Peeling composition and method for peeling adhesive

Abstract

To provide a peeling composition for removing an adhesive that can further suppress the generation of a volatile organic compounds (VOC) and has sufficient washability for the adhesive, and a method for peeling an adhesive using the peeling composition.SOLUTION: The present invention is a peeling composition for peeling an adhesive, and is characterized by containing limonene and a component (A): hydrocarbon which may have a substituent group and has a boiling point of 200°C or more. The invention is a method for removing an adhesive from a substrate to which it is adhered, including a dissolution step of bringing the peeling composition of the present invention into contact with the adhesive to dissolve the adhesive.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a stripping composition and a method for stripping adhesives. [Background technology]

[0002] In recent years, with the increasing sophistication of mobile phones, digital AV devices, IC cards, etc., there is an increasing demand for smaller, thinner, and more highly integrated semiconductor silicon chips. For example, system-in-package (SiP), which mounts multiple semiconductor chips in a single semiconductor package, is a very important technology for making the mounted chips smaller, thinner, and more highly integrated, and for realizing high performance, small size, and light weight of electronic devices. In order to meet the demand for such thinning and high integration, not only conventional wire bonding technology but also through electrode technology, which stacks chips with through electrodes and forms bumps on the backside of the chips, is required.

[0003] In the manufacture of semiconductor chips, the semiconductor wafer itself is thin and fragile, and the circuit pattern has irregularities, so it is easily damaged if an external force is applied during transportation to the grinding or dicing process. For this reason, a wafer handling system (WHS) has been developed that maintains the strength of the wafer and prevents the occurrence of cracks and warping of the wafer by bonding a support base made of glass, hard plastic, etc. to the wafer to be ground. Because the wafer handling system can maintain the strength of the wafer, it is possible to automate the transportation of thinned semiconductor wafers.

[0004] The wafer and the support base are attached to each other using an adhesive tape, a thermoplastic resin, an adhesive, etc. After the wafer to which the support base is attached is thinned, the support base is peeled off and removed from the wafer before dicing the wafer. The adhesive remaining on the wafer is then washed away using a composition containing a solvent.

[0005] For example, Patent Document 1 describes a stripping composition for dissolving an adhesive to peel off a substrate from a support plate, the stripping composition containing at least one solvent selected from the group consisting of cyclic hydrocarbons and terpene solvents (e.g., p-menthane) and containing 5% by weight or less of high-boiling-point impurities having a boiling point 25° C. or more higher than the boiling point of the solvent. Patent Document 2 describes a kit used for the steps of forming a temporary adhesive layer on a wafer using a composition containing a temporary adhesive and solvent A, cleaning at least a portion of the excess temporary adhesive on the wafer using a composition containing solvent B, and peeling one of the wafer and the supporting base from a laminate of the wafer and the supporting base bonded together via the temporary adhesive layer at a temperature below 40°C, and cleaning the temporary adhesive remaining on the wafer or the supporting base with a composition containing solvent C. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Patent No. 6093187 [Patent Document 2] Patent No. 6450451 Summary of the Invention [Problem to be solved by the invention]

[0007] In the manufacture of semiconductor chips as described above, compositions used to wash and remove adhesive remaining on wafers and the like are required to have sufficient cleaning properties against the adhesive.

[0008] In recent years, there has been a demand for reducing emissions of volatile organic compounds (VOCs) due to concerns about air pollution. VOCs are a general term for organic chemical substances that volatilize into the air at room temperature and pressure. VOCs can cause health damage when released into the environment, and therefore restrictions on VOCs are being implemented in various countries. However, conventional compositions used to clean and remove adhesives remaining on wafers and the like are not sufficient in reducing the generation of VOCs.

[0009] The present invention has been made in consideration of the above circumstances, and an object of the present invention is to provide a stripping composition for removing adhesives that can further suppress the generation of VOCs and has sufficient cleanability for adhesives, and a method for removing adhesives that uses this stripping composition. [Means for solving the problem]

[0010] In order to solve the above problems, the present invention employs the following configuration.

[0011] A first aspect of the present invention is a stripping composition for stripping an adhesive, which contains limonene and component (A): a hydrocarbon having a boiling point of 200°C or higher, which may have a substituent.

[0012] A second aspect of the present invention is a method for peeling an adhesive from a substrate to which the adhesive is adhered, comprising a dissolving step of contacting the peeling composition according to the first aspect with the adhesive to dissolve the adhesive. Effect of the Invention

[0013] According to the present invention, it is possible to provide a stripping composition for removing adhesives, which can further suppress the generation of VOCs and has sufficient cleanability for adhesives, and a method for removing adhesives using this stripping composition. [Brief description of the drawings]

[0014] [Figure 1A]5A to 5C are schematic diagrams illustrating an example of a dissolving step in a method for peeling off an adhesive according to an embodiment. [Figure 1B] 1 is a schematic diagram showing a substrate after a dissolving step in a method for removing an adhesive according to an embodiment. FIG. [Figure 2A] 1 is a schematic diagram showing an example of a laminate to which a method for peeling an adhesive according to an embodiment is applied; [Figure 2B] 1 is a schematic diagram illustrating an example of a separation step in a method for peeling off an adhesive according to an embodiment, showing a state in which light is irradiated onto a separation layer 4 in the separation step. [Figure 2C] 1 is a schematic diagram illustrating an example of a separation step in a method for peeling off an adhesive according to an embodiment, and 4' denotes a separation layer altered by light irradiation. [Figure 2D] 1 is a schematic diagram illustrating an example of a separation step in a method for peeling off an adhesive according to an embodiment, showing a state in which a supporting base 2 has been separated from a substrate 1. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] (Stripping composition) A first aspect of the present invention is a stripping composition for stripping an adhesive. One embodiment of the stripping composition contains limonene and component (A): a hydrocarbon that may have a substituent and has a boiling point of 200° C. or higher. Such a stripping composition is particularly suitable as a composition used for cleaning and removing adhesive remaining on a wafer or the like in the production of semiconductor chips.

[0016] <Limonene> Limonene is a chiral compound and may be used in any of the d-form (CAS Registry Number 5989-27-5), l-form (CAS Registry Number 5989-54-8), and racemic form (CAS Registry Number 138-86-3). From the viewpoint of handling and the like, it is preferable to use the d-form. The content of limonene in the stripping composition is preferably from 40 to 80 mass %, more preferably from 45 to 75 mass %, and even more preferably from 50 to 70 mass %, based on the total mass of the stripping composition. When the limonene content is equal to or more than the lower limit of the preferred range, the cleaning and removal effect on adhesives is easily improved, while when the limonene content is equal to or less than the upper limit of the preferred range, the amount of VOC emissions is easily kept low.

[0017] <Component (A)> The component (A) in this embodiment is a hydrocarbon having a boiling point of 200° C. or higher, which may have a substituent. The "boiling point" referred to here is the boiling point (normal boiling point) when the external pressure is 1 atmosphere, or 101.325 kPa. The boiling point of component (A) is at least 200° C., preferably at least 210° C., and more preferably at least 220° C. When the boiling point of component (A) is at least the aforementioned lower limit, the amount of VOCs generated is further reduced. The upper limit of the boiling point of the component (A) is, for example, 300°C or lower, and may be 280°C or lower, or 260°C or lower.

[0018] Examples of the substituent that the hydrocarbon in the component (A) may have include an acyloxy group having 1 to 3 carbon atoms and an alkoxy group having 1 to 3 carbon atoms.

[0019] Either chain hydrocarbons or cyclic hydrocarbons may be used as component (A). Chain hydrocarbons may be linear or branched. Cyclic hydrocarbons may be monocyclic or polycyclic. The component (A) contained in the stripping composition of the present embodiment may be one type alone, or two or more types may be used in combination. A preferred example of the component (A) is at least one selected from the group consisting of paraffins, naphthenes, and terpenes.

[0020] The content of the component (A) in the stripping composition is preferably 20 to 60 mass %, more preferably 25 to 55 mass %, and even more preferably 30 to 50 mass %, based on the total mass of the stripping composition. When the content of component (A) is equal to or greater than the lower limit of the preferred range, the amount of VOCs generated is more likely to be reduced, whereas when the content is equal to or less than the upper limit of the preferred range, the cleaning and removing effect on adhesives is more likely to be maintained satisfactorily.

[0021] <Paraffin> The paraffin as the component (A) in this embodiment may be straight-chain (normal paraffin) or branched-chain (isoparaffin), and is preferably branched-chain (isoparaffin). The paraffin as component (A) preferably has a boiling point of 210 to 265°C, more preferably 220 to 260°C, and even more preferably 225 to 255°C. The "boiling point of paraffin" as used herein means the range between the initial boiling point and the dry point in distillation. Alternatively, paraffin as the component (A) may be, for example, a chain saturated hydrocarbon having 9 to 13 carbon atoms, and preferably includes mixtures thereof.

[0022] The content of paraffin in the stripping composition is preferably from 20 to 40 mass %, more preferably from 20 to 35 mass %, and even more preferably from 25 to 35 mass %, based on the total mass of the stripping composition.

[0023] Commercially available paraffins that can be used as the component (A) include, for example, the isoparaffin-based solvent Isopar series manufactured by ExxonMobil Corp. Specifically, Isopar M (CAS registration number 125-12-2, boiling point 227 to 254° C.) and the like can be used.

[0024] In the stripping composition of the present embodiment, when the component (A) contains paraffin, the mixing ratio of limonene to paraffin as the component (A), expressed as a mass ratio of limonene / paraffin, is preferably 90 / 10 to 60 / 40, more preferably 80 / 20 to 60 / 40, and even more preferably 75 / 25 to 65 / 35. When the mass ratio of limonene / paraffin is equal to or greater than the lower limit of the above-mentioned preferred range, the amount of VOCs generated is more likely to be reduced, whereas when the mass ratio is equal to or less than the upper limit of the above-mentioned preferred range, the cleaning and removing effect on adhesives is more likely to be maintained satisfactorily.

[0025] <Naphthene> The naphthene as component (A) in this embodiment is a cycloalkane, and preferably has a boiling point of 200 to 250°C, more preferably 200 to 245°C, and even more preferably 220 to 240°C. The "boiling point of naphthenes" as used herein means the range between the initial boiling point and the dry point in distillation.

[0026] The content of naphthene in the stripping composition is preferably 20 to 60 mass %, more preferably 25 to 55 mass %, and even more preferably 30 to 50 mass %, based on the total mass of the stripping composition.

[0027] Examples of naphthenes that can be used as the component (A) include commercially available naphthene-based solvents such as the Naphtesol series manufactured by ENEOS Corp. Specifically, naphthesol grade 220 (CAS registration number 64742-47-8, boiling point 221 to 240° C.) and naphthesol grade 200 (CAS registration number 64742-47-8, boiling point 201 to 217° C.) can be used. In addition, examples of naphthenes that can be used as component (A) include commercially available naphthene-based solvents such as the Exxol series manufactured by ExxonMobil Corp. Specifically, Exxol D80 (CAS registration number 64742-48-9, boiling point 200° C.) can be used. Naphthenes that can be used as component (A) are preferably those selected from the group consisting of CAS Registry Number 64742-47-8 and CAS Registry Number 64742-48-9, and more preferably those having CAS Registry Number 64742-47-8.

[0028] In the stripping composition of the present embodiment, when the component (A) contains naphthene, the mixing ratio of limonene to naphthene as the component (A), expressed as a mass ratio of limonene / naphthene, is preferably 90 / 10 to 50 / 50, more preferably 80 / 20 to 60 / 40, and even more preferably 75 / 25 to 65 / 35. When the mass ratio of limonene / naphthene is equal to or greater than the lower limit of the above-mentioned preferred range, the amount of VOCs generated is more likely to be reduced, whereas when the mass ratio is equal to or less than the upper limit of the above-mentioned preferred range, the cleaning and removing effect on adhesives is more likely to be maintained satisfactorily.

[0029] <Terpenes as component (A)> The terpenes as component (A) in this embodiment include hydrocarbons having isoprene as a structural unit, and derivatives of hydrocarbons having isoprene as a structural unit having a functional group (such as a carbonyl group, a hydroxyl group, an acyloxy group, or an alkoxy group). The terpenes as the component (A) preferably have a boiling point of 210 to 235°C, more preferably 215 to 230°C, and even more preferably 220 to 225°C. The "boiling point of terpenes" as used herein means the range between the initial boiling point and the dry point in distillation.

[0030] The content of terpenes as component (A) in the stripping composition is preferably 40 to 60 mass %, more preferably 40 to 55 mass %, and even more preferably 45 to 55 mass %, based on the total mass of the stripping composition.

[0031] Examples of terpenes that can be used as component (A) include dihydroterpinyl acetate (CAS registration number 58985-18-5), dihydroterpineol (CAS registration numbers 498-81-7 (8-ol), 21129-27-1 (1-ol)), dihydroterpinyloxyethanol (CAS registration number 247074-38-0), and terpinyl methyl ether (CAS registration number 14576-08-0), all of which are manufactured by Japan Terpene Chemical Co., Ltd. Terpenes that can be used as component (A) are preferably those selected from the group consisting of CAS Registry Number 58985-18-5, CAS Registry Number 498-81-7, CAS Registry Number 21129-27-1, CAS Registry Number 247074-38-0, and CAS Registry Number 14576-08-0, and more preferably those with CAS Registry Number 58985-18-5.

[0032] In the stripping composition of the present embodiment, when the component (A) contains terpenes, the mixing ratio of limonene to the terpenes as the component (A), expressed as a mass ratio of limonene / terpenes, is preferably 60 / 40 to 40 / 60, more preferably 55 / 45 to 40 / 60, and even more preferably 55 / 45 to 45 / 55. When the mass ratio of limonene / terpenes is equal to or greater than the lower limit of the preferred range, the amount of VOCs generated is more likely to be reduced, whereas when the mass ratio is equal to or less than the upper limit of the preferred range, the cleaning and removing effect on adhesives is more likely to be maintained satisfactorily.

[0033] <Optional ingredients> The stripping composition of the present embodiment may contain other components in addition to limonene and component (A), such as a surfactant and an organic solvent other than component (A).

[0034] <Surfactants> The stripping composition of the present embodiment may or may not contain a surfactant. The surfactant may be a nonionic surfactant or a silicon-based surfactant. Examples of nonionic surfactants include acetylene glycol surfactants, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan fatty acid esters, etc. Among these, acetylene glycol surfactants and polyoxyethylene alkyl ethers are more preferred. The acetylene glycol surfactant is available as a commercial product, and examples thereof include the Surfynol series manufactured by Air Products and Chemicals, Inc. (USA). Specific examples thereof include Surfynol 104E, Surfynol 420, Surfynol 440, Surfynol 465, and Surfynol 485.

[0035] Polyoxyethylene alkyl ethers are commercially available, and examples thereof include the Noigen series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., the Softanol series manufactured by Nippon Shokubai Co., Ltd., and the Finesurf series manufactured by Aoki Yushi Kogyo Co., Ltd. Specific examples thereof include Noigen XL-40, Noigen XL-80, Noigen TDS-50, Noigen TDS-70, Softanol 30, Softanol 50, Softanol 70, Softanol 90, Finesurf TD-70, Finesurf TD-75, and Finesurf TD-80.

[0036] Examples of the silicone surfactant include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, etc. Silicon surfactants are available as commercial products, and examples of such products include BYK-331, BYK-310, and BYK-322 manufactured by BYK-Chemie Japan Co., Ltd.

[0037] When the stripping composition of the present embodiment contains a surfactant, the surfactant may be one type or two or more types. The content of the surfactant in the stripping composition of the present embodiment is, for example, 0 to 10% by mass, and preferably 0 to 5% by mass, based on the total mass of the stripping composition.

[0038] [glue] The peeling composition of the present embodiment is used to peel off an adhesive. The adhesive to which the peeling composition of the present embodiment is applied is not particularly limited, but a preferred example is an adhesive used to bond a substrate and a support in a semiconductor manufacturing process. Such adhesives include, for example, those containing hydrogenated styrene-based elastomers. The adhesives may contain additive resins such as hydrocarbon resins and acrylic-styrene-based resins, as well as release agents. In addition, the adhesives may contain other components such as plasticizers and thermal polymerization inhibitors.

[0039] [Hydrogenated styrene elastomer] Hydrogenated styrenic elastomers are hydrogenated block copolymers of styrene and conjugated dienes.

[0040] Hydrogenated styrene-based elastomers are less likely to be altered by decomposition, polymerization, etc. Therefore, by using hydrogenated styrene-based elastomers, it is possible to improve the thermal stability of the adhesive layer formed by the adhesive. In addition, by using hydrogenated styrene-based elastomers, it is possible to further increase the heat resistance of the adhesive layer, and to increase the resistance of the adhesive layer to resist solvents.

[0041] As the hydrogenated styrene-based elastomer, a diblock polymer in which one end of an elastomer block is polymerized with a styrene block, and a triblock polymer in which both ends of an elastomer block are polymerized with a styrene block can be used. If a hydrogenated styrene-based elastomer that is a triblock polymer is used, the adhesive layer can have higher heat resistance.

[0042] Examples of hydrogenated styrene-based elastomers include polystyrene-poly(ethylene / propylene) block copolymers (SEP), styrene-isoprene-styrene block copolymers (SIS), styrene-butadiene-styrene block copolymers (SBS), styrene-butadiene-butylene-styrene block copolymers (SBBS), and hydrogenated products thereof, such as styrene-ethylene-butylene-styrene block copolymers (SEBS), styrene-ethylene-propylene-styrene block copolymers (styrene-isoprene-styrene block copolymers) (SEPS), and hydrogenated products of styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS).

[0043] Examples of commercially available products that can be used as hydrogenated styrene-based elastomers include "Septon (product name)" manufactured by Kuraray Co., Ltd., "Hybler (product name)" manufactured by Kuraray Co., Ltd., "Tuftec (product name)" manufactured by Asahi Kasei Corporation, and "Dynaron (product name)" manufactured by JSR Corporation.

[0044] More specifically, for example, styrene-ethylene-ethylene-propylene-styrene block copolymers (SEEPS) include Septon 4033 (manufactured by Kuraray Co., Ltd.) and Septon 4044 (manufactured by Kuraray Co., Ltd.). As a reactive crosslinking type styrene-ethylene-butylene-styrene block copolymer having a reactive polystyrene-based hard block, Septon V9827 (manufactured by Kuraray Co., Ltd.) can be mentioned. As a polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modified), Septon HG252 (manufactured by Kuraray Co., Ltd.) can be mentioned. As a polystyrene-poly(ethylene / propylene) block copolymer (SEP), Septon 2004 (manufactured by Kuraray Co., Ltd.) can be mentioned. As a styrene-ethylene / butylene-styrene triblock copolymer (SEBS), Tuftec H1051 (manufactured by Asahi Kasei Chemicals Corporation) can be mentioned.

[0045] The hydrogenated styrene-based elastomer may further contain a (meth)acrylic acid ester.

[0046] The hydrogenated styrene elastomer contains a styrene unit as a structural unit of the main chain, and the "styrene unit" may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group.

[0047] The hydrogenated styrene elastomer preferably has a styrene unit content in the range of 14% by mass to 50% by mass, more preferably in the range of 17% by mass to 40% by mass. The hydrogenated styrene elastomer preferably has a mass average molecular weight in the range of 40,000 to 200,000.

[0048] A mixture of multiple hydrogenated styrene elastomers may be used. In this case, it is more preferable that at least one of the multiple hydrogenated styrene elastomers has a styrene unit content in the range of 14% by mass or more and 50% by mass or less, or a weight average molecular weight in the range of 40,000 to 200,000.

[0049] For example, when the adhesive contains multiple types of hydrogenated styrene-based elastomers, for example, when SEPTON 4033 (trade name) manufactured by Kuraray Co., Ltd., which has a styrene unit content of 30% by mass, and SEPTON 2063 (trade name) manufactured by Kuraray Co., Ltd., which has a styrene unit content of 13% by mass, are mixed in a mass ratio of 1:1, the styrene content of the entire elastomer contained in the adhesive is 21 to 22% by mass, and therefore 14% by mass or more. Also, for example, when a styrene unit containing 10% by mass and a styrene unit containing 60% by mass are mixed in a mass ratio of 1:1, the styrene content is 35% by mass, and the styrene unit content is in the range of 14% by mass or more and 50% by mass or less. The adhesive may be in such a form. It is preferable that the multiple types of hydrogenated styrene-based elastomers contained in the adhesive all contain styrene units within the above range and have a weight average molecular weight within the above range.

[0050] Thus, as long as the hydrogenated styrene-based elastomer has a styrene unit content in the range of 14% by mass or more and 50% by mass or less and a weight average molecular weight of the hydrogenated styrene-based elastomer in the range of 40,000 to 200,000 or less, it can be suitably removed by the stripping composition according to the present embodiment. By having the styrene unit content and weight average molecular weight in the above ranges, it is possible to exhibit excellent resistance to resist solvents (e.g., PGMEA, PGME, etc.), acids (hydrofluoric acid, etc.), and alkalis (TMAH, etc.) to which the wafer is exposed when subjected to a resist lithography process.

[0051] The content of the hydrogenated styrene-based elastomer in the adhesive is, for example, preferably in the range of 50 parts by mass or more and 99 parts by mass or less, more preferably in the range of 60 parts by mass or more and 99 parts by mass or less, and most preferably in the range of 70 parts by mass or more and 95 parts by mass or less, relative to 100 parts by mass of the total amount of the hydrogenated styrene-based elastomer and the added resin. By keeping the content within these ranges, the wafer and the support can be suitably bonded together while maintaining heat resistance.

[0052] [Added resin] The adhesive may contain at least one additive resin selected from the group consisting of a hydrocarbon resin, an acrylic-styrene resin, and a maleimide resin, which may adjust the adhesiveness of the adhesive layer formed by the adhesive.

[0053] Hydrocarbon resin The adhesive may include a hydrocarbon resin as an additive resin. The hydrocarbon resin has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. Examples of the hydrocarbon resin include, but are not limited to, a cycloolefin polymer (hereinafter also referred to as "resin (A)"), and at least one resin selected from the group consisting of a terpene resin, a rosin resin, and a petroleum resin (hereinafter also referred to as "resin (B)").

[0054] The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin-based monomer. Specific examples of the resin include a ring-opening (co)polymer of a monomer component containing a cycloolefin-based monomer, and a resin obtained by addition (co)polymerization of a monomer component containing a cycloolefin-based monomer.

[0055] Examples of the cycloolefin monomers contained in the monomer components constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and dihydroxypentadiene, tetracyclic compounds such as tetracyclododecene, pentacyclic compounds such as cyclopentadiene trimer, heptacyclic compounds such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.)-substituted compounds, alkenyl (vinyl, etc.)-substituted compounds, alkylidene (ethylidene, etc.)-substituted compounds, aryl (phenyl, tolyl, naphthyl, etc.)-substituted compounds of these polycyclic compounds. Among these, norbornene monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted compounds thereof are preferred.

[0056] The monomer component constituting the resin (A) may contain other monomers copolymerizable with the above-mentioned cycloolefin monomers, for example, may contain an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, and α-olefins. The alkene monomer may be linear or branched.

[0057] It is preferable that the monomer component constituting the resin (A) contains a cycloolefin monomer from the viewpoint of high heat resistance (low thermal decomposition, thermal weight loss). The ratio of the cycloolefin monomer to the entire monomer components constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 20 mol% or more. The ratio of the cycloolefin monomer to the entire monomer components constituting the resin (A) is not particularly limited, but from the viewpoint of solubility and stability over time in the solution, it is preferably 80 mol% or less, and more preferably 70 mol% or less.

[0058] Resin (A) may contain a linear or branched alkene monomer as a monomer component constituting resin (A). From the viewpoints of solubility and flexibility, the ratio of the alkene monomer to the total monomer components constituting resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, and even more preferably 30 to 80 mol%.

[0059] It is preferable that the resin (A) is a resin that does not have a polar group, such as a resin obtained by polymerizing a monomer component consisting of a cycloolefin monomer and an alkene monomer, in order to suppress gas generation at high temperatures.

[0060] The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be appropriately set according to conventional methods.

[0061] Commercially available products that can be used as the resin (A) include, for example, "TOPAS" manufactured by Polyplastics Co., Ltd., "APEL" manufactured by Mitsui Chemicals, Inc., "ZEONOR" and "ZEONEX" manufactured by Zeon Corporation, and "ARTON" manufactured by JSR Corporation.

[0062] As the resin (A), for example, a cycloolefin copolymer having a repeating unit represented by the following chemical formula (1) and a repeating unit represented by the following chemical formula (2) can be used as an additive resin for the adhesive.

[0063] [ka] [In the formula, n is 0 or an integer of 1 to 3.]

[0064] Examples of such cycloolefin copolymers include APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals, Inc.).

[0065] The glass transition temperature (Tg) of the resin (A) is preferably 60° C. or higher, and particularly preferably 70° C. or higher. When the glass transition temperature of the resin (A) is 60° C. or higher, lamination It is possible to suppress softening of the adhesive layer when the body is exposed to a high temperature environment.

[0066] Resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins, and petroleum resins. Specifically, examples of terpene resins include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, and hydrogenated terpene phenol resins. Examples of rosin resins include rosin, rosin esters, hydrogenated rosin, hydrogenated rosin esters, polymerized rosin, polymerized rosin esters, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and coumarone-indene petroleum resins. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferred.

[0067] The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160° C. When the softening point of the resin (B) is 80° C. or higher, the laminate can be prevented from softening when exposed to a high-temperature environment, and poor adhesion does not occur. On the other hand, when the softening point of the resin (B) is 160° C. or lower, the peeling speed when peeling the laminate is good.

[0068] The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the amount of degassing is reduced in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the peeling speed when peeling the laminate is good. Note that the weight average molecular weight of the resin (B) in this embodiment means the molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

[0069] The hydrocarbon resin may be a mixture of resin (A) and resin (B). By mixing, the heat resistance and peeling speed are improved. For example, the mixing ratio of resin (A) to resin (B) is preferably (A):(B)=80:20 to 55:45 (mass ratio), which is excellent in peeling speed, heat resistance in a high-temperature environment, and flexibility.

[0070] Acrylic-styrene resin The additive resin may be an acrylic-styrene resin, such as a resin polymerized using styrene or a derivative of styrene and a (meth)acrylic acid ester as a monomer.

[0071] Examples of (meth)acrylic acid esters include (meth)acrylic acid alkyl esters having a chain structure, (meth)acrylic acid esters having an aliphatic ring, and (meth)acrylic acid esters having an aromatic ring. Examples of (meth)acrylic acid alkyl esters having a chain structure include acrylic long-chain alkyl esters having an alkyl group with 15 to 20 carbon atoms, and acrylic alkyl esters having an alkyl group with 1 to 14 carbon atoms. Examples of acrylic long-chain alkyl esters include alkyl esters of acrylic acid or methacrylic acid in which the alkyl group is an n-pentadecyl group, an n-hexadecyl group, an n-heptadecyl group, an n-octadecyl group, an n-nonadecyl group, an n-eicosyl group, or the like. The alkyl group may be branched.

[0072] Examples of acrylic alkyl esters having an alkyl group with 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives, such as alkyl esters of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, an ethyl group, a propyl group, a butyl group, a 2-ethylhexyl group, an isooctyl group, an isononyl group, an isodecyl group, a dodecyl group, a lauryl group, or a tridecyl group.

[0073] Examples of (meth)acrylic acid esters having an aliphatic ring include cyclohexyl (meth)acrylic acid. acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, dicyclopentanyl (meth)acrylate, etc. Among them, isobornyl (meth)acrylate and dicyclopentanyl (meth)acrylate are preferred.

[0074] The (meth)acrylic acid ester having an aromatic ring is not particularly limited, but examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, an anthracenyl group, a phenoxymethyl group, and a phenoxyethyl group. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

[0075] Maleimide resin As the additive resin, a maleimide resin may be used. The maleimide resin is a resin having a repeating unit having a maleimide skeleton. Examples of the maleimide resin include a monomer having an alkyl group such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, and N-stearylmaleimide. maleimides having a cyclic aliphatic hydrocarbon group, such as N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, and N-cyclooctylmaleimide; and aromatic maleimides having an aryl group, such as N-phenylmaleimide, Nm-methylphenylmaleimide, No-methylphenylmaleimide, and Np-methylphenylmaleimide.

[0076] [Release Agent] The adhesive may include a release agent, which may adjust the adhesion of the adhesive layer to the substrate and support.

[0077] [Other ingredients] In addition to the above components, the adhesive may contain other compatible substances, such as plasticizers, adhesive assistants, stabilizers, colorants, thermal polymerization inhibitors, surfactants, diluting solvents, and other commonly used additives.

[0078] As described above, the stripping composition according to this embodiment contains limonene and component (A): a hydrocarbon that may have a substituent and has a boiling point of 200° C. or higher. By using limonene and component (A) in combination, the generation of volatile organic compounds (VOCs) can be further suppressed, and a sufficient cleaning effect can be obtained for adhesives. For example, the stripping composition according to the present embodiment can reduce the amount of VOCs generated compared to the case where limonene is contained alone, and the stripping composition according to the present embodiment can improve the cleaning properties for adhesives compared to the case where p-menthane is contained alone.

[0079] (How to remove adhesive) A second aspect of the present invention is a method for peeling an adhesive from a substrate to which the adhesive is attached, comprising the step of contacting the peeling composition according to the first aspect with the adhesive to dissolve the adhesive.

[0080] 1A and 1B are schematic process diagrams illustrating one embodiment of a method for peeling off an adhesive. FIG. 1A is a diagram illustrating an example of a dissolving step. An adhesive layer 3 made of an adhesive is attached to a substrate 1 shown in FIG. 1A. In FIG. 1A, a peeling composition 30 according to the first aspect is sprayed from a spray 20, and the peeling composition 30 is brought into contact with the adhesive layer 3 to dissolve the adhesive layer 3. FIG. 1B shows the substrate 1 from which the adhesive layer 3 has been removed.

[0081] [Dissolution process] As shown in Fig. 1A, in the dissolving step, a peeling composition 30 is brought into contact with an adhesive layer 3 to dissolve the adhesive layer 3. The adhesive layer 3 is formed from an adhesive. Examples of the adhesive include the adhesives exemplified above.

[0082] In the example of Fig. 1A, in the dissolving step, the peeling composition 30 is sprayed by the spray 20 to contact the adhesive layer 3. By spraying the peeling composition 30 by the spray 20, the peeling composition 30 can be brought into contact with the adhesive layer 3. This makes it possible to wash away the residue of the adhesive layer 3 adhering to the substrate 1, and to more suitably clean the substrate 1.

[0083] The spray 20 typically includes a two-fluid spray nozzle.

[0084] In the method for peeling an adhesive of the present embodiment, the peeling composition 30 according to the first aspect is used to dissolve the adhesive attached to the substrate, so that the adhesive layer 3 can be quickly dissolved while further suppressing the generation of VOCs.

[0085] [Optional process] The method for peeling off an adhesive of the present embodiment may include other steps in addition to the dissolving step. Examples of the other steps include a separation step.

[0086] [Separation process] The method of the present embodiment may include, prior to the dissolving step, a separation step of separating the support from a laminate in which the support, the adhesive layer, and the substrate are laminated in this order. An example of a separation process is a process in which the support comprises a support base made of a light-transmitting material and a separation layer that is altered by irradiation with light, the separation layer being disposed between the support base and the adhesive layer, and the separation layer is altered by irradiating light through the support base to separate the support from the laminate.

[0087] 2A to 2D are schematic process diagrams illustrating an example of the separation process. 2A includes a support 24 consisting of a supporting base 2 and a separation layer 4, in addition to a substrate 1 and an adhesive layer 3. In the laminate 10, the substrate 1, the adhesive layer 3, and the support 24 are laminated in this order. The adhesive layer 3 and the separation layer 4 are adjacent to each other. FIG. 2B is a diagram showing light (arrow) being irradiated onto separation layer 4 through support base 2. FIG. 2C shows a state in which the separation layer 4 has been altered by light irradiation to become an altered separation layer 4' and an altered support 24'. FIG. 2D shows a state in which the supporting base 2 has been separated from the laminate 10.

[0088] The separation layer 4 shown in Fig. 2A is made of a material that changes its properties when irradiated with light, and is disposed between the support 2 and the adhesive layer 3. The support base 2 is made of a material that transmits light. Therefore, as shown in Fig. 2B, the separation layer 4 can be changed by irradiating light to the separation layer 4 through the support base 2.

[0089] In this specification, the term "alteration" of the separation layer refers to a phenomenon in which the separation layer is in a state where it can be destroyed by a slight external force, or where the adhesive strength between the separation layer and a layer in contact with the separation layer is reduced. The alteration of the separation layer may be (exothermic or non-exothermic) decomposition, crosslinking, change in configuration, or dissociation of functional groups due to the absorbed light energy (and the accompanying hardening, degassing, contraction, or expansion of the separation layer), etc.

[0090] In this way, by modifying the separation layer 4, it is possible to obtain a modified separation layer 4', which reduces the adhesive strength of the separation layer 4 (FIG. 2C). Therefore, by applying a slight force to the laminate 10, it becomes possible to separate the modified support 24' (or supporting base 2) from the laminate 10 (FIG. 2D). In this specification, the expression "separating the support from the laminate" includes separating the support base 2 from the laminate 10. It also includes the case where residues of the altered separation layer 4' remain on the laminate 10.

[0091] Therefore, after the altered support 24' is separated from the laminate 10, in the dissolution process, it becomes possible to suitably bring the peeling composition of the first embodiment into contact with the adhesive layer 3 attached to the substrate 1.

[0092] The laser light irradiation conditions in the separation step may be appropriately adjusted depending on the type of separation layer, and are not particularly limited. For example, the average output value of the laser light is preferably in the range of 1.0W or more and 5.0W or less, and more preferably in the range of 3.0W or more and 4.0W or less. The repetition frequency of the laser light is preferably in the range of 20kHz or more and 60kHz or less, and more preferably in the range of 30kHz or more and 50kHz or less. The wavelength of the laser light is preferably in the range of 300nm or more and 700nm or less, and more preferably in the range of 450nm or more and 650nm or less. According to such conditions, the energy of the pulse light irradiated to the separation layer 4 can be made to be an appropriate condition for altering the separation layer 4. Therefore, it is possible to prevent the substrate 1 from being damaged by the laser light.

[0093] Moreover, the beam spot diameter of the pulsed light and the irradiation pitch of the pulsed light may be any pitch that prevents adjacent beam spots from overlapping and allows the separation layer 4 to be altered.

[0094] [Each component of the laminate] Next, each component of the laminate 10 in FIG. 2A will be described.

[0095] 〔substrate〕 The substrate (bare chip) is supported by a support and is subjected to processes such as thinning, mounting, etc. Structures such as integrated circuits and metal bumps are mounted on the substrate. The substrate is typically a silicon wafer substrate, but is not limited thereto, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

[0096] The substrate may be a semiconductor element or other element, and may have a single-layer or multi-layer structure. When the substrate is a semiconductor element, the electronic component obtained by dicing the device layer is a semiconductor device. Preferably, the substrate is a semiconductor element.

[0097] [Adhesive layer] The adhesive layer 3 in the laminate 10 in Fig. 2A is a dried adhesive. Examples of the adhesive include those described in the <<Adhesive>> section of the peeling composition above. The thickness of the adhesive layer 3 is preferably, for example, in the range of 1 µm or more and 200 µm or less, and more preferably in the range of 5 µm or more and 150 µm or less.

[0098] [Support] The support is a member that supports the substrate, and the substrate is fixed onto the support via an adhesive layer. In the example of Fig. 2A, the support 24 includes a support base 2 and a separation layer 4 provided on the support base 2. When the separation layer 4 is not provided, the support base 2 serves as the support.

[0099] ≪Supporting base≫ The supporting base is a member that has a property of transmitting light and supports the substrate. When a separation layer is provided as in FIG. 2A, the supporting base is bonded to the substrate via the separation layer and the adhesive layer. When no separation layer is provided, the supporting base is bonded to the substrate via the adhesive layer. Therefore, the supporting base preferably has a strength required to prevent damage or deformation of the substrate during thinning of the device, transportation of the substrate, mounting on the substrate, etc. In addition, the supporting base preferably transmits light of a wavelength that can alter the separation layer. Examples of the material of the support base include glass, silicon, acrylic resin, etc. Examples of the shape of the support base include, but are not limited to, rectangular and circular. In order to achieve higher density integration and improve production efficiency, the support base may be a circular support base with a larger size, or a large panel with a rectangular shape in plan view.

[0100] ≪Separation layer≫ The separation layer is adjacent to the adhesive layer and is altered by irradiation with light to enable separation of the supporting base from the substrate attached to the support. This separation layer can be formed using a composition for forming a separation layer described later, for example, by firing the components contained in the composition for forming a separation layer or by a chemical vapor deposition (CVD) method. This separation layer is suitably altered by absorbing light irradiated through the support substrate. The separation layer is preferably formed only from a material that absorbs light, but may also be a layer containing a material that does not have a structure that absorbs light.

[0101] The thickness of the separation layer is preferably, for example, in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer is in the range of 0.05 μm or more and 50 μm or less, the desired alteration can be caused in the separation layer by short-time light irradiation and low-energy light irradiation. In addition, from the viewpoint of productivity, the thickness of the separation layer is particularly preferably in the range of 1 μm or less.

[0102] It is preferable that the surface of the separation layer that contacts the adhesive layer is flat (having no irregularities formed thereon), which makes it easy to form the adhesive layer and to uniformly attach the substrate or wiring layer to the supporting base.

[0103] ·Composition for forming separation layer The separation layer forming composition, which is a material for forming the separation layer, may contain, for example, a fluorocarbon, a polymer having a repeating unit including a structure having light absorption properties, an inorganic substance, a compound having an infrared absorbing structure, an infrared absorbing substance, a reactive polysilsesquioxane, or a resin component having a phenol skeleton. In addition, the composition for forming the separation layer may contain, as optional components, a filler, a plasticizer, a thermal acid generator component, a photoacid generator component, an organic solvent component, a surfactant, a sensitizer, or a component that can improve the separability of the supporting substrate.

[0104] Fluorocarbon The separation layer may contain fluorocarbon. The separation layer made of fluorocarbon is adapted to change its properties by absorbing light, and as a result, loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (e.g., lifting the support, etc.), the separation layer is destroyed, making it easy to separate the support from the substrate or wiring layer. The fluorocarbon constituting the separation layer can be suitably formed into a film by the plasma CVD method. Each type of fluorocarbon absorbs light having a specific range of wavelengths. By irradiating the separation layer with light having a wavelength in the range absorbed by the fluorocarbon used in the separation layer, the fluorocarbon can be suitably altered. The light absorptance of the separation layer is preferably 80% or more.

[0105] The light to be irradiated to the separation layer may be, depending on the wavelength that can be absorbed by the fluorocarbon, a solid-state laser such as a YAG laser, a ruby ​​laser, a glass laser, a YVO4 laser, an LD laser, or a fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, an excimer laser, an Ar laser, or a He-Ne laser, a semiconductor laser, a free electron laser, or a non-laser light. The wavelength that can alter the fluorocarbon may be, for example, a wavelength in the range of 600 nm or less.

[0106] Polymer having a repeating unit containing a structure having light absorption The separating layer may contain a polymer having a repeating unit including a structure having light absorbing properties, the polymer being altered when irradiated with light. Examples of the light-absorbing structure include an atomic group containing a conjugated π-electron system consisting of a substituted or unsubstituted benzene ring, a fused ring, or a heterocyclic ring. More specifically, examples of the light-absorbing structure include a cardo structure, or a benzophenone structure, a diphenylsulfoxide structure, a diphenylsulfone structure (bisphenylsulfone structure), a diphenyl structure, or a diphenylamine structure present in the side chain of the polymer. The light absorbing structure can absorb light having a wavelength in a desired range depending on the type of the structure. For example, the wavelength of light that can be absorbed by the light absorbing structure is preferably within the range of 100 to 2000 nm, and more preferably within the range of 100 to 500 nm.

[0107] Examples of light that can be absorbed by the above-mentioned light-absorbing structure include light emitted from a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F2 excimer laser (wavelength 157 nm), a XeCl laser (wavelength 308 nm), a XeF laser (wavelength 351 nm) or a solid-state UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line (wavelength 365 nm).

[0108] ·Inorganic matter The separation layer may be made of an inorganic material. The inorganic material may be any material that changes its properties by absorbing light, and may be, for example, one or more materials selected from the group consisting of metals, metal compounds, and carbon. The metal compounds are compounds containing metal atoms, and examples of such compounds include metal oxides and metal nitrides. Such inorganic substances include one or more selected from the group consisting of gold, silver, copper, iron, nickel, aluminum, titanium, chromium, SiO2, SiN, Si3N4, TiN, and carbon. Incidentally, carbon is a concept which may include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like. Each of the inorganic substances absorbs light having a specific range of wavelengths depending on the type of inorganic substance.

[0109] The light to be irradiated to the separation layer made of an inorganic material may be, for example, a solid laser such as a YAG laser, a ruby ​​laser, a glass laser, a YVO4 laser, an LD laser, or a fiber laser; a liquid laser such as a dye laser; a gas laser such as a CO2 laser, an excimer laser, an Ar laser, or a He-Ne laser; a semiconductor laser; a free electron laser; or a non-laser light, depending on the wavelength that can be absorbed by the inorganic material. The separation layer made of an inorganic material can be formed on the supporting substrate by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, and spin coating.

[0110] Compounds with infrared absorbing structures The separating layer may contain a compound having an infrared absorbing structure, which is altered by absorbing infrared rays. Examples of structures having infrared absorbing properties or compounds having such structures include alkanes, alkenes (vinyl, trans, cis, vinylidene, tri-substituted, tetra-substituted, conjugated, cumulenic, cyclic), alkynes (mono-substituted, di-substituted), monocyclic aromatics (benzene, mono-substituted, di-substituted, tri-substituted), alcohols or phenols (free OH, intramolecular hydrogen bond, intermolecular hydrogen bond, saturated secondary, saturated tertiary, unsaturated secondary, unsaturated tertiary), acetals, ketals, aliphatic ethers, aromatic ethers, vinyl ethers, oxirane ring ethers, peroxide ethers, ketones, dialkyl carbonyls, aromatic carbonyls, enols of 1,3-diketones, o-hydroxyaryl ketones, dialkyl aldehydes, aromatic aldehydes, carboxylic acids (dimers, carboxylate anions), formates, acetates, conjugated esters, non-conjugated esters, aromatic esters, lactones (β-, γ-, δ-), aliphatic acid chlorides, aromatic acid salts. compounds, acid anhydrides (conjugated, non-conjugated, cyclic, acyclic), primary amides, secondary amides, lactams, primary amines (aliphatic, aromatic), secondary amines (aliphatic, aromatic), tertiary amines (aliphatic, aromatic), primary amine salts, secondary amine salts, tertiary amine salts, ammonium ions, aliphatic nitriles, aromatic nitriles, carbodiimides, aliphatic isonitriles, aromatic isonitriles, isocyanates, thiocyanates, aliphatic isothiocyanates, aromatic isothiocyanates, aliphatic nitro compounds, aromatic nitro compounds, nitroamines, nitrosamines, nitrates, nitrites, nitroso bonds (aliphatic, aromatic, monomers, dimers), sulfur compounds such as mercaptans, thiophenols, or thiolic acids, thiocarbonyl groups, sulfoxides, sulfones, sulfonyl chlorides, primary sulfonamides, secondary sulfonamides, sulfates, carbon-halogen bonds, Si-A 1 Join(A 1 is H, C, O or halogen), PA 2 Join(A 2 is H, C or O) or Ti-O bond.

[0111] Examples of the structure containing the carbon-halogen bond include -CH2Cl, -CH2Br, -CH2I, -CF2-, -CF3, -CH=CF2, -CF=CF2, aryl fluoride, and aryl chloride.

[0112] The above Si-A 1 Examples of structures containing bonds include SiH, SiH2, SiH3, Si-CH3, Si-CH2-, Si-C6H5, SiO-aliphatic, Si-OCH3, Si-OCH2CH3, Si-OC6H5, Si-O-Si, Si-OH, SiF, SiF2, and SiF3. Si-A 1 As the structure containing bonds, it is particularly preferable that a siloxane skeleton or a silsesquioxane skeleton is formed.

[0113] The above P.A. 2 Examples of structures containing bonds include PH, PH2, P-CH3, P-CH2-, P-C6H5, and A 3 3-PO(A 3 is an aliphatic group or an aromatic group), (A 4 O)3-PO(A 4 is an alkyl group), P-OCH3, P-OCH2CH3, P-OC6H5, POP, P-OH or O=P-OH.

[0114] Examples of the compounds containing the Ti-O bond include (i) alkoxy titanium such as tetra-i-propoxy titanium, tetra-n-butoxy titanium, tetrakis(2-ethylhexyloxy) titanium, and titanium-i-propoxyoctylene glycolate; (ii) chelate titanium such as di-i-propoxy bis(acetylacetonato) titanium and propanedioxy titanium bis(ethylacetoacetate); and (iii) i-C3H7O-[-Ti(Oi-C3H7)2-O-]. n -i-C3H7 or n-C4H9O-[-Ti(On-C4H9)2-O-] n(iv) titanium acylates such as tri-n-butoxytitanium monostearate, titanium stearate, di-i-propoxytitanium diisostearate, and (2-n-butoxycarbonylbenzoyloxy)tributoxytitanium; and (v) water-soluble titanium compounds such as di-n-butoxy bis(triethanolaminato)titanium. Among these, di-n-butoxy bis(triethanolaminato)titanium (Ti(OC4H9)2[OC2H4N(C2H4OH)2]2) is preferred as a compound containing a Ti-O bond.

[0115] The infrared absorbing structure can absorb infrared rays having a wavelength in a desired range by selecting the type thereof. Specifically, the infrared absorbing structure can absorb infrared rays having a wavelength in the range of, for example, 1 to 20 μm, and more preferably in the range of 2 to 15 μm. Furthermore, when the above structure is a Si-O bond, a Si-C bond or a Ti-O bond, the thickness is preferably within the range of 9 to 11 μm.

[0116] Those skilled in the art can easily understand the infrared wavelengths that each of the above structures can absorb. For example, the absorption bands of each structure can be found in the non-patent literature "Spectroscopic Identification of Organic Compounds (5th Edition) -Combined Use of MS, IR, NMR, and UV-" (published in 1992) (pp. 146 to 151).

[0117] The compound having an infrared absorbing structure used for forming the separation layer is not particularly limited as long as it can be dissolved in a solvent for coating and can be solidified to form a solid layer among the compounds having the above-mentioned structure.However, in order to effectively change the compound in the separation layer and facilitate the separation between the support base and the substrate, it is preferable that the absorption of infrared rays in the separation layer is large, that is, the transmittance of infrared rays when the separation layer is irradiated with infrared rays is low.Specifically, it is preferable that the transmittance of infrared rays in the separation layer is lower than 90%, and more preferably the transmittance of infrared rays is lower than 80%.

[0118] Infrared absorbing material The separating layer may contain an infrared absorbing material. The infrared absorbing material may be any material that changes its properties by absorbing light, and suitable examples of the infrared absorbing material include carbon black, iron particles, and aluminum particles. Each type of infrared absorbing material absorbs light having a specific range of wavelengths. By irradiating the separation layer with light having a wavelength within the range absorbed by the infrared absorbing material used in the separation layer, the infrared absorbing material can be suitably altered.

[0119] Reactive polysilsesquioxane The separation layer can be formed by polymerizing a reactive polysilsesquioxane, which has high chemical resistance and high heat resistance.

[0120] "Reactive polysilsesquioxane" refers to a polysilsesquioxane having a silanol group or a functional group capable of forming a silanol group by hydrolysis at the end of the polysilsesquioxane skeleton. The silanol groups or the functional groups capable of forming a silanol group can be polymerized with each other by condensing them. In addition, as long as the reactive polysilsesquioxane has a silsesquioxane skeleton having a random structure, a cage structure, a ladder structure, or the like, it is possible to adopt a reactive polysilsesquioxane having a silsesquioxane skeleton having a silanol group or a functional group capable of forming a silanol group.

[0121] The siloxane content of the reactive polysilsesquioxane is preferably from 70 to 99 mol %, and more preferably from 80 to 99 mol %. When the siloxane content of the reactive polysilsesquioxane is within the above-mentioned preferred range, a separation layer can be formed that can be suitably altered by irradiation with infrared rays (preferably far infrared rays, more preferably light with a wavelength of 9 to 11 μm).

[0122] The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500 to 50,000, and more preferably 1,000 to 10,000. When the weight average molecular weight (Mw) of the reactive polysilsesquioxane is within the above-mentioned preferred range, it can be suitably dissolved in a solvent and can be suitably applied onto a supporting substrate.

[0123] Examples of commercially available reactive polysilsesquioxanes that can be used include SR-13, SR-21, SR-23, and SR-33 (trade names) manufactured by Konishi Chemical Industry Co., Ltd.

[0124] Resin components with phenolic skeleton The separation layer may contain a resin component having a phenol skeleton, which is easily altered (oxidized, etc.) by heating or the like, thereby increasing the photoreactivity. The term "having a phenol skeleton" as used herein means that it contains a hydroxybenzene structure. The resin component having a phenol skeleton has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the resin component is 1000 or more, the film-forming ability is improved. The molecular weight of the resin component is more preferably 1000 to 30000, further preferably 1500 to 20000, and particularly preferably 2000 to 15000. When the molecular weight of the resin component is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the separation layer-forming composition in a solvent is increased. The molecular weight of the resin component is determined by polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

[0125] Examples of the resin component having a phenol skeleton include novolac-type phenol resins, resol-type phenol resins, hydroxystyrene resins, hydroxyphenylsilsesquioxane resins, hydroxybenzylsilsesquioxane resins, acrylic resins containing a phenol skeleton, resins having a repeating unit represented by the general formula (P2) described below, etc. Among these, novolac-type phenol resins and resol-type phenol resins are more preferred.

[0126] In the laminate 10 of FIG. 2A, the support base 2 and the separation layer 4 are adjacent to each other, but this is not limited thereto, and other layers may be formed between the support base 2 and the separation layer 4. In this case, the other layers may be made of a material that transmits light. This allows layers that impart desirable properties to the laminate to be added as appropriate without preventing the incidence of light into the separation layer 4. The wavelength of light that can be used varies depending on the type of material that constitutes the separation layer 4. Therefore, the material that constitutes the other layers does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of wavelengths that can alter the material that constitutes the separation layer 4.

[0127] The method for peeling off the adhesive of the present embodiment is not limited to the above embodiment. For example, the support may be composed of only the support base without including the separation layer.

[0128] In this case, the dissolving step is carried out, for example, by contacting the peeling composition according to the first embodiment with the adhesive layer in a laminate in which a support base, an adhesive layer and a substrate are laminated in this order. This allows the adhesive layer to be suitably dissolved and removed by the peeling composition according to the first embodiment. Therefore, even if the laminate does not have a separation layer, the dissolving step can separate the support base from the laminate and remove the adhesive residue from the substrate.

[0129] Also, for example, a support base having a plurality of through holes penetrating in the thickness direction may be used as the support base. In this case, the adhesive layer of the laminate is dissolved by carrying out a step (dissolving step) of contacting the peeling composition according to the first embodiment with the adhesive layer through the plurality of through holes provided in the support base, and the support base can be separated from the laminate. Thereafter, the adhesive layer remaining on the substrate is contacted with the peeling composition according to the first embodiment to dissolve the adhesive layer, thereby removing the adhesive residue from the substrate.

[0130] The method for peeling off the adhesive of this embodiment may be another embodiment. For example, a part of the outer periphery of the adhesive layer in the laminate is removed by a blade or the like, and then an organic solvent such as ethanol is supplied to the part from which the adhesive layer 3 has been removed by the blade. Thereafter, for example, the substrate in the laminate is fixed, and the supporting base is held by a holding means such as a clamp and a force is applied to the laminate, so that the supporting base is separated from the laminate.

[0131] In the above method, since an organic solvent such as ethanol is supplied to the portion from which the adhesive layer has been removed by the blade, the adhesiveness of the portion from which the adhesive layer has been partially removed in the laminate can be reduced, and therefore the force can be suitably concentrated on the portion from which the adhesive layer has been partially removed.

[0132] In addition, the adhesive layer can be formed using an adhesive containing a release agent, thereby adjusting the adhesiveness of the adhesive layer, which allows the support base to be easily separated from the substrate without applying excessive force to the laminate.

[0133] After the supporting base is separated from the laminate as described above, a step (dissolving step) of contacting the adhesive layer remaining on the substrate with the peeling composition according to the first embodiment is carried out, whereby the adhesive layer can be dissolved and the residue derived from the adhesive can be removed from the substrate.

[0134] As described above, the method for peeling off the adhesive according to the present embodiment is not particularly limited as long as the peeling composition according to the first aspect can be brought into contact with the adhesive layer formed using the adhesive in the dissolving step, and the method for separating the support (support base) from the substrate is not particularly limited. EXAMPLES

[0135] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0136] <Preparation of Stripping Composition> (Examples 1 to 6, Comparative Examples 1 to 9) The following components were used to prepare the stripping composition of each example, as shown in Tables 1 and 2. The numerical values ​​for each component shown in Tables 1 and 2 indicate the content (mass %) in the composition.

[0137] D-Limonene: CAS registration number 5989-27-5, boiling point 176°C; manufactured by Yasuhara Chemical Co., Ltd.

[0138] ISOPAR TM M: Paraffin, CAS registration number 125-12-2, boiling point 227-254°C; manufactured by ExxonMobil.

[0139] Naphtesol Grade 200: Naphthene, CAS registration number 64742-47-8, boiling point 201-217°C; manufactured by ENEOS Corporation. Naphthesol Grade 220: Naphthene, CAS registration number 64742-47-8, boiling point 221-240°C; manufactured by ENEOS Corporation.

[0140] Dihydroterpinyl acetate: terpene, CAS registration number 58985-18-5, boiling point 220-225°C; manufactured by Nippon Terpene Chemical Co., Ltd.

[0141] p-Menthane: CAS registration number 99-82-21, boiling point 168°C; manufactured by Nippon Terpene Chemical Co., Ltd.

[0142] <Measurement of Volatile Organic Compounds (VOC)> 20 mL of the stripping composition of each example was placed in a 50 mL beaker, and the beaker was covered with a 2 L plastic container. The beaker was then left to stand for 30 seconds to fill with steam from the stripping composition. After that, the measurement nozzle of a VOC gas detector "Miniray 3000+" (manufactured by Honeywell) was inserted into a hole previously made in the plastic container, and VOC measurements were performed. The VOC value stabilized about 30 seconds after the start of measurement, and this value was recorded as the amount of VOC generated. The results are shown in Tables 1 to 2 as "VOC (ppm)".

[0143] <Evaluation of adhesive solubility> (Preparation of Adhesive Composition) A resin mixture was obtained by mixing 90 parts by mass of Septon (trade name) HG252 (hydrogenated styrene-based elastomer; manufactured by Kuraray Co., Ltd., SEEPS-OH; polystyrene-poly(ethylene-ethylene / propylene) block-polystyrene terminal hydroxyl group modified) and 10 parts by mass of acrylic resin A1. The resin mixture was then dissolved in a mixed solvent of 80 parts by mass of decahydronaphthalene and 20 parts by mass of butyl acetate to a concentration of 25% by mass. Next, 1 part by mass of IRGANOX (trade name) 1010 (manufactured by BASF) was added to 100 parts by mass of the resin mixture, and 20 parts by mass of butyl acetate was mixed with 80 parts by mass of decahydronaphthalene in which the resin mixture was dissolved to obtain an adhesive composition.

[0144] Acrylic resin A1 (Mw=10,000) is a random polymer having the following structure (wherein l / m / n=60 / 20 / 20 molar ratio).

[0145] [ka]

[0146] (evaluation) The adhesive composition prepared as above was applied onto a silicon substrate by a spin coater method, and baked on a hot plate under atmospheric pressure at 100°C, 160°C, and 220°C for 4 minutes each to form an adhesive layer with a thickness of 50 μm. The silicon substrate with the adhesive layer formed thereon was immersed in the peeling composition of each example, and the dissolution rate of the adhesive layer was measured at 23°C. The results are shown in Tables 1 to 2 as "dissolution rate (nm / sec)".

[0147] [Table 1]

[0148] [Table 2]

[0149] From the results shown in Tables 1 and 2, it was confirmed that the stripping compositions of Examples 1 to 6 suppressed the generation of VOCs and had sufficient cleaning properties for adhesives.

[0150] On the other hand, the stripping compositions of Comparative Examples 1 to 4 suppressed the generation of VOCs, but had poor solubility of the adhesive layer. Although the stripping compositions of Comparative Examples 6, 7, and 9 suppressed the generation of VOCs, the solubility of the adhesive layer was inferior to that of the stripping composition of Comparative Example 5 (p-menthane). The stripping compositions of Comparative Examples 5 and 8 had good solubility in the adhesive layer, but did not sufficiently suppress the generation of VOCs. [Explanation of symbols]

[0151] 1 Board 2 Support base 3 Adhesive layer 4 separation layer 10 Laminate 20 Spray 30 Stripping composition

Claims

1. A stripping composition for stripping an adhesive, comprising: Limonene and Component (A): a hydrocarbon having a boiling point of 200° C. or higher, which may have a substituent; A stripping composition comprising:

2. 2. The stripping composition according to claim 1, wherein the component (A) is at least one selected from the group consisting of paraffins, naphthenes, and terpenes.

3. The component (A) contains paraffin, The stripping composition according to claim 2, wherein a mixing ratio of the limonene to the paraffin is 90 / 10 to 60 / 40 in terms of a mass ratio expressed as limonene / paraffin.

4. The component (A) contains naphthene, The stripping composition according to claim 2, wherein a mixing ratio of the limonene and the naphthene is 90 / 10 to 50 / 50 in terms of a mass ratio expressed as limonene / naphthene.

5. The component (A) contains terpenes, The stripping composition according to claim 2, wherein a mixing ratio of the limonene to the terpenes is 60 / 40 to 40 / 60 in terms of a mass ratio of limonene / terpenes.

6. 1. A method for removing an adhesive from a substrate to which the adhesive is attached, comprising the steps of: A dissolving step of contacting the peeling composition according to any one of claims 1 to 5 with the adhesive to dissolve the adhesive. How to remove adhesive.

7. The method further includes a separation step of separating the support from a laminate in which the support, the adhesive layer, and the substrate are laminated in this order before the dissolving step. The method for removing the adhesive of claim 6.

8. the support includes a support base made of a light-transmitting material and a separation layer that changes in quality when irradiated with light, the separation layer being disposed between the support base and the adhesive layer; The separation step is a step of irradiating the separation layer with light through the support base to alter the separation layer, and separating the support from the laminate. The method for removing the adhesive of claim 7.

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