°C to prepare a solution (solid content: 35% by weight) of an acrylic copolymer (2) with a weight-average molecular weight of 560,000.

[0265] [Example 1] (Making adhesive sheets) 100 parts by weight of silicone adhesive 1 (addition reaction type silicone adhesive, trade name "X-40-3306", manufactured by Shin-Etsu Chemical Co., Ltd.), 1.4 parts by weight of platinum catalyst 1 (trade name "CAT-PL-50T", manufactured by Shin-Etsu Chemical Co., Ltd.), and 5 parts by weight of silicone release agent 1 (addition reaction type silicone release agent mainly composed of dimethylpolysiloxane, trade name "KS-776A", manufactured by Shin-Etsu Chemical Co., Ltd.) were added, diluted with toluene to a total solid content of 25% by weight, and mixed with a disperser to prepare a silicone adhesive composition (silicone adhesive composition 1). A silicone-based adhesive composition 1 was applied to the silicone-primer-treated side of a base film (1) (a polyester film with one side treated with a silicone primer, 25 μm thick, product name "Diafoil MRF#25", manufactured by Mitsubishi Plastics, Inc.) so that the adhesive thickness after drying was 10 μm. The film was then cured and dried at a drying temperature of 120°C for a drying time of 5 minutes. In this way, a film having a silicone-based adhesive layer (1) on the silicone-primer-treated layer of the base film (1) was obtained. Furthermore, a release liner (1) (untreated polyethylene terephthalate film, 25 μm thick, product name "Lumirror S10#25", manufactured by Toray Industries, Inc.) was laminated onto the adhesive surface of the silicone adhesive film to protect the silicone adhesive layer, thereby obtaining a laminate (1) having a laminated structure of [release liner (1) layer] / [silicone adhesive (1) layer] / [base film (1) layer]. Next, to the solution of the acrylic copolymer (1) obtained in Production Example 1, 6.0 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 2 parts by weight of leuco dye (product name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.), and 7 parts by weight of photoacid generator (product name "CPI-100P", manufactured by Sunapro Co., Ltd.) were added per 100 parts by weight of solids. The solution was diluted with toluene so that the total solids content was 25% by weight, and the acrylic adhesive composition was stirred with a disperser. This acrylic adhesive composition was applied to the release layer side of the release liner (2) (released polyethylene terephthalate film, thickness 38 μm, product name "MRF#38", manufactured by Mitsubishi Chemical Corporation) using a fountain roll so that the thickness after drying was 25 μm. The liner was then cured and dried under conditions of a drying temperature of 130°C and a drying time of 30 seconds. In this way, an acrylic adhesive layer (1) was formed on the release liner (2). Next, the base film (1) side (the side not treated with silicone primer) of the laminate (1) obtained above was bonded to the surface of the acrylic adhesive layer (1) to obtain an adhesive sheet having a laminated structure of [release liner (1) layer] / [silicone adhesive (1) layer (first adhesive layer)] / [base film (1) layer] / [acrylic adhesive (1) layer (second adhesive layer)] / [release liner (2) layer].

[0266] [Example 2] An adhesive sheet having a laminated structure of [Release Liner (1) layer] / [Silicone-based Adhesive (1) layer (First Adhesive Layer)] / [Base Film (1) layer] / [Acrylic-based Adhesive (2) layer (Second Adhesive Layer)] / [Release Liner (2) layer] was obtained in the same manner as in Example 1, except that 7 parts by weight of a photoacid generator (product name "CPI-110P", manufactured by Sunapro Co., Ltd.) was added instead of the photoacid generator (product name "CPI-100P", manufactured by Sunapro Co., Ltd.).

[0267] [Example 3] An adhesive sheet having a laminated structure of [Release Liner (1) layer] / [Silicone-based adhesive (1) layer (first adhesive layer)] / [Base film (1) layer] / [Acrylic-based adhesive (3) layer (second adhesive layer)] / [Release Liner (2) layer] was obtained in the same manner as in Example 1, except that 7 parts by weight of a photoacid generator (product name "CPI-310B", manufactured by Sunapro Co., Ltd.) was added instead of a photoacid generator (product name "CPI-100P", manufactured by Sunapro Co., Ltd.).

