Composition for separation layer formation, support substrate with separation layer, laminate, method for manufacturing the same, and method for manufacturing electronic component

Abstract

The present application relates to a separation layer forming composition, a support substrate with a separation layer, a laminate and a method for manufacturing the same, and a method for manufacturing an electronic component. The present application provides a separation layer forming composition and the like capable of forming a separation layer in a laminate provided with a separation layer between a support substrate and a substrate, in which the photo-reactivity is further improved and the separation property of the support substrate from the laminate is improved. A separation layer forming composition is used for forming a separation layer in a laminate (10) provided with a separation layer (2) and an adhesive layer (3) between a support substrate (1) that transmits light and a substrate (4), the separation layer being denatured by irradiation of light from the support substrate side to thereby separate the support substrate from the laminate, the separation layer forming composition containing a resin component (P) having a repeating unit represented by general formula (p1). In general formula (p1), L P1 represents a divalent linking group. R P1 represents a condensed polycyclic aromatic group that can have a substituent.[Chemical Formula 1]

Description

Technical Field

[0001] This invention relates to compositions for forming release layers, support substrates with release layers, laminates, methods for manufacturing the same, and methods for manufacturing electronic components. Background Technology

[0002] Semiconductor packages (electronic components) containing semiconductor elements exist in various forms depending on their size, such as WLP (Wafer Level Package) and PLP (Panel Level Package).

[0003] Examples of semiconductor packaging technologies include fan-in and fan-out technologies. As a semiconductor package based on fan-in technology, a fan-in Wafer Level Package (WLP) is known, in which terminals located at the end of the bare die are reconfigured within the chip area. As a semiconductor package based on fan-out technology, a fan-out Wafer Level Package (WLP) is known, in which terminals are reconfigured outside the chip area.

[0004] In recent years, fan-out technology, in particular, has attracted attention as a method that can be applied to the arrangement and packaging of semiconductor components on panels, such as fan-out panel level packages (PLPs), and can achieve further high integration, thinning and miniaturization in semiconductor packaging.

[0005] To achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled components. However, reducing the substrate thickness reduces its strength, making it more susceptible to breakage during semiconductor package manufacturing. In contrast, a laminate is used, which is obtained by bonding a support substrate onto the substrate.

[0006] Patent Document 1 discloses the following method: a light-transmitting support substrate and a substrate are bonded together with a photothermal conversion layer (separation layer) and an adhesive layer disposed on the support substrate side; after processing the substrate, radioactive energy (light) is irradiated from the support substrate side onto the separation layer, causing the separation layer to denature and decompose; thereby separating the processed substrate from the support substrate to manufacture a laminate.

[0007] Existing technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2004-64040 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] As described in Patent Document 1, when miniaturization of semiconductor packaging is achieved by using a laminate obtained by attaching a support substrate to a substrate, the separability of the support substrate from the laminate becomes a problem.

[0012] The present invention was made in view of the above circumstances, and its objective is to provide: a composition for forming a separation layer in a laminate having a separation layer between a support substrate and a substrate, which further improves photoreactivity and improves the separability of the support substrate from the laminate; a support substrate with a separation layer using the same; a laminate; a method for manufacturing the same; and a method for manufacturing an electronic component.

[0013] Methods for solving problems

[0014] To address the aforementioned issues, the present invention employs the following configuration.

[0015] That is, the first aspect of the present invention is a composition for forming a separation layer, characterized in that it is used to form the aforementioned separation layer in a laminate having a separation layer between a support substrate and a substrate that allows light to pass through, the separation layer being able to be deformed by irradiation from the aforementioned support substrate side, thereby separating the aforementioned support substrate from the aforementioned laminate, the composition for forming the separation layer containing a resin component (P) having repeating units represented by the following general formula (p1).

[0016] [Chemical Formula 1]

[0017]

[0018] [In the formula, L] P1 This indicates a divalent linker. R P1 This indicates a fused polycyclic aromatic group that may have substituents.

[0019] The second aspect of the present invention is a support substrate with a separation layer, characterized in that it comprises: a support substrate; and a separation layer formed on the support substrate using the separation layer forming composition involved in the first aspect.

[0020] The third aspect of the present invention is a laminate, characterized in that it is a laminate having a separation layer between a light-transmitting support substrate and a substrate, wherein the separation layer is a sintered body of the separation layer forming composition involved in the first aspect.

[0021] The fourth aspect of the present invention is a method for manufacturing a laminate, characterized in that it is a method for manufacturing a laminate having a separation layer between a light-transmitting support substrate and a substrate, the manufacturing method comprising the following steps: a separation layer forming step, wherein the separation layer forming composition of the first aspect is applied to at least one of the aforementioned substrate or the aforementioned support substrate, and then fired to form the aforementioned separation layer; and a lamination step, wherein the aforementioned substrate and the aforementioned support substrate are laminated with the aforementioned separation layer in between.

[0022] The fifth aspect of the present invention is a method for manufacturing an electronic component, characterized by comprising the following steps: a separation step in which, after obtaining a laminate using the manufacturing method of the laminate involved in the fourth aspect, light is irradiated onto the separation layer through the aforementioned support substrate to denature the separation layer, thereby separating the aforementioned support substrate from the aforementioned laminate; and a removal step in which, after the aforementioned separation step, the aforementioned separation layer attached to the aforementioned substrate is removed.

[0023] Invention Effects

[0024] According to the present invention, a separation layer forming composition that can be formed in a laminate having a separation layer between a support substrate and a substrate, which further improves photoreactivity and improves the separability of the support substrate from the laminate, a support substrate with a separation layer using the same, a laminate, a method for manufacturing the same, and a method for manufacturing electronic components can be provided. Attached Figure Description

[0025] [ Figure 1 This is a schematic diagram illustrating one embodiment of a laminate to which the present invention is applied.

[0026] [ Figure 2 This is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate. Figure 2 (a) is a diagram illustrating the separation layer formation process. Figure 2 (b) is a diagram illustrating the lamination process.

[0027] [ Figure 3 [A schematic process diagram illustrating other embodiments of the manufacturing method of the laminate.] Figure 3 (a) A diagram illustrating a laminate manufactured using the manufacturing method of the first embodiment. Figure 3 (b) is a diagram illustrating the sealing process.

[0028] [ Figure 4 [A schematic process diagram illustrating other embodiments of the manufacturing method of the laminate.] Figure 4 (a) A diagram showing a sealing body manufactured using the manufacturing method of the second embodiment. Figure 4 (b) is a diagram illustrating the grinding process. Figure 4 (c) is a diagram illustrating the rewiring process.

[0029] [ Figure 5 This is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 5 (a) A diagram showing a laminate manufactured using the manufacturing method of the third embodiment. Figure 5 (b) is a diagram illustrating the separation process. Figure 5 (c) is a diagram illustrating the removal process.

[0030] [ Figure 6 This is a schematic process diagram illustrating another embodiment of the manufacturing method of semiconductor package (electronic component). Figure 6 (a) A schematic diagram illustrating other embodiments of the laminate to which the present invention is applied. Figure 6 (b) is a diagram illustrating the separation process. Figure 6 (c) is a diagram illustrating the removal process.

[0031] Explanation of reference numerals in the attached figures

[0032] 1 Supporting substrate, 2 Release layer, 3 Adhesive layer, 4 Substrate, 5 Sealing material layer, 6 Rewiring layer, 10 Laminate, 20 Sealing layer, 30 Laminate, 40 Electronic component, 50 Laminate, 51 Supporting substrate, 52 Release layer, 54 Substrate, 55 Sealing material layer, 57 Wiring layer, 60 Electronic component Detailed Implementation

[0033] In this specification and claims, the term "aliphatic" is a relative concept compared to aromatic compounds, and is defined as groups, compounds, etc., that do not possess aromaticity.

[0034] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0035] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0036] "Halogenated alkyl" is a group in which some or all of the hydrogen atoms of an alkyl group are replaced by halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0037] "Fluoroalkyl" refers to a group in which some or all of the hydrogen atoms of an alkyl group are replaced by fluorine atoms.

[0038] The term "repeating unit" refers to the monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer).

[0039] The cases described as "may have substituents" include both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH2-) is replaced by a divalent group.

[0040] The term "styrene" encompasses both styrene and compounds formed by replacing the hydrogen atom at the α-position of styrene with other substituents such as alkyl or haloalkyl groups. It should be noted that the α-position (the carbon atom at the α-position), unless otherwise specified, refers to the carbon atom bonded to the benzene ring.

[0041] The alkyl group used as the substituent at the α-position is preferably a straight-chain or branched alkyl group. Specifically, examples include alkyl groups with 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.).

[0042] Furthermore, the alkyl halogroup that serves as the substituent at the α-position can be specifically a group formed by replacing part or all of the hydrogen atoms of the aforementioned alkyl halogroup with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0043] In this specification and claims, based on the structure shown in the chemical formula, a chiral carbon may be present, and enantiomers and diastereomers may be present. In this case, a single chemical formula is used to represent these isomers. These isomers may be used alone or in mixtures.

[0044] (Composition for forming the separation layer)

[0045] The separation layer forming composition according to the first aspect of the present invention is used to form the aforementioned separation layer in a laminate having a separation layer between a light-transmitting support substrate and a substrate. The separation layer can be denatured by irradiation from the support substrate side, thereby causing the support substrate to separate from the laminate. The separation layer forming composition of this embodiment contains at least a resin component (P) having repeating units represented by the general formula (p1).

[0046] Figure 1 An embodiment of a laminate in which the present invention is applied is shown.

[0047] Figure 1 The laminate 10 shown has a separation layer 2 and an adhesive layer 3 between the support substrate 1 and the substrate 4, and the separation layer 2, the adhesive layer 3 and the substrate 4 are sequentially stacked on the support substrate 1.

[0048] The support substrate 1 is formed of a light-transmitting material. In the laminate 10, the separation layer 2 is denatured and decomposed by irradiating light from the support substrate 1 side, thereby separating the support substrate 1 from the laminate 10.

[0049] The separation layer 2 in the laminate 10 can be formed using the separation layer forming composition of this embodiment.

[0050] <Resin Components (P)>

[0051] Resin component (P) (hereinafter also referred to as "(P) component") is a resin component having repeating units represented by the general formula (p1).

[0052] (P) The component has a fused polycyclic aromatic group (R) in the repeating unit that may have substituents. P1 Therefore, in the separation layer formed by the composition for forming a separation layer containing (P) component, laser reactivity is enhanced, photoreactivity is further improved, and the separation of the support matrix from the laminate is improved.

[0053] Furthermore, the (P) component has a divalent linker (L) in the repeating unit. P1 Therefore, the (P) component is easily denatured (oxidized, etc.) by heating or the like. In the separation layer formed by the separation layer forming composition containing the (P) component, light absorption is improved and photoreactivity is excellent.

[0054] exist Figure 1 In a laminate 10 comprising a release layer 2 formed using a release layer forming composition containing component (P), the release layer 2 is denatured and easily peeled off from the substrate 4 by irradiation with light from the support substrate 1 side, thus separating the support substrate 1. Furthermore, the release layer 2 containing component (P) leaves minimal residue on the substrate 4 upon peeling, exhibiting good removability from the substrate 4. Moreover, since the (P) component has divalent linking groups (L...) in the repeating units... P1 Therefore, the heat resistance of the separation layer 2 containing (P) component is improved, and it also has high chemical resistance.

[0055] Furthermore, due to the strong laser reactivity of the (P) component, laser damage to the separation layer 2 containing the (P) component is suppressed. In addition, the laser intensity can be increased, which can shorten the process time.

[0056] (P) Components can be components that have other repeating units besides the repeating units represented by the general formula (p1).

[0057] Repeating units represented by the general formula (p1)

[0058] (P) component has repeating units represented by the following general formula (p1) (hereinafter also referred to as "repeating unit (p1)").

[0059] [Chemical Formula 2]

[0060]

[0061] [In the formula, L] P1 This indicates a divalent linker. R P1 This indicates a fused polycyclic aromatic group that may have substituents.

[0062] In the aforementioned formula (p1), L P1 The divalent linker can contain aromatic rings, multiple aromatic rings, or a ring structure formed by the fusion of aromatic rings and aliphatic rings.

[0063] L P1 When the divalent linker contains an aromatic ring, there is no particular limitation as long as the aromatic ring is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12.

[0064] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by the substitution of a portion of the carbon atoms in the aforementioned aromatic hydrocarbon rings by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0065] The divalent linker may contain one or more aromatic rings, but from the perspective of better photoreactivity, two or more are preferred.

[0066] Alternatively, in the aforementioned equation (p1), L P1 The divalent linker in the L-type is preferably a divalent linker containing a heteroatom. p1 Examples of various backbone linking groups introduced to impart the desired properties can be cited.

[0067] Examples of skeletons mentioned above that are "linking groups with various skeletons" include naphthalene skeleton, anthracene skeleton, thallium skeleton, fluorene skeleton, bisphenol A skeleton, etc.

[0068] As L p1 Examples include ether-bonded groups of bisphenols, ether-bonded groups of diols, ester-bonded groