JP7315376B2 - SUBSTRATE CLEANING METHOD, SUBSTRATE CLEANING APPARATUS, AND SUBSTRATE CLEANING KIT - Google Patents

Description

The present invention relates to a substrate cleaning method, a substrate cleaning apparatus, and a substrate cleaning kit.

2. Description of the Related Art In recent years, as an example of a method of manufacturing an electronic device, a method called a so-called fan-out PLP (Fan-out Panel Level Package) technology has been known. In the fan-out PLP technique, for example, a laminate is formed by laminating a substrate having electronic components on a support such as a glass plate via a separation layer that changes in quality due to light absorption or heating and an adhesive layer. It has been proposed to apply light or heat to the separation layer to change its properties after the laminate is treated, separate the substrate from the support, and remove the bonding layer adhering to the substrate (see, for example, Patent Document 1).

Japanese Patent Application Laid-Open No. 2004-064040

In Patent Document 1, the adhesive layer remaining on the substrate after separation of the support is removed with a cleaning liquid. Even if the adhesive layer is dissolved and removed with this cleaning liquid, the residue of the separation layer may remain without being washed away from the substrate. If the substrate remains with the residue of the separation layer, the quality of the finally obtained electronic device may be degraded.

SUMMARY OF THE INVENTION An object of the present invention is to provide a substrate cleaning method, a substrate cleaning apparatus, and a substrate cleaning kit capable of removing a residue of a separation layer from a substrate after separation of a support.

According to an embodiment of the present invention, there is provided a substrate cleaning method for changing the quality of the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, and cleaning the substrate separated from the support, comprising: a first cleaning step of cleaning the substrate with a first cleaning liquid in which a predetermined resin is dissolved in a first solvent capable of dissolving the adhesive layer; and a second cleaning step of cleaning the substrate with a second cleaning liquid having a second solvent capable of dissolving the adhesive layer after the first cleaning step, wherein the predetermined resin Provided is a method for cleaning a substrate in which the content is 3 to 5% by weight in one cleaning liquid, and the solid content concentration of the second cleaning liquid is 0.5% by weight or less.
According to an embodiment of the present invention, there is provided a substrate cleaning method for changing the quality of the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, and cleaning the substrate separated from the support, comprising: a first cleaning step of cleaning the substrate with a first cleaning liquid obtained by dissolving a predetermined amount of resin in an amount smaller than the content of a predetermined resin in the adhesive used for forming the adhesive layer in a first solvent capable of dissolving the adhesive layer; and a resin formed on the substrate by the adhesive layer and the predetermined resin after the first cleaning step. and a second cleaning step of cleaning the substrate with a second cleaning liquid having a solid content concentration of 0.5% by weight or less and containing a second solvent capable of dissolving the layer.
A first aspect of the present invention is a substrate cleaning method for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, comprising: a first cleaning step of cleaning the substrate with a first cleaning liquid in which a predetermined resin is dissolved in a first solvent capable of dissolving the adhesive layer; and a second cleaning step of cleaning the substrate with a second cleaning liquid having a second solvent capable of dissolving the adhesive layer after the first cleaning step. provided.

According to an aspect of the present invention, there is provided a substrate cleaning apparatus for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, comprising: a first cleaning unit for cleaning the substrate with a first cleaning liquid in which a predetermined resin is dissolved in a first solvent capable of dissolving the adhesive layer; A substrate cleaning apparatus is provided in which one cleaning liquid contains 3 to 5% by weight, and the second cleaning liquid has a solid content concentration of 0.5% by weight or less.
According to an aspect of the present invention, a substrate cleaning apparatus for cleaning a substrate separated from a support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, the first cleaning unit cleaning the substrate with a first cleaning liquid obtained by dissolving a predetermined amount of resin in an amount smaller than the content of the predetermined resin in the adhesive used for forming the adhesive layer in a first solvent capable of dissolving the adhesive layer; A substrate cleaning apparatus is provided, comprising: a second cleaning section for cleaning a substrate with a second cleaning liquid having a solid content concentration of 0.5% by weight or less, which contains a second solvent capable of dissolving a layer.
In a second aspect of the present invention, there is provided a substrate cleaning apparatus for cleaning the substrate separated from the support by changing the quality of the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, the substrate cleaning apparatus comprising: a first cleaning section for cleaning the substrate with a first cleaning liquid in which a predetermined resin is dissolved in a first solvent capable of dissolving the adhesive layer; and a second cleaning section for cleaning the substrate with a second cleaning liquid having a second solvent capable of dissolving the adhesive layer after the first cleaning step. provided.

According to an aspect of the present invention, there is provided a substrate cleaning kit for altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, and cleaning the substrate separated from the support, the kit comprising: a first cleaning liquid for cleaning the substrate by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer; is contained in the first cleaning liquid in an amount of 3 to 5% by weight, and the second cleaning liquid has a solid content concentration of 0.5% by weight or less.
According to an aspect of the present invention, there is provided a substrate cleaning kit for altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, and cleaning the substrate separated from the support, wherein a first solvent capable of dissolving the adhesive layer is dissolved in a predetermined resin in an amount smaller than the content of the predetermined resin in the adhesive used for forming the adhesive layer, and a first cleaning liquid for cleaning the substrate is used after cleaning with the first cleaning liquid, and the adhesive layer and the predetermined resin are used on the substrate. A substrate cleaning kit is provided, comprising a second cleaning liquid for cleaning the substrate, the second solvent having a solid content concentration of 0.5% by weight or less capable of dissolving the resin layer formed on the substrate.
In a third aspect of the present invention, there is provided a substrate cleaning kit for altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order, and cleaning the substrate separated from the support, the kit comprising: a first cleaning liquid for cleaning the substrate by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer; A substrate cleaning kit is provided.

According to the aspect of the present invention, the residue of the separation layer can be removed from the substrate after separation of the support. As a result, quality deterioration of the electronic device can be prevented.

4 is a flowchart including an example of a substrate cleaning method according to an embodiment; It is a figure which shows 1 process of the manufacturing method of an electronic device. FIG. 3 is a diagram following FIG. 2 showing one step of the method for manufacturing the electronic device; FIG. 4 is a diagram following FIG. 3 showing one step of the method for manufacturing the electronic device; FIG. 5 is a diagram following FIG. 4 showing one step of the method for manufacturing the electronic device; FIG. 6 is a diagram following FIG. 5 showing a step of the method for manufacturing the electronic device; FIG. 7 is a diagram subsequent to FIG. 6 showing one step of the method for manufacturing the electronic device; FIG. 8 is a diagram following FIG. 7 showing a step of the method for manufacturing the electronic device; It is a figure which shows a 1st washing|cleaning process. It is a figure which shows the state of the board|substrate after a 1st washing|cleaning process. It is a figure which shows a 2nd washing|cleaning process. It is a figure which shows the state of the board|substrate after a 2nd washing|cleaning process. It is a figure which shows an example of the substrate cleaning apparatus which concerns on embodiment. It is a figure which shows the other example of the substrate cleaning apparatus which concerns on embodiment.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described with reference to the drawings. However, the invention is not limited to this embodiment. In addition, in the drawings, in order to make each configuration of the embodiment easier to understand, some parts are enlarged or emphasized, or some parts are simplified, and the actual structure, shape, scale, etc. may differ.

<Substrate cleaning method>
FIG. 1 is a flowchart including an example of a substrate cleaning method according to an embodiment. The flowchart of FIG. 1 shows an example of an electronic device manufacturing method including an example of a substrate cleaning method according to an embodiment. In this embodiment, a method for manufacturing an electronic device by so-called fan-out PLP technology will be described as an example. As shown in FIG. 1, the electronic device manufacturing method includes a separation layer forming step (step S01), an adhesive layer forming step (step S02), a substrate forming step (step S03), a mold polishing step (step S04), a separation layer deterioration step (step S05), a support peeling step (step S06), a first cleaning step (step S07), and a second cleaning step (step S08).

The first cleaning process (step S07) and the second cleaning process (step S08) in FIG. 1 show an example of the substrate cleaning method according to the embodiment. The separation layer forming step (step S01), the adhesive layer forming step (step S02), the substrate forming step (step S03), and the mold polishing step (step S04) are for forming the laminate 100. FIG. A laminate 100 is a structure in which a support 1, a separation layer 2, an adhesive layer 3, and a substrate 4 are laminated in this order (see FIG. 6). Hereinafter, each step in the method for manufacturing an electronic device will be described along the flowchart shown in FIG.

[Separation layer forming step (step S01)]
First, in step S01, a separation layer is formed on the support. FIG. 2 is a diagram showing a separation layer forming step, which is one step of the method for manufacturing an electronic device. As shown in FIG. 2, the separation layer 2 is formed on one side of the support 1 .

(support)
A support 1 is attached to a substrate 4 (4A) via a separation layer 2 and an adhesive layer 3 (see FIGS. 5 and 6) to support the substrate 4. As shown in FIG. The support 1 preferably has strength necessary to prevent damage and deformation of the substrate 4 . Moreover, the support 1 is preferably made of a material that transmits light of a predetermined wavelength (light of a wavelength capable of altering the separation layer 2, which will be described later). As the material of the support 1, for example, glass, silicon, acrylic resin, or the like is used. The shape of the support 1 may be, for example, a rectangular shape or a circular shape in plan view, but is not limited to these.

The support 1 may have a coating layer or the like on the substrate made of the materials described above. The coating layer may be a single layer or multiple layers. Examples of the coating layer include a layer (cured film) containing a cured resin. Examples of curable resins include, but are not limited to, epoxy resins, acrylic resins, copolymers of hydrocarbon-based monomers and acrylic monomers, and the like. A coating layer may, for example, be arranged between the support 1 and the separating layer 2 . The support 1 has a thickness of, for example, about 500 to 1500 μm, but is not limited to this thickness.

(separation layer)
The separating layer 2 is placed in contact with the adhesive layer 3 (see FIG. 3). The separation layer 2 is altered by light irradiation, heating, immersion in a solvent, or the like. The term "alteration" of the separation layer 2 means a state in which the separation layer 2 can be destroyed by receiving a slight external force, or a phenomenon in which the adhesive force between the separation layer 2 and a layer in contact with it is reduced. A method for forming the separation layer 2 is not particularly limited, and a known method can be used. For example, methods such as spin coating, dipping, roller blade, spray coating, slit coating, and chemical vapor deposition (CVD) are used.

The thickness of the separation layer 2 is, for example, more preferably 0.05 to 50 μm, more preferably 0.3 to 1 μm. If the thickness of the separation layer 2 is within the range of 0.05 to 50 μm, the separation layer 2 can be subjected to desired alteration by short-time light irradiation, low-energy light irradiation, short-time heating, short-time immersion in a solvent, or the like. Moreover, it is particularly preferable that the thickness of the separation layer 2 is within the range of 1 μm or less from the viewpoint of productivity.

As described above, the separation layer forming composition, which is the material for forming the separation layer 2, may be a substance that changes the quality of the formed separation layer 2 by short-time light irradiation, low-energy light irradiation, short-time heating, short-time immersion in a solvent, or the like. Examples of the composition for forming the separation layer include a resin component having a phenol skeleton, a polymer having a repeating unit containing a light-absorbing structure, a fluorocarbon, an inorganic substance, a compound having an infrared-absorbing structure, an infrared-absorbing substance, a reactive polysilsesquioxane, or those containing these. Further, the separation layer-forming composition may contain, as optional components, fillers, plasticizers, thermal acid generator components, photoacid generator components, organic solvent components, surfactants, sensitizers, or components capable of improving the separation of the support substrate.

<<Resin component having a phenol skeleton>>
Since the separation layer 2 has a phenol skeleton, it is easily altered (oxidized, etc.) by heating and the like, and photoreactivity is increased. Here, "having a phenol skeleton" means containing a hydroxybenzene structure. The resin component having a phenol skeleton has 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 1,000 to 30,000, still more preferably 1,500 to 20,000, and particularly preferably 2,000 to 15,000. When the molecular weight of the resin component is equal to or less than the upper limit of the preferred range, the solubility of the composition for forming a separation layer in a solvent is enhanced. As the molecular weight of the resin component, the weight average molecular weight (Mw) converted to polystyrene by GPC (gel permeation chromatography) is used.

Examples of the resin component having a phenol skeleton include novolak-type phenol resins, resole-type phenol resins, hydroxystyrene resins, hydroxyphenylsilsesquioxane resins, hydroxybenzylsilsesquioxane resins, phenol skeleton-containing acrylic resins, and resins having a repeating unit represented by the following general formula (P2) (hereinafter referred to as "resin (P2)"). Among these, novolac type phenolic resins, resol type phenolic resins, resin (P2) and the like are more preferable.

［前記式中、Ｌ^ｐ１は、２価の連結基である。Ｒ^Ｐは、（ｎ_Ｐ０＋１）価の芳香族炭化水素基である。ｎ_Ｐ０は、１～３の整数である。］

[In the above formula, L ^p1 is a divalent linking group. R ^P is a (n _P0 +1) valent aromatic hydrocarbon group. n _P0 is an integer of 1-3. ]

In formula (P2), L ^p1 is a divalent linking group, preferably a divalent linking group containing a hetero atom. L ^p1 includes linking groups into which various skeletons are introduced in order to impart desired properties.
In formula (P2), R ^P is a (n _P0 +1)-valent aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group for R ^P include groups obtained by removing (n _P0 +1) hydrogen atoms from an aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene, and aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.
Examples of the aromatic hydrocarbon group for R ^P also include a group obtained by removing (n _P0 +1) hydrogen atoms from an aromatic compound containing two or more aromatic rings (eg, biphenyl, fluorene, etc.).
In formula (P2), n _P0 is an integer of 1 to 3, preferably 1 or 2, and particularly preferably 1.

As the resin (P2), a resin produced by reacting aminophenols, aminonaphthols or anilines with a compound having two epoxy groups in one molecule can also be used.
Aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 2-amino-4-methylphenol, 3-amino-2-methylphenol, 5-amino-2-methylphenol and the like. Aminonaphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, 5-amino-1-naphthol and the like.

Examples of compounds having two epoxy groups in one molecule include bisphenol-type epoxy resins such as EPICLON850, EPICLON830 (manufactured by DIC Corporation) and jERYX-4000 (manufactured by Mitsubishi Chemical Corporation); Diol-type epoxy resins such as X-911, DENACOL EX-920, and DENACOL EX-930 (manufactured by Nagase ChemteX Corporation); 05 (manufactured by Shin-Etsu Chemical Co., Ltd.) and other silicone type epoxy resins.
The heat treatment temperature for this reaction is preferably 60° C. or higher and 250° C. or lower, more preferably 80° C. or higher and 180° C. or lower.

<<Polymer having a repeating unit containing a light-absorbing structure>>
The separation layer 2 may contain a polymer having a repeating unit including a light-absorbing structure. This polymer changes in quality upon exposure to light. A structure having light absorption properties includes, for example, an atomic group containing a conjugated π-electron system composed of a substituted or unsubstituted benzene ring, condensed ring, or heterocyclic ring. More specifically, the light-absorbing structure includes a cardo structure, or a benzophenone structure, diphenylsulfoxide structure, diphenylsulfone structure (bisphenylsulfone structure), diphenyl structure, or diphenylamine structure present in the side chain of the polymer.

The light-absorbing structure can absorb light having a desired range of wavelengths depending on its type. For example, the wavelength of light that can be absorbed by the structure having light absorption properties is preferably in the range of 100 to 2000 nm, more preferably in the range of 100 to 500 nm.

The light that can be absorbed by the structure having the above light absorption property is, for example, light emitted from a high-pressure mercury lamp (wavelength 254 nm or more and 436 nm or less), KrF excimer laser (wavelength 248 nm), ArF excimer laser (wavelength 193 nm), _F2 excimer laser (wavelength 157 nm), XeCl laser (wavelength 308 nm), XeF laser (wavelength 351 nm) or solid-state UV laser (wavelength 355 nm), or g-line (wavelength 436 nm), h-line (wavelength 405 nm) or i-line (wavelength 365 nm).

<<Fluorocarbon>>
The separating layer 2 may consist of fluorocarbon. Since the separation layer 2 is composed of fluorocarbon, it is changed in quality by absorbing light, and as a result, it loses its strength or adhesiveness before being irradiated with light. Therefore, by applying a slight external force (for example, by lifting the support 1), the separation layer 2 is broken and the support 1 and the substrate 4 can be easily separated. The fluorocarbon forming the separation layer 2 can be preferably formed into a film by plasma CVD (chemical vapor deposition).

Fluorocarbons absorb light with a range of wavelengths unique to their type. By irradiating the separation layer with light having a wavelength in the range absorbed by the fluorocarbon used in the separation layer 2, the fluorocarbon can be degraded appropriately. It is preferable that the absorption rate of light in the separation layer 2 is 80% or more.

As the light irradiated to the separation layer 2, depending on the wavelength that can be absorbed by the fluorocarbon, for example, solid lasers such as YAG laser, ruby laser, glass laser, YVO4 laser, LD laser, fiber laser, liquid laser such as dye laser, gas laser such as CO2 laser, excimer laser, Ar laser, He—Ne laser, laser light such as semiconductor laser, free electron laser, or non-laser light may be used as appropriate. The wavelength capable of altering the fluorocarbon is not limited to this, but for example, a wavelength in the range of 600 nm or less can be used.

<<Inorganic substance>>
The separation layer 2 may be made of an inorganic material. The inorganic substance may be one that changes in quality by absorbing light, and preferably includes one or more selected from the group consisting of metals, metal compounds, and carbon. A metal compound is a compound containing a metal atom, and examples thereof include metal oxides and metal nitrides. Examples of 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. Carbon is a concept that can include allotropes of carbon, and includes, for example, diamond, fullerene, diamond-like carbon, carbon nanotubes, and the like. The inorganic materials described above absorb light having wavelengths in a range unique to their type.