[0268] [Example 4] An adhesive sheet having a laminated structure of [Release Liner (1) layer] / [Silicone-based adhesive (1) layer (first adhesive layer)] / [Base film (2) layer] / [Acrylic-based adhesive (4) layer (second adhesive layer)] / [Release Liner (2) layer] was obtained in the same manner as in Example 1, except that 7 parts by weight of a photoacid generator (product name "CPI-100P", manufactured by Sunapro Co., Ltd.) was replaced with a photoacid generator (product name "SP-056", manufactured by ADEKA Corporation), and a base film (2) (polyimide film, thickness 25 μm, product name "Kapton 100H", manufactured by Toray DuPont) was used instead of base film (1).

[0269] [Example 5] Instead of the base film (2), a base film (3) (TAC film, thickness 80 μm, product name "Fujitac TD80UL", manufactured by Fujifilm Corporation) was used, and in the same manner as in Example 4, a laminate structure of [release liner (1) layer] / [silicone-based adhesive (1) layer (first adhesive layer)] / [base film (3) layer] / [acrylic-based adhesive (4) layer (second adhesive layer)] / [release liner (2) layer] was obtained.

[0270] [Example 6] With respect to 100 parts by weight of the solid content of the acrylic copolymer (2) obtained in Production Example 2, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, 0.02 parts by weight of Envirez OL-1 (manufactured by Tokyo Fine Chemical Co., Ltd.) as a crosslinking catalyst, 2 parts by weight of a leuco dye (product name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.), and 7 parts by weight of a photoacid generator (product name "SP-056", manufactured by ADEKA Corporation) were added, and the mixture was diluted with ethyl acetate so that the total solid content was 25% by weight and stirred with a disperser. In the same manner as in Example 1, except that the obtained acrylic adhesive composition was applied to the release liner (2), a laminate structure of [release liner (1) layer] / [silicone-based adhesive (1) layer (first adhesive layer)] / [base film (1) layer] / [acrylic-based adhesive (5) layer (second adhesive layer)] / [release liner (2) layer] was obtained.

[0271] [Example 7] As a prepolymer-type urethane adhesive composition (1), to a solution of Ciabein SH-109 (manufactured by Toyo Chem Co., Ltd.), 3.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, 2 parts by weight of leuco dye (product name "S-205", manufactured by Yamada Chemical Industries, Ltd.), and 7 parts by weight of photoacid generator (product name "SP-056", manufactured by ADEKA Corporation) were added per 100 parts by weight of solids, diluted with ethyl acetate so that the total solids content was 25% by weight, stirred with a disperser, and the resulting urethane adhesive composition was applied to a release liner (2). Except for these steps, an adhesive sheet having a laminated structure of [Release liner (1) layer] / [Silicone adhesive (1) layer (first adhesive layer)] / [Base film (1) layer] / [Urethane adhesive (1) layer (second adhesive layer)] / [Release liner (2) layer] was obtained in the same manner as in Example 1.

[0272] [Example 8] 100 parts by weight of silicone adhesive 1 (addition reaction type silicone adhesive, trade name "X-40-3306", manufactured by Shin-Etsu Chemical Co., Ltd.), 1.4 parts by weight of platinum catalyst 1 (trade name "CAT-PL-50T", manufactured by Shin-Etsu Chemical Co., Ltd.), 5 parts by weight of silicone release agent 1 (addition reaction type silicone release agent mainly composed of dimethylpolysiloxane, trade name "KS-776A", manufactured by Shin-Etsu Chemical Co., Ltd.), and 5 parts by weight of ultraviolet absorber (trade name "TINUVIN 384-2", manufactured by BASF) were added, diluted with toluene to a total solid content of 25% by weight, and mixed with a disperser to prepare a silicone adhesive composition (silicone adhesive composition 2). A silicone-based adhesive composition 2 was applied to a base film (4) (COP film, 55 μm thick, trade name "ZeonorFilm", manufactured by Zeon Corporation of Japan) so that the adhesive thickness after drying was 10 μm. The film was then cured and dried at a drying temperature of 120°C for a drying time of 5 minutes. In this way, a film having a silicone-based adhesive layer (2) on the base film (4) was obtained. Furthermore, a release liner (1) (untreated polyethylene terephthalate film, 25 μm thick, product name "Lumirror S10#25", manufactured by Toray Industries, Inc.) was laminated onto the adhesive surface of the silicone adhesive film to protect the silicone adhesive layer, thereby obtaining a laminate (2) having a laminated structure of [release liner (1) layer] / [silicone adhesive (2) layer] / [base film (4) layer]. Next, to the solution of the acrylic copolymer (2) obtained in Production Example 2, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, 2 parts by weight of leuco dye (product name "S-205", manufactured by Yamada Chemical Industries, Ltd.), and 7 parts by weight of photoacid generator (product name "SP-056", manufactured by ADEKA Corporation) were added per 100 parts by weight of solids. The solution was diluted with toluene so that the total solids content was 25% by weight, and the acrylic adhesive composition was stirred with a disperser. This acrylic adhesive composition was applied to the release layer side of the release liner (2) (release-treated polyethylene terephthalate film, thickness 38 μm, product name "MRF#38", manufactured by Mitsubishi Chemical Corporation) using a fountain roll so that the thickness after drying was 25 μm. The liner was then cured and dried under conditions of a drying temperature of 130°C and a drying time of 30 seconds. In this way, an acrylic adhesive layer (6) was formed on the release liner (2). Next, the base film (4) side of the laminate (2) obtained above was bonded to the surface of the acrylic adhesive layer (6) to obtain an adhesive sheet having a laminated structure of [release liner (1) layer] / [silicone adhesive (2) layer (first adhesive layer)] / [base film (4) layer] / [acrylic adhesive (6) layer (second adhesive layer)] / [release liner (2) layer].

[0273] [Comparative Example 1] Except for adding 6.0 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, and 2 parts by weight of leuco dye (product name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) to 100 parts by weight of solids of the acrylic copolymer (2) obtained in Production Example 2, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, and 2 parts by weight of leuco dye (product name "S-205", manufactured by Yamada Chemical Industry Co., Ltd.) to 100 parts by weight of solids, diluting with ethyl acetate so that the total solids content is 25% by weight, stirring with a disperser, and applying the obtained acrylic adhesive composition to the release liner (2), an adhesive sheet having a laminated structure of [release liner (1) layer] / [silicone adhesive (1) layer (first adhesive layer)] / [base film (1) layer] / [acrylic adhesive (7) layer (second adhesive layer)] / [release liner (2) layer] was obtained in the same manner as in Example 1.

[0274] [Comparative Example 2] Except for adding 6.0 parts by weight of TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a crosslinking agent, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, and 7 parts by weight of a photoacid generator (product name "SP-056", manufactured by ADEKA Corporation) to 100 parts by weight of solids of the acrylic copolymer (2) obtained in Production Example 2, 4.0 parts by weight of Coronate HX (manufactured by Tosoh Corporation) as a crosslinking agent, and 7 parts by weight of a photoacid generator (product name "SP-056", manufactured by ADEKA Corporation) as a crosslinking agent, and diluting with ethyl acetate so that the total solids content is 25% by weight, and stirring with a disperser, an adhesive sheet having a laminated structure of [peel liner (1) layer] / [silicone adhesive (1) layer (first adhesive layer)] / [base film (1) layer] / [acrylic adhesive (8) layer (second adhesive layer)] / [peel liner (2) layer] was obtained in the same manner as in Example 1.

[0275] <Rating> The adhesive sheets obtained in the examples and comparative examples were evaluated as follows. The results are shown in Table 1.

[0276] (Change in total light transmittance) After peeling off the release liners from both sides of the adhesive sheet having the laminated structure described in each example, the initial total light transmittance was measured using a haze meter (HM-150, manufactured by Murakami Color Technology Laboratory) with the first adhesive layer facing the light source. Next, a UV irradiation device (UV LIGHT SOURCE UL750, manufactured by HOYA Corporation) is used to irradiate the release liner (2) at an illuminance of 100 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2 The second adhesive layer was discolored by irradiating it with light, and after peeling off the peel-off liners on both sides, the total light transmittance after discoloration was measured using a haze meter, as in the initial stage. The absolute value of the difference between the initial and discolored total light transmittances was defined as the change in total light transmittance.

[0277] (Alignment) A photomask equipped with alignment marks with a line width of 300 μm is placed on the release liner (2) of the adhesive sheet for each example, and a UV irradiation device (UV LIGHT SOURCE UL750, manufactured by HOYA Corporation) is used to irradiate the photomask at an illuminance of 100 mW / cm². 2 , cumulative light intensity 1000 mJ / cm 2 Alignment marks were created by irradiating with light. Then, the release liner (2) was peeled off, the second adhesive layer was bonded to alkali-free glass, and the alignment marks were read and evaluated through the glass using the following method. CCD camera: CA-H500C (manufactured by Keyence Corporation) Analysis: ShapeTrax3 (manufactured by Keyence Corporation) Judgment: Items with a correlation value of 90 or higher are marked with ○, and items with a correlation value less than 90 are marked with ×.

[0278] (Discoloration due to exposure to external light from the sheet side) After peeling off the release liner (2) of the adhesive sheet for each example, the second adhesive layer was bonded to alkali-free glass to prepare evaluation samples. Then, the release liner (1) was peeled off, and the adhesive sheets of each example and comparative example were left for 240 hours under the condition that fluorescent light was shone from the first adhesive layer side, and the presence or absence of discoloration was visually checked. Samples that did not show discoloration were marked with ○, and those that did show discoloration were marked with ×. Note that comparative examples 1 and 2 do not have alignment properties (discoloration properties), so naturally no discoloration was observed. [Table 1]

[0279] Variations of the present invention are listed below. [Note 1] A method for processing a member temporarily fixed on a support plate, A step of preparing an adhesive sheet containing a color-changing component that can change color in response to external stimuli, The steps include fixing the adhesive sheet onto the support plate, The process involves applying the external stimulus to a predetermined position on the adhesive sheet fixed to the support plate to cause discoloration and form an alignment mark on the adhesive sheet, A step of temporarily fixing the member onto the adhesive sheet fixed on the support plate, A method for processing the aforementioned member, including the above. [Note 2] The processing method according to Appendix 1, wherein in the step of temporarily fixing the member onto the adhesive sheet, the member is temporarily fixed using the alignment marks formed on the adhesive sheet as an indicator. [Note 3] Furthermore, the processing method described in Appendix 1 or 2, including the following steps. A process of performing processing other than the temporary fixing on the member that has been temporarily fixed on the adhesive sheet. [Note 4] The processing method described in Appendix 3, wherein the processing is performed using the alignment marks formed on the adhesive sheet as indicators. [Note 5] Furthermore, the processing method described in any one of the appendices 1 to 4, including the following steps. Steps to peel the member from the adhesive sheet. [Note 6] The processing method according to any one of the appendices 1 to 5, wherein the aforementioned component is a semiconductor wafer or a semiconductor chip. [Note 7] The processing method according to any one of the appendices 1 to 6, wherein the external stimulus is irradiation with active energy rays. [Explanation of Symbols]

[0280] 1A Adhesive Sheet 1B Adhesive Sheet 10 Adhesive layer S base material 11 Adhesive layer 12 Adhesive layer 110,120 Peel-off Liner 21 Support plate 22 Photomasks 23. Alignment marks (discolored areas) U-activated energy rays L laser light P processing 30 Temporary fixing material 31 components 32. Processed parts

Claims

1. A method for processing a member temporarily fixed on a support plate, A step of preparing a double-sided adhesive sheet containing a color-changing component that can change color in response to external stimuli, The process of attaching one adhesive surface of the double-sided adhesive sheet to the support plate and fixing it in place, The process involves applying the external stimulus to a predetermined position on the double-sided adhesive sheet fixed to the support plate to cause discoloration and form an alignment mark on the double-sided adhesive sheet. The steps include: temporarily fixing the member to the other adhesive surface of the double-sided adhesive sheet fixed on the support plate; A method for processing the aforementioned member, including the above.

2. The processing method according to claim 1, wherein in the step of temporarily fixing the member onto the double-sided adhesive sheet, the member is temporarily fixed using the alignment marks formed on the double-sided adhesive sheet as an indicator.

3. Furthermore, the processing method according to claim 1, further comprising the following steps. A process of performing processing other than the temporary fixing on the member that has been temporarily fixed on the double-sided adhesive sheet.

4. Furthermore, the processing method according to claim 2, further comprising the following steps. A process of performing processing other than the temporary fixing on the member that has been temporarily fixed on the double-sided adhesive sheet.

5. The processing method according to claim 3, wherein the processing is performed using the alignment marks formed on the double-sided adhesive sheet as indicators.

6. The processing method according to claim 4, wherein the processing is performed using the alignment marks formed on the double-sided adhesive sheet as indicators.

7. Furthermore, the processing method according to any one of claims 1 to 6, further comprising the following steps. Steps to peel the member from the double-sided adhesive sheet.

8. The processing method according to any one of claims 1 to 6, wherein the member is a semiconductor wafer or a semiconductor chip.

9. The processing method according to any one of claims 1 to 6, wherein the external stimulus is irradiation with active energy rays.

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