As the light to be irradiated to the separation layer 2 made of an inorganic substance, a YAG laser, a ruby laser, a glass laser, a YVO laser, an LD laser, a solid laser such as 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, a gas laser such as a He-Ne laser, a semiconductor laser, a free electron laser, or a non-laser beam may be appropriately used according to a wavelength that can be absorbed by the inorganic substance. The separation layer 2 made of inorganic material can be formed on the support 1 by known techniques such as sputtering, chemical vapor deposition (CVD), plating, plasma CVD, spin coating, and the like.

<<Compound having an infrared absorbing structure>>
The separation layer 2 may contain a compound having an infrared absorbing structure. This compound having an infrared-absorbing structure changes in quality by absorbing infrared rays.赤外線吸収性を有している構造、又はこの構造を有する化合物としては、例えば、アルカン、アルケン（ビニル、トランス、シス、ビニリデン、三置換、四置換、共役、クムレン、環式）、アルキン（一置換、二置換）、単環式芳香族（ベンゼン、一置換、二置換、三置換）、アルコールもしくはフェノール類（自由ＯＨ、分子内水素結合、分子間水素結合、飽和第二級、飽和第三級、不飽和第二級、不飽和第三級）、アセタール、ケタール、脂肪族エーテル、芳香族エーテル、ビニルエーテル、オキシラン環エーテル、過酸化物エーテル、ケトン、ジアルキルカルボニル、芳香族カルボニル、１，３－ジケトンのエノール、ｏ－ヒドロキシアリールケトン、ジアルキルアルデヒド、芳香族アルデヒド、カルボン酸（二量体、カルボン酸アニオン）、ギ酸エステル、酢酸エステル、共役エステル、非共役エステル、芳香族エステル、ラクトン（β－、γ－、δ－）、脂肪族酸塩化物、芳香族酸塩化物、酸無水物（共役、非共役、環式、非環式）、第一級アミド、第二級アミド、ラクタム、第一級アミン（脂肪族、芳香族）、第二級アミン（脂肪族、芳香族）、第三級アミン（脂肪族、芳香族）、第一級アミン塩、第二級アミン塩、第三級アミン塩、アンモニウムイオン、脂肪族ニトリル、芳香族ニトリル、カルボジイミド、脂肪族イソニトリル、芳香族イソニトリル、イソシアン酸エステル、チオシアン酸エステル、脂肪族イソチオシアン酸エステル、芳香族イソチオシアン酸エステル、脂肪族ニトロ化合物、芳香族ニトロ化合物、ニトロアミン、ニトロソアミン、硝酸エステル、亜硝酸エステル、ニトロソ結合（脂肪族、芳香族、単量体、二量体）、メルカプタンもしくはチオフェノールもしくはチオール酸等の硫黄化合物、チオカルボニル基、スルホキシド、スルホン、塩化スルホニル、第一級スルホンアミド、第二級スルホンアミド、硫酸エステル、炭素－ハロゲン結合、Ｓｉ－Ａ ^１結合（Ａ ^１は、Ｈ、Ｃ、Ｏ又はハロゲン）、Ｐ－Ａ ^２結合（Ａ ^２は、Ｈ、Ｃ又はＯ）又はＴｉ－Ｏ結合が挙げられる。

Examples of the above structures containing a carbon-halogen bond include -CH ₂ Cl, -CH ₂ Br, -CH ₂ I, -CF ₂ -, -CF ₃ , -CH=CF ₂ , -CF=CF ₂ , aryl fluorides or aryl chlorides.

Examples of structures containing the Si—A ¹ bond include SiH, SiH ₂ , SiH ₃ , Si—CH ₃ , Si—CH ₂ —, Si—C ₆ H ₅ , SiO-aliphatic, Si—OCH ₃ , Si—OCH ₂ CH ₃ , Si—OC ₆ H ₅ , Si—O—Si, Si—OH, SiF, SiF ₂ or SiF ₃ . As the structure containing the Si—A ¹ bond, it is particularly preferable to form a siloxane skeleton or a silsesquioxane skeleton.

Structures containing the above PA ² bond include, for example, PH, PH ₂ , P—CH ₃ , P—CH ₂ —, P—C ₆ H ₅ , A ³³ _-P —O (A ³ is an aliphatic group or an aromatic group), (A ⁴ O) ₃ -P—O (A ⁴ is an alkyl group), P—OCH ₃ , P—OCH ₂ CH ₃ , P—OC ₆ H ₅ , P—O—P, P—OH or O═P—OH and the like.

上記のＴｉ－Ｏ結合を含む化合物としては、例えば、（ｉ）テトラ－ｉ－プロポキシチタン、テトラ－ｎ－ブトキシチタン、テトラキス（２－エチルヘキシルオキシ）チタン又はチタニウム－ｉ－プロポキシオクチレングリコレート等のアルコキシチタン；（ｉｉ）ジ－ｉ－プロポキシ・ビス（アセチルアセトナト）チタン又はプロパンジオキシチタンビス（エチルアセトアセテート）等のキレートチタン；（ｉｉｉ）ｉ－Ｃ _３ Ｈ _７ Ｏ－［－Ｔｉ（Ｏ－ｉ－Ｃ _３ Ｈ _７ ） _２ －Ｏ－］ _ｎ －ｉ－Ｃ _３ Ｈ _７又はｎ－Ｃ _４ Ｈ _９ Ｏ－［－Ｔｉ（Ｏ－ｎ－Ｃ _４ Ｈ _９ ） _２ －Ｏ－］ _ｎ －ｎ－Ｃ _４ Ｈ _９等のチタンポリマー；（ｉｖ）トリ－ｎ－ブトキシチタンモノステアレート、チタニウムステアレート、ジ－ｉ－プロポキシチタンジイソステアレート又は（２－ｎ－ブトキシカルボニルベンゾイルオキシ）トリブトキシチタン等のアシレートチタン；（ｖ）ジ－ｎ－ブトキシ・ビス（トリエタノールアミナト）チタン等の水溶性チタン化合物等が挙げられる。 Among these, di-n-butoxybis(triethanolamineto)titanium (Ti(OC ₄ H ₉ ) ₂ [OC ₂ H ₄ N(C ₂ H ₄ OH) ₂ ] ₂ ) is preferable as the compound containing a Ti—O bond.

The infrared-absorbing structure described above can absorb infrared radiation having a desired range of wavelengths by selection of its type. Specifically, the wavelength of infrared rays that can be absorbed by the infrared-absorbing structure is, for example, in the range of 1 to 20 μm, and more preferably in the range of 2 to 15 μm. Furthermore, when the structure is Si--O bond, Si--C bond or Ti--O bond, the range is preferably 9 to 11 μm.

A person skilled in the art can easily understand the infrared wavelengths that can be absorbed by each of the above structures. For example, as the absorption band in each structure, reference can be made to the non-patent document: "Spectral Identification Method for Organic Compounds (5th Edition)-Combination of MS, IR, NMR, and UV-" by SILVERSTEIN, BASSLER, and MORRILL (published in 1992), pp. 146 to 151.

The compound having an infrared-absorbing structure used to form the separation layer 2 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 structure described above. However, in order to effectively change the properties of the compound in the separation layer 2 and facilitate the separation of the supporting base and the substrate, it is preferable that the separation layer 2 absorbs a large amount of infrared rays, that is, that the infrared transmittance when the separation layer 2 is irradiated with infrared rays is low. Specifically, the infrared transmittance of the separation layer 2 is preferably lower than 90%, and more preferably lower than 80%.

<<Infrared absorbing material>>
The separation layer 2 may contain an infrared absorbing substance. This infrared absorbing material may be any material that changes in quality by absorbing light, and for example, carbon black, iron particles, or aluminum particles can be preferably used. Infrared absorbing substances absorb light having wavelengths in a range unique to their type. By irradiating the separation layer 2 with light having a wavelength in the range absorbed by the infrared absorption substance used in the separation layer 2, the infrared absorption substance can be suitably altered.

<<Reactive polysilsesquioxane>>
Separation layer 2 can be formed by polymerizing reactive polysilsesquioxane. The separation layer thus formed has high chemical resistance and high heat resistance.

“Reactive polysilsesquioxane” refers to polysilsesquioxane having a silanol group at the terminal of the polysilsesquioxane skeleton or a functional group capable of forming a silanol group by hydrolysis. By condensing the silanol groups or functional groups capable of forming silanol groups, they can be polymerized together. In addition, as the reactive polysilsesquioxane, a reactive polysilsesquioxane having a silsesquioxane skeleton such as a random structure, a cage structure, or a ladder structure can be employed as long as it has a silanol group or a functional group capable of forming a silanol group.

The siloxane content of the reactive polysilsesquioxane is preferably 70-99 mol %, more preferably 80-99 mol %. If the siloxane content of the reactive polysilsesquioxane is within the preferred range described above, it is possible to form a separation layer 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). The weight average molecular weight (Mw) of the reactive polysilsesquioxane is preferably 500-50,000, more preferably 1,000-10,000. If the weight-average molecular weight (Mw) of the reactive polysilsesquioxane is within the preferred range described above, it can be suitably dissolved in a solvent and applied onto the support plate. Commercially available products that can be used as the reactive polysilsesquioxane include, for example, SR-13, SR-21, SR-23 and SR-33 (trade names) manufactured by Konishi Chemical Industry Co., Ltd.

[Adhesive Layer Forming Step (Step S02)]
Next, in step S02, an adhesive layer is formed on the support. FIG. 3 is a diagram showing a step of forming an adhesive layer, which is one step of the method of manufacturing an electronic device. As shown in FIG. 3, the adhesive layer 3 is formed on the side of the separation layer 2 on which the support 1 is not present. As for the method for forming the adhesive layer 3, a solution obtained by dissolving an adhesive (composed of an adhesive layer-forming substance) in a solvent may be applied to form the adhesive layer 3, or an adhesive tape coated on both sides with an adhesive may be attached to the separation layer 2. The method of applying the adhesive is not particularly limited, and examples thereof include a spin coating method, a dipping method, a roller blade method, a doctor blade method, a spray method, and a slit nozzle method. Alternatively, the adhesive may be applied onto the separation layer 2 and then dried by heating or the like.

The thickness of the adhesive layer 3 is, for example, preferably in the range of 1 to 200 μm, more preferably in the range of 5 to 150 μm. Moreover, the adhesive layer 3 is preferably thicker than the separation layer 2 . The adhesive composition that constitutes the adhesive will be described together with the description of the first cleaning step and the second cleaning step, which will be described later.

[Substrate forming step (step S03)]
Next, in step S03, a substrate is formed on the support. FIG. 4 is a diagram showing a substrate forming step, which is one step of the method of manufacturing an electronic device. FIG. 5 is a diagram showing a substrate forming step, which is one step of the electronic device manufacturing method, following FIG. 4 . First, as shown in FIG. 4, the plurality of electronic components 41 are arranged on the surface 3a, which is the side of the adhesive layer 3 on which the separation layer 2 is not present. The placement of the electronic component 41 is performed by a conveying device (die bonder, mounter) or the like (not shown). Note that the electronic component 41 may be adhered by the adhesive layer 3 to maintain its arrangement position. Further, after the plurality of electronic components 41 are arranged, the electronic components 41 may be pressure-bonded to the adhesive layer 3 by a conveying device or the like while heating (for example, about 100° C.) under vacuum.

After the plurality of electronic components 41 are arranged, as shown in FIG. 5, a mold 42 is formed so as to cover the entire surface of the adhesive layer surface 3a including the electronic components 41. As shown in FIG. The electronic component 41 is buried in the mold 42 to form the substrate 4A. Further, by the substrate forming process of step S03, the laminate 100A is formed by laminating the support 1, the separation layer 2, the adhesive layer 3, and the substrate 4A in this order.

Note that the mold 42 may be formed so as to expose a portion (for example, the upper surface) of the electronic component 41 . Also, the mold 42 may be formed using, for example, a material that can transmit light for altering the separation layer 2 . Examples of such materials include glass, silicon, acrylic resin, and the like.

[Mold Polishing Step (Step S04)]
Next, in step S04, the mold is polished. FIG. 6 is a diagram showing a mold polishing step, which is one step of the electronic device manufacturing method. As shown in FIG. 6, the side of the mold 42 where the support 1 does not exist, that is, the upper surface 42a of the mold 42 is polished by a polishing device (not shown). The electronic component 41 is exposed from the mold 42 by the mold polishing process of step S04. By polishing the mold 42, the upper surface 41a of the electronic component 41 and the new upper surface 42b of the mold 42 after polishing become substantially flush with each other.

A known method can be applied to the method of polishing the mold 42 . In addition, when the mold 42 is formed by exposing a part of the electronic component 41 in the substrate forming process of step S03, this mold polishing process can be omitted. Further, the laminate 100 in which the support 1, the separation layer 2, the adhesive layer 3, and the substrate 4 are laminated in this order is formed by the mold polishing step of step S04.

After the mold polishing step, wiring may be formed on the upper surface 42b of the electronic component 41 and the mold 42 using a conductive material. Also, an electronic component 41 may be arranged so as to be electrically connected to this wiring, and a mold 42 may be newly formed so as to cover this electronic component 41 . Incidentally, bumps, solder, or the like are used for connection between the wiring and the electronic component 41 . In this way, the substrate 4 may be formed by stacking a plurality of layers on which the electronic components 41 are arranged.

[Separation layer deterioration step (step S05)]
Next, in step S05, the separation layer is altered. FIG. 7 is a diagram showing a separation layer deterioration step, which is one step of the method of manufacturing an electronic device. As shown in FIG. 7, in the laminate 100, the separation layer 2 is irradiated with light L from the irradiation device IR from the side of the support 1 where the separation layer 2 is not present, and the separation layer 2 is altered. The light L is transmitted through the support 1 and applied to the separation layer 2 . As the light L emitted from the irradiation device IR, light having a wavelength capable of altering the separation layer 2 is used. Degeneration of the separation layer 2 can occur due to (exothermic or non-exothermic) decomposition, cross-linking, change in configuration, dissociation of functional groups (and accompanying curing, degassing, shrinkage or expansion of the separation layer 2), etc., due to the energy of the absorbed light L.

The degeneration of the separation layer 2 causes the separation layer 2 to be destroyed by a slight external force, or the adhesive force between the separation layer 2 and the contacting layers (the support 1 and the adhesive layer 3) is reduced. That is, the support 1 can be separated from the substrate 4 . In FIG. 7, the laminate 100 is turned upside down from the state shown in FIG. 6, that is, the upper side of the support 1 (with the substrate 4 as the lower side), and the light L is irradiated downward from the upper irradiation device IR, but it is not limited to this form. For example, the light L may be irradiated from the lower side of the support 1 by the irradiation device IR with the substrate 4 as the upper side.

[Support Peeling Step (Step S06)]
Next, in step S06, the support is peeled off. FIG. 8 is a diagram showing a support peeling step, which is one step of the method for manufacturing an electronic device. As shown in FIG. 8, by lifting the support 1 while holding the substrate 4 with the substrate 4 facing downward, the separation layer 2 is broken and the support 1 is separated from the substrate 4 . That is, the substrate 4 and the support 1 are separated. For the work of lifting the support 1, for example, a device that lifts the support 1 by suction may be used. The substrate 4 is attached to a stage or the like, and is separated from the support 1 by lifting the support 1 .

As shown in FIG. 8, the adhesive layer 3 remains on the substrate 4 from which the support 1 has been removed. Residues 2a of the degraded separation layer 2 remain on the surface 3a of the adhesive layer 3 without being completely removed. Moreover, the residue 2 a of the degraded separation layer 2 may enter the adhesive layer 3 . In this state, if a single solvent capable of dissolving the adhesive layer 3 is used to dissolve and remove the adhesive layer 3 while flowing it over the surface 3a of the adhesive layer 3, all or part of the residue 2a of the separation layer 2 remains on the adhesive layer 3 while the adhesive layer 3 is dissolved, and the residue 2a may remain on the surface of the substrate 4 even after the adhesive layer 3 is removed. In this embodiment, the residue 2a is prevented from remaining on the surface of the substrate 4 by the first cleaning process and the second cleaning process, which will be described later.

[First cleaning step (step S07)]
In step S07, the substrate 4 with the adhesive layer 3 remaining is washed with a first washing liquid. FIG. 9 is a diagram showing a first cleaning step, which is one step of the method for manufacturing an electronic device. As shown in FIG. 9, the first cleaning liquid R1 is supplied from the nozzle 612 to the substrate 4 (adhesive layer 3) with the adhesive layer 3 facing upward. The first cleaning liquid R<b>1 is supplied from above substantially the center of the substrate 4 , flows over the upper surface of the adhesive layer 3 , and flows down from the edge of the substrate 4 . Note that the substrate 4 may be rotated around the vertical axis when the first cleaning liquid R1 is supplied. As the first cleaning liquid R1, a liquid obtained by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer 3 is used. The first solvent is a solvent capable of dissolving the adhesive composition contained in the adhesive used to form the adhesive layer 3 in the adhesive layer forming step (step S02) described above. First, the adhesive composition will be explained.

(Adhesive composition)
Examples of the adhesive composition include various adhesive compositions known in the art, such as acrylic, novolac, naphthoquinone, hydrocarbon, polyimide, elastomer, and polysulfone. Examples of adhesive compositions include those containing other components such as thermoplastic resins, diluent solvents, and additives. The thermoplastic resin may be any one that exhibits adhesive strength. For example, hydrocarbon resins, acrylic-styrene resins, maleimide resins, elastomer resins, polysulfone resins, etc., or combinations thereof can be preferably used. The adhesive composition contains a diluent solvent.

<<hydrocarbon resin>>
A hydrocarbon resin is a resin having a hydrocarbon skeleton and formed by polymerizing a monomer composition. Hydrocarbon resins include, but are not limited to, cycloolefin polymers (hereinafter referred to as "resin (A)"), and at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins (hereinafter referred to as "resin (B)").

Suitable examples of the resin (A) include ring-opening polymers of monomer components containing cycloolefin monomers and addition polymers obtained by addition polymerization of monomer components containing cycloolefin monomers. The cycloolefin polymer may have a monomer copolymerizable with the cycloolefin monomer as a monomer unit.

Moreover, it is preferable to contain a cycloolefin monomer as a monomer component constituting the resin (A) from the viewpoint of high heat resistance (low thermal decomposition and thermal weight loss). The ratio of the cycloolefin monomer to the total 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. In addition, the ratio of the cycloolefin monomer to the total monomer components constituting the resin (A) is not particularly limited, but from the viewpoint of solubility and stability over time in a solution, it is preferably 80 mol% or less, more preferably 70 mol% or less.

Moreover, a linear or branched alkene monomer may be contained as a monomer component constituting the resin (A). The ratio of the alkene monomer to the total monomer components constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol%, and even more preferably 30 to 80 mol%, from the viewpoint of solubility and flexibility. The resin (A) is preferably a resin having no 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. The polymerization method, polymerization conditions, and the like for polymerizing the monomer components are not particularly limited, and may be appropriately set according to conventional methods.

Examples of commercially available cycloolefin polymers that can be used as the resin (A) include "TOPAS (trade name)" manufactured by Polyplastics Co., Ltd., "APEL (trade name)" manufactured by Mitsui Chemicals, Inc., "ZEONOR (trade name)" manufactured by Zeon Corporation, "ZEONEX (trade name)" manufactured by Zeon Corporation, and "ARTON (trade name)" manufactured by JSR Corporation. The glass transition temperature (Tg) of the resin (A) is preferably 60°C or higher, particularly preferably 70°C or higher. When the resin (A) has a glass transition temperature of 60° C. or higher, softening of the adhesive layer can be suppressed when exposed to a high-temperature environment.

The resin (B) is at least one resin selected from the group consisting of terpene-based resins, rosin-based resins and petroleum resins. Specifically, terpene-based resins include, for example, terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, and hydrogenated terpene phenol resins. Examples of rosin-based resins include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, 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 preferable.

Although the softening point of the resin (B) is not particularly limited, it is preferably 80 to 160°C. When the softening point of the resin (B) is 80 to 160° C., it is possible to suppress softening when exposed to a high-temperature environment, and adhesion failure does not occur. The weight average molecular weight of 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 dissolution rate of the adhesive layer in the hydrocarbon solvent becomes favorable. Therefore, the residue of the adhesive layer on the device layer after separation of the support can be rapidly dissolved and removed. The weight average molecular weight of the resin (B) in the present embodiment means the polystyrene-equivalent molecular weight measured by gel permeation chromatography (GPC).

As the hydrocarbon resin, a mixture of the resin (A) and the resin (B) may be used. By mixing, good heat resistance can be obtained. For example, the mixing ratio of the resin (A) and the resin (B) is preferably (A):(B)=80:20 to 55:45 (mass ratio) because it is excellent in heat resistance and flexibility in a high temperature environment.

<<Acrylic-styrene resin>>
Examples of acrylic-styrene resins include resins obtained by polymerizing styrene or styrene derivatives and (meth)acrylic acid esters as monomers.

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 long-chain acrylic alkyl esters having alkyl groups of 15 to 20 carbon atoms and acrylic alkyl esters having alkyl groups of 1 to 14 carbon atoms. Examples of acrylic long-chain alkyl esters include acrylic or methacrylic acid alkyl esters in which the alkyl group is n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl or the like. In addition, the said alkyl group may be branched.

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

Examples of (meth)acrylic acid esters having an aliphatic ring include cyclohexyl (meth)acrylate, cyclopentyl (meth)acrylate, 1-adamantyl (meth)acrylate, norbornyl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanyl (meth)acrylate, tetracyclododecanyl (meth)acrylate, and dicyclopentanyl (meth)acrylate, with isobornyl methacrylate and dicyclopentanyl (meth)acrylate being more preferred.

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. In addition, the aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferred.

<<Maleimide resin>>
Examples of maleimide resins include monomers 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, and Nn-octyl. Maleimide, N-laurylmaleimide, maleimide having an alkyl group such as N-stearylmaleimide, maleimide having an aliphatic hydrocarbon group such as N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide , Np-methylphenylmaleimide, and other resins obtained by polymerizing aromatic maleimides having an aryl group.

<<Elastomer Resin>>
The elastomer resin (hereinafter sometimes referred to as "elastomer") preferably contains a styrene unit as a structural unit of the main chain, and the "styrene unit" may have a substituent. Examples of substituents include alkyl groups having 1 to 5 carbon atoms, alkoxy groups having 1 to 5 carbon atoms, alkoxyalkyl groups having 1 to 5 carbon atoms, acetoxy groups, and carboxyl groups. Moreover, it is more preferable that the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less. Furthermore, the elastomer preferably has a weight average molecular weight within the range of 10,000 or more and 200,000 or less.

When the styrene unit content is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the adhesive layer can be removed more easily and quickly because it is easily dissolved in the hydrocarbon-based solvent described later. In addition, since the styrene unit content and weight average molecular weight are within the above ranges, excellent resistance to resist solvents (e.g. PGMEA, PGME, etc.), acids (hydrofluoric acid, etc.), and alkalis (TMAH, etc.) used in resist lithography is exhibited.

The elastomer may further be mixed with the (meth)acrylic acid ester described above. The content of styrene units is more preferably 17% by weight or more, and more preferably 40% by weight or less. A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

As the elastomer, various elastomers can be used as long as the content of styrene units is in the range of 14% by weight or more and 50% by weight or less and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less. For example, polystyrene-poly(ethylene/propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS), and hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolymer with reactive cross-linked styrene block (Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), styrene-ethylene-butylene-styrene block copolymer with reactive cross-linked styrene block (Septon V9827 (manufactured by Kuraray Co., Ltd.) having a reactive polystyrene hard block), polystyrene-poly (ethylene-ethylene/propylene) ) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modified), etc., and elastomers having a styrene unit content and a weight average molecular weight within the aforementioned ranges can be used.

Among elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, the stability against heat is improved, and deterioration such as decomposition or polymerization is less likely to occur. It is also more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents. Further, among elastomers, those having styrene block polymers at both ends are more preferable. This is because by blocking both ends with styrene, which has high thermal stability, higher heat resistance is exhibited. More specifically, the elastomer is more preferably a hydrogenated block copolymer of styrene and a conjugated diene. Stability against heat is improved, and deterioration such as decomposition and polymerization hardly occurs. In addition, by blocking styrene, which has high thermal stability, at both ends, higher heat resistance is exhibited. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

Commercially available products that can be used as the elastomer contained in the adhesive composition include, for example, "Septon (trade name)" manufactured by Kuraray Co., Ltd., "Hiblr (trade name)" manufactured by Kuraray Co., Ltd., "Tuftec (trade name)" manufactured by Asahi Kasei Corporation, and "Dynalon (trade name)" manufactured by JSR Corporation.

The content of the elastomer contained in the adhesive composition is, for example, preferably 50 parts by weight or more and 99 parts by weight or less, more preferably 60 parts by weight or more and 99 parts by weight or less, and most preferably 70 parts by weight or more and 95 parts by weight or less, with the total amount of the adhesive composition being 100 parts by weight. By setting the thickness within these ranges, the substrate can be suitably fixed to the support while maintaining heat resistance.

Also, the elastomer may be a mixture of multiple types. That is, the adhesive composition may contain multiple types of elastomers. At least one of the plurality of types of elastomers may contain a styrene unit as a structural unit of the main chain. In addition, at least one of the plurality of types of elastomers has a styrene unit content of 14% by weight or more and 50% by weight or less, or a weight average molecular weight of 10,000 or more and 200,000 or less, which falls within the scope of the present invention. In addition, when the adhesive composition contains a plurality of types of elastomers, the content of styrene units may be adjusted so as to be within the above range as a result of mixing. For example, when Septon 4033 manufactured by Kuraray Co., Ltd. and having a styrene unit content of 30% by weight and Septon 2063 having a styrene unit content of 13% by weight are mixed at a weight ratio of 1:1, the styrene content of the entire elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. Further, for example, if a styrene unit content of 10% by weight and a styrene unit content of 60% by weight are mixed at a weight ratio of 1:1, the content is 35% by weight, which is within the above range. The present invention may take such a form. Most preferably, the plurality of types of elastomers contained in the adhesive composition all contain styrene units within the above ranges and have weight average molecular weights within the above ranges.

<<Polysulfone resin>>
The adhesive composition may contain a polysulfone-based resin. By forming the adhesive layer 3 with a polysulfone-based resin, even if a high-temperature treatment is performed when forming the mold 42 in the substrate forming step, the adhesive layer 3 is dissolved in the subsequent steps, and the substrate 4 can be separated from the support 1. If the adhesive layer 3 contains a polysulfone resin, a high-temperature process of treating at a high temperature of 300° C. or higher, for example, can be used in the substrate forming process. The polysulfone-based resin has a structure composed of at least one structural unit selected from structural units represented by the following general formula (ad1) and structural units represented by the following general formula (ad2).

［式中、Ｒ^Ｃ３、Ｒ^Ｃ４、Ｒ^Ｃ５は、それぞれ独立して、フェニレン基、ナフチレン基及びアントリレン基からなる群より選択される基であり、Ｘ’は、炭素数１～３のアルキレン基である。］

[wherein R ^C3 , R ^C4 and R ^C5 are each independently a group selected from the group consisting of a phenylene group, a naphthylene group and an anthrylene group, and X′ is an alkylene group having 1 to 3 carbon atoms. ]

Since the polysulfone-based resin includes at least one of the polysulfone structural unit represented by the above formula (ad1) and the polyethersulfone structural unit represented by the above formula (ad2), it is possible to prevent the adhesive layer from becoming insoluble due to decomposition, polymerization, etc. even if the adhesive layer is formed on the support and then subjected to high temperature conditions. Moreover, the polysulfone-based resin is stable even when heated to a higher temperature if it is a polysulfone resin composed of the polysulfone structural unit represented by the above formula (ad1).

The weight average molecular weight (Mw) of the polysulfone resin is preferably in the range of 30,000 or more and 70,000 or less, more preferably in the range of 30,000 or more and 50,000 or less. If the weight average molecular weight (Mw) of the polysulfone-based resin is within the range of 30,000 or more, it is possible to obtain an adhesive composition that can be used at a high temperature of 300° C. or more, for example. Moreover, if the weight average molecular weight (Mw) of the polysulfone-based resin is within the range of 70,000 or less, it can be suitably dissolved in the solvent. That is, it is possible to obtain an adhesive composition that can be suitably removed with a solvent.

<<dilution solvent>>
Examples of diluent solvents include linear hydrocarbons such as hexane, heptane, octane, nonane, isononane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; , 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujang, kalan, longifolene, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cine Terpene solvents such as ol, 1,8-cineol, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol Ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, a compound having an ester bond such as propylene glycol monoacetate, monomethyl ether of the above polyhydric alcohols or compounds having an ester bond, monoethyl ether, monopropyl ether, monoalkyl ether such as monobutyl ether, or derivatives of polyhydric alcohols such as compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether (P cyclic ethers such as dioxane; esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, and ethyl ethoxypropionate; Moreover, it is also possible to mix and use these.

The adhesive composition may contain additives. In addition, the adhesive composition may contain other miscible substances as long as the essential properties are not impaired. Such additives include, for example, additional resins for improving the performance of adhesives, curable monomers, polymerization inhibitors, polymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, surfactants, and other commonly used various additives can be further used.

(Prescribed resin)
A predetermined resin dissolved in the first cleaning liquid R1 will be described. The predetermined resin includes, for example, the resin contained in the adhesive composition described above. As the predetermined resin, a resin that can be dissolved in a first solvent, which will be described later, is selected. The predetermined resin may be the same resin as the resin contained in the adhesive used to form the adhesive layer 3, or may be a different resin. Moreover, a single type of resin may be used as the predetermined resin, or a mixture of a plurality of types of resin may be used.

The content (% by weight) of the predetermined resin in the first cleaning liquid R1 is preferably smaller than the content (% by weight) of the resin in the adhesive used to form the adhesive layer 3 . This is because when the content of the predetermined resin in the first cleaning liquid R1 is greater than the content (% by weight) of the resin contained in the adhesive used to form the adhesive layer 3, the first cleaning liquid R1 dissolves and removes the adhesive layer 3, while a large amount of the predetermined resin contained in the first cleaning liquid R1 remains on the substrate 4. Moreover, it is preferable that the predetermined resin is contained in the first cleaning liquid R1 in an amount of 3 to 5% by weight. If the prescribed resin is less than 3% by weight, there is a high possibility that the residue 2a of the separation layer 2 on the substrate 4a will remain.

(first solvent)
The first solvent is a solvent capable of dissolving the adhesive layer 3 , that is, a solvent that dissolves the adhesive composition forming the adhesive layer 3 . The first solvent is not particularly limited as long as it can dissolve the adhesive layer 3, and can be appropriately selected according to the adhesive layer 3 (adhesive composition). For the first solvent, for example, one having the same polarity as, or a polarity close to, the diluting solvent used for the adhesive when forming the adhesive layer 3 is used. In addition, it may be the same as the diluent solvent used for the adhesive when forming the adhesive layer 3 . Examples of the first solvent capable of dissolving the adhesive layer 3 include hydrocarbon-based solvents and ester-based solvents. Optional components such as additives may be added to the first solvent as appropriate. Optional components are not particularly limited, but include, for example, surfactants. Alternatively, a mixture of a hydrocarbon solvent and an ester solvent may be used. Moreover, a single type of solvent may be used as the first solvent, or a plurality of types of solvents may be mixed and used.

<<Hydrocarbon solvent>>
The hydrocarbon solvent may be an aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent. Here, "aliphatic" is a concept relative to aromatic, and means groups, compounds, etc. that do not have aromaticity. Aliphatic hydrocarbon solvents include alkane hydrocarbon solvents. The alkane-based hydrocarbon solvent may be linear, branched, or cyclic. Examples of straight-chain or branched-chain alkane hydrocarbon solvents include straight-chain or branched-chain alkanes having 4 to 20 carbon atoms, such as butane, pentane, 2-methylbutane, 3-methylpentane, hexane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, 2,2,4-trimethylpentane, 2,2,3-trimethylhexane, nonane, isononane, methyloctane, decane, undecane, dodecane, 2,2,4,6,6-pentamethylheptane, tridecane, pentadecane, tetradecane, hexadecane and the like. Examples of hydrocarbon-based solvents of cyclic alkanes include cyclic alkanes having 4 to 20 carbon atoms, such as monocycloalkanes such as cyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, cycloheptane and cyclooctane, and bicycloalkanes such as decalin. Among these, ethylcyclohexane and decalin are preferable as the alkane-based hydrocarbon solvent. In addition, as the aliphatic hydrocarbon solvent, a terpene hydrocarbon solvent can also be used. Terpene-based hydrocarbon solvents include, for example, D-limonene and P-menthane.

Examples of aromatic hydrocarbon solvents include benzene, naphthalene, tetrahydronaphthalene, and the like. Further, it is preferable to remove impurities having a boiling point higher than that of the hydrocarbon-based solvent, for example, by distillation or the like. As a result, it is possible to prevent high-boiling-point impurities contained in the hydrocarbon-based solvent from remaining on the substrate 4 as a residue when the adhesive is removed by washing.

<<Ester solvent>>
Examples of ester solvents include methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, propylene glycol monomethyl ether acetate (PGMEA), and the like.

In this first cleaning step, the adhesive layer 3 is dissolved and removed by the first cleaning liquid R1, and a predetermined resin dissolved in the first cleaning liquid R1 is applied. The surface 3a of the adhesive layer 3 or the residue 2a of the separation layer 2 remaining in the adhesive layer 3 is washed away from the adhesive layer 3 (substrate 4) by the flow of the first cleaning liquid R1, and is prevented from adhering to the substrate 4 by the predetermined resin of the first cleaning liquid R1. As a result, it is possible to prevent the residue 2a from remaining on the surface of the substrate 4 where the adhesive layer 3 is removed. After the first cleaning step, the predetermined resin of the first cleaning liquid R1 remains on the surface of the substrate 4, and a layer (film) is formed from this resin.

FIG. 10 is a diagram showing the state of the substrate 4 after the first cleaning process. As shown in FIG. 10, a resin layer 5 is formed on the surface 4a of the substrate 4 by a predetermined resin of the first cleaning liquid R1. That is, the adhesive layer 3 is dissolved and removed from the surface 4a of the substrate 4, and the residue 2a of the separation layer 2 is also removed, but the resin layer 5 is formed by the first cleaning liquid R1.

[Second cleaning step (step S08)]
Next, in step S08, the substrate 4 with the resin layer 5 formed thereon is washed with a second washing liquid. FIG. 11 is a diagram showing a second cleaning step, which is one step of the electronic device manufacturing method. As shown in FIG. 11, the second cleaning liquid R2 is supplied from the nozzle 622 to the substrate 4 (resin layer 5) with the resin layer 5 facing upward. The second cleaning liquid R<b>2 is supplied from above the substrate 4 at substantially the center, flows over the upper surface of the resin layer 5 , and falls from the edge of the substrate 4 . Note that the substrate 4 may be rotated around the vertical axis when the second cleaning liquid R2 is supplied. A second solvent capable of dissolving the resin layer 5 is used as the second cleaning liquid R2.

(Second solvent)
A solvent capable of dissolving the resin layer 5 is used as the second solvent. The second solvent is not particularly limited as long as it can dissolve the resin layer 5 , and can be appropriately selected according to the composition of the resin layer 5 . The second solvent used has the same polarity or a polarity close to that of the first solvent. That is, the second solvent can dissolve the adhesive layer 3 . The second solvent may be the same as or different from the first solvent described above. Moreover, since the second solvent has the same polarity as the first solvent, or has a polarity close to that of the first solvent, it may be the same as the solvent for diluting the adhesive used to form the adhesive layer 3 . Moreover, a single type of solvent may be used as the second solvent, or a plurality of types of solvents may be mixed and used.

In this second cleaning step, the resin layer 5 is dissolved and removed by the second cleaning liquid R2. As the second cleaning liquid R2, a cleaning liquid in which the resin or the like is not dissolved or the concentration of the resin or the like is low is preferable. That is, the solid content concentration of such a cleaning liquid is preferably set to 0.5% by weight or less, more preferably 0.3% by weight or less, and even more preferably 0.1% by weight or less.
FIG. 12 shows the state of the substrate 4 after the second cleaning process. As shown in FIG. 12, a resin layer 5 is formed on the surface 4a of the substrate 4 by a predetermined resin of the first cleaning liquid R1. That is, the resin layer 5 is dissolved and removed from the surface 4a of the substrate 4, and no new layer is formed. Even if the residue 2a of the separation layer 2 slightly remains on the substrate 4 after the first cleaning process, it may be removed from the substrate 4 by this second cleaning process.

After the second cleaning step, for example, individual electronic devices are obtained by dicing the substrate 4 along preset lines. Any device can be used as the dicing device.

<Substrate cleaning equipment>
FIG. 13 is a diagram illustrating an example of a substrate cleaning apparatus according to the embodiment; The substrate cleaning apparatus 6 shown in FIG. 13 can perform the above-described first cleaning process and second cleaning process. As shown in FIG. 13 , the substrate cleaning apparatus 6 has a first cleaning section 61 , a second cleaning section 62 and a stage 63 . Note that the stage 63 is shared by the first cleaning section 61 and the second cleaning section 62 . Further, the stage 63 may have a suction mechanism for holding the substrate 4 placed thereon. Further, the stage 63 may be configured to rotate around the vertical axis by a drive source such as an electric motor.

The first cleaning section 61 is provided to perform the above-described first cleaning process. The first cleaning section 61 includes a first cleaning liquid supply device 611 and a nozzle 612 . The first cleaning liquid supplying device 611 supplies the nozzle 612 with the first cleaning liquid R1 (see FIG. 9). The first cleaning liquid supplying device 611 is formed including, for example, a liquid feeding mechanism such as a pump, and by driving the liquid feeding mechanism, the first cleaning liquid R1 is supplied from a tank storing the first cleaning liquid R1 to the nozzle 612 through a pipe. The nozzle 612 is arranged above the stage 63 and ejects downward the first cleaning liquid R1 sent from the first cleaning liquid supplying device 611 . Note that the nozzle 612 may be horizontally movable.

In the first cleaning unit 61, the first cleaning liquid R1 can be supplied to the substrate 4 by ejecting the first cleaning liquid R1 from the nozzle 612 while the substrate 4 is placed on the stage 63, and the above-described first cleaning process can be performed. It should be noted that the loading and unloading of the substrate 4 with respect to the stage 63 is performed by a transport device (not shown).

The second cleaning section 61 is provided to perform the above-described second cleaning process. The second cleaning section 62 includes a second cleaning liquid supplying device 621 and a nozzle 622 . The second cleaning liquid supplying device 621 supplies the second cleaning liquid R2 (see FIG. 11) to the nozzle 622 . The second cleaning liquid supplying device 621 is formed including, for example, a liquid feeding mechanism such as a pump, and by driving this liquid feeding mechanism, the second cleaning liquid R2 is supplied from the tank storing the second cleaning liquid R2 to the nozzle 622 through the pipe. The nozzle 622 is arranged above the stage 63 and ejects downward the second cleaning liquid R2 sent from the second cleaning liquid supplying device 621 . Note that the nozzle 622 may be horizontally movable.

In the second cleaning unit 62, the second cleaning liquid R2 can be supplied to the substrate 4 by ejecting the second cleaning liquid R2 from the nozzle 622 while the substrate 4 is placed on the stage 63, and the second cleaning process can be performed. In the substrate cleaning apparatus 6, dedicated nozzles 611 and 621 are used for the first cleaning liquid R1 and the second cleaning liquid R2. Therefore, the control device (not shown) may control the nozzle 611 to be arranged above the center of the substrate 4 when performing the first cleaning process, and to arrange the nozzle 621 above the center of the substrate 4 after retracting the nozzle 611 when performing the second cleaning process.

FIG. 14 is a diagram showing another example of the substrate cleaning apparatus according to the embodiment; The substrate cleaning apparatus 6A shown in FIG. 14 can perform the above-described first cleaning process and second cleaning process. The same reference numerals are assigned to the same components as those of the substrate cleaning apparatus 6 described above, and the description thereof will be omitted or simplified. As shown in FIG. 14, the substrate cleaning apparatus 6A has a first cleaning section 61, a second cleaning section 62, a stage 63, and a switching section 64. As shown in FIG.

The first cleaning section 61 and the second cleaning section 62 are provided with a shared nozzle 641 . The nozzle 641 is arranged above the center of the substrate 4 placed on the stage 63 . Note that the nozzle 641 may be horizontally movable. The switching unit 64 switches between a flow path for supplying the first cleaning liquid R1 from the first cleaning liquid supply device 611 of the first cleaning section 61 to the nozzle 641 and a flow path for supplying the second cleaning liquid R2 from the second cleaning liquid supply device 621 of the second cleaning section 62 to the nozzle 641. Therefore, when performing the first cleaning process, the switching unit 64 causes the nozzle 641 to eject the first cleaning liquid R1, and when performing the second cleaning process, the switching unit 64 switches the flow path to eject the second cleaning liquid R2 from the nozzle 641. Switching of the flow path by the switching unit 64 may be controlled by a control device (not shown).

In the substrate cleaning apparatuses 6 and 6A described above, the stage 63 is shared by the first cleaning section 61 and the second cleaning section 62, but the configuration is not limited to this. For example, two stages 63 may be arranged, one of which is the stage 63 dedicated to the first cleaning section 61 and the other of which is the second cleaning section 62 . Further, the first cleaning process and the second cleaning process may be performed by separate substrate cleaning apparatuses.

<Board cleaning kit>
The kit according to the present embodiment is used to degrade the separation layer 2 in the laminate 100 in which the support 1, the separation layer 2, the adhesive layer 3, and the substrate 4 are laminated in this order, and to wash the substrate 4 separated from the support 1. The substrate cleaning kit includes: a first cleaning liquid R1 for cleaning the substrate 4 by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer 3; This substrate cleaning kit can be used for the substrate cleaning method described above.

As described above, according to the present embodiment, most of the residue 2a remaining on the surface 3a of the adhesive layer 3 and the adhesive layer 3 can be removed from the substrate 4 by performing the first cleaning step and the second cleaning step after the support 2 is peeled off from the substrate 4. As a result, since the unnecessary residue 2a and the like on the substrate 4 is extremely small, the subsequent steps can be performed with high accuracy, thereby preventing deterioration in the quality of the electronic device.

Next, although examples will be described, the present invention is not limited to these examples.
Formation of Laminate First, the composition for forming a separation layer was spin-coated on a supporting substrate and heated at a temperature of 90° C. for 300 seconds to form a film. Then, the formed film was calcined at 300° C. for 10 minutes in an atmospheric environment to form a separation layer having a thickness of 0.3 μm on the support.
Next, an adhesive composition was spin-coated on the separation layer and heated at 90° C. for 4 minutes, 160° C. for 4 minutes, and 220° C. for 4 minutes to form an adhesion layer having a thickness of 50 μm on the separation layer.
Next, using a die bonder, a substrate made of silicon was press-bonded onto the adhesive layer to obtain a laminate.

The following composition was used for the separation layer forming composition.
TZNR (registered trademark)-CTRL9 (manufactured by Tokyo Ohka Kogyo Co., Ltd.): Resin having an aminophenol skeleton (GSP-01, GSP-02 (manufactured by Gun Ei Chemical Industry Co., Ltd.))
The following adhesive compositions were used.
TZNR®-A4017 (manufactured by Tokyo Ohka Kogyo Co., Ltd.): Elastomer adhesive containing H1051 (manufactured by Asahi Kasei Corp.) and Septon 2002 (manufactured by Kuraray Co., Ltd.).

-Peeling off the support From the support side of the laminate, the separation layer was irradiated with a laser beam having a wavelength of 532 nm under the conditions of a scanning speed of 6400 mm/sec, a frequency of 40 kHz, an output (current value) of 22 A, and an irradiation pitch of 180 µm. After that, the support was peeled off from the substrate of this laminate.

First Washing Step As the first solvent of the first washing solution, three types of "mixture of decalin and butyl acetate", "mixture of butyl acetate and p-menthane", and "p-menthane" were used.
As a predetermined resin, "Septon 2002 (manufactured by Kuraray Co., Ltd.)", a styrene-based thermoplastic elastomer, which is an adhesive composition, was dissolved in three types of first solvents so as to be 3% by weight, 3.5% by weight, and 5% by weight, respectively, relative to the first cleaning liquid.

Each of the first cleaning solutions prepared as described above was subjected to paddle cleaning for 1 minute and spin cleaning for 1 minute at a flow rate of 90 g/min on the substrate after the support was peeled off. After that, drying was performed for 1 minute.

- Second cleaning process Each substrate subjected to the first cleaning process was cleaned with a second cleaning liquid containing a second solvent. The second solvent of the second cleaning liquid was the same as the first solvent. That is, when the first solvent of the first cleaning liquid was the "mixed liquid of decalin and butyl acetate", the "mixed liquid of decalin and butyl acetate" was used as the second solvent of the second cleaning liquid. Further, when the first solvent of the first cleaning liquid was "a mixed liquid of butyl acetate and p-menthane", a "mixed liquid of butyl acetate and p-menthane" was used as the second solvent of the second cleaning liquid. Further, when the first solvent of the first cleaning liquid was "p-menthane", "p-menthane" was used as the second solvent of the second cleaning liquid.

The cleaning with the second cleaning liquid was performed at a flow rate of 90 g/min for 1 minute of paddle cleaning and 1 minute of spin cleaning. After that, drying was performed for 1 minute. After the second cleaning step, the residue (having a diameter of 10 μm or more) remaining on the surface of the substrate was measured with a particle counter for evaluation. Table 1 shows the evaluation results. In Table 1, the ◯ mark indicates that the number of residues is 30 or less, and the X mark indicates that the number of residues is 31 or more. In Table 1, - indicates unmeasured.

(Comparative example)
Three types of cleaning liquids, ie, "mixture of decalin and butyl acetate,""mixture of butyl acetate and p-menthane," and "p-menthane," were used for the substrate after peeling off the support. The cleaning with this cleaning liquid was performed at a flow rate of 90 g/min for paddle cleaning for 1 minute and spin cleaning for 1 minute. After that, drying was performed for 1 minute. After cleaning, the residue (having a diameter of 10 μm or more) remaining on the surface of the substrate was measured by a particle counter for evaluation. Table 2 shows the evaluation results. In Table 2, the ◯ mark indicates that the number of residues is 30 or less, and the X mark indicates that the number of residues is 31 or more. In addition, since the resin is not dissolved in the cleaning liquid of the comparative example, the concentration is indicated as 0%.

As shown in Table 2, when "mixture of decalin and butyl acetate", "mixture of butyl acetate and p-menthane", and "p-menthane" were used alone, it was confirmed that 31 or more residues with a diameter of 10 μm or more remained on the surface of the substrate. On the other hand, as shown in Table 1, it was confirmed that if the first cleaning step is performed using the first cleaning solution in which Septon 2002 is dissolved in three types of first solvents at a concentration of 3 to 5% by weight, and then the first cleaning step is performed using the second cleaning solution containing the same second solvent as the first solvent, the number of residues having a diameter of 10 μm or more remaining on the surface of the substrate may be reduced to 30 or less.

Although the embodiments and examples have been described above, the present invention is not limited to the above description, and various modifications can be made without departing from the gist of the present invention. For example, in the above-described embodiment, the method of forming the laminate 100 (100A) is an example, and the laminate 100 (100A) may be formed by other methods.

Reference Signs List 1 Support 2 Separation layer 2a Residue 3 Adhesive layer 3a Surface 4, 4A Substrate 41 Electronic component 41a Top surface 42 Mold 42a, 42b Top surface 5 Resin layer 6, 6A Substrate cleaning device 61 First cleaning unit 611 First cleaning liquid supply device 612 Nozzle 62 Second cleaning unit 621 Second cleaning liquid supply device 622 Nozzle 64 Switching portion 641 Nozzle

Claims (14)

A substrate cleaning method for cleaning the substrate separated from the support by deteriorating the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning step of cleaning the substrate with a first cleaning liquid obtained by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer;
After the first cleaning step, a second cleaning step of cleaning the substrate with a second cleaning liquid having a second solvent capable of dissolving the adhesive layer,
The substrate cleaning method, wherein the predetermined resin is contained in the first cleaning liquid in an amount of 3 to 5% by weight, and the solid content concentration in the second cleaning liquid is 0.5% by weight or less. A substrate cleaning method for cleaning the substrate separated from the support by deteriorating the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning step of cleaning the substrate with a first cleaning liquid obtained by dissolving a predetermined resin in an amount smaller than the content of the predetermined resin in the adhesive used for forming the adhesive layer in a first solvent capable of dissolving the adhesive layer;
A substrate cleaning method comprising, after the first cleaning step, cleaning the substrate with a second cleaning liquid having a solid content concentration of 0.5% by weight or less, which contains a second solvent capable of dissolving a resin layer formed on the substrate by the adhesive layer and the predetermined resin. 3. The substrate cleaning method according to claim 1 , wherein the substrate includes electronic components. The separation layer is altered by light irradiation,
The substrate cleaning method according to any one of claims 1 to 3 , wherein the separation layer is altered by irradiating the laminate with the light, and the first cleaning step is performed on the substrate separated from the support. The adhesive layer in the laminate is formed by applying and drying a solution in which an adhesive is dissolved,
5. The substrate cleaning method according to any one of claims 1 to 4 , wherein one or both of the first solvent and the second solvent match or have a polarity close to that of the solvent of the solution used to form the adhesive layer. 6. The substrate cleaning method of claim 5 , wherein one or both of the first solvent and the second solvent are the same as the solvent of the solution. The substrate cleaning method according to any one of claims 1 to 6 , wherein one or both of the first cleaning liquid and the second cleaning liquid contain a hydrocarbon-based solvent. 8. The substrate cleaning method according to claim 7 , wherein one or both of said first cleaning liquid and said second cleaning liquid further contain an ester solvent in addition to said hydrocarbon solvent. The substrate cleaning method according to any one of claims 1 to 8 , wherein said predetermined resin is a resin contained in an adhesive used to form said adhesive layer. 10. The substrate cleaning method according to any one of claims 1 to 9 , wherein said predetermined resin is a styrene-based thermoplastic elastomer or a cyclic olefin copolymer. A substrate cleaning apparatus for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning unit that cleans the substrate with a first cleaning liquid obtained by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer;
a second cleaning unit for cleaning the substrate with a second cleaning liquid having a second solvent capable of dissolving the adhesive layer after the first cleaning step;
The substrate cleaning apparatus, wherein the predetermined resin is contained in the first cleaning liquid in an amount of 3 to 5% by weight, and the solid content concentration in the second cleaning liquid is 0.5% by weight or less. A substrate cleaning apparatus for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning unit that cleans the substrate with a first cleaning liquid obtained by dissolving a predetermined resin in an amount smaller than the content of the predetermined resin in the adhesive used for forming the adhesive layer in a first solvent capable of dissolving the adhesive layer;
a substrate cleaning apparatus for cleaning the substrate with a second cleaning liquid having a solid content concentration of 0.5% by weight or less and having a second solvent capable of dissolving a resin layer formed on the substrate from the adhesive layer and the predetermined resin after the first cleaning step. A substrate cleaning kit for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning liquid for cleaning the substrate by dissolving a predetermined resin in a first solvent capable of dissolving the adhesive layer;
a second cleaning liquid for cleaning the substrate, which is used after cleaning with the first cleaning liquid, has a second solvent capable of dissolving the adhesive layer, and
The substrate cleaning kit, wherein the predetermined resin is contained in the first cleaning liquid in an amount of 3 to 5% by weight, and the solid content concentration in the second cleaning liquid is 0.5% by weight or less. A substrate cleaning kit for cleaning the substrate separated from the support by altering the separation layer in a laminate in which a support, a separation layer, an adhesive layer, and a substrate are laminated in this order,
a first cleaning liquid for cleaning the substrate by dissolving a predetermined resin in an amount smaller than the content of the predetermined resin in the adhesive used to form the adhesive layer in a first solvent capable of dissolving the adhesive layer;
A substrate cleaning kit comprising a second solvent having a solid content concentration of 0.5% by weight or less, which is used after cleaning with the first cleaning liquid and capable of dissolving the resin layer formed on the substrate by the adhesive layer and the predetermined resin, and a second cleaning liquid for cleaning the substrate.

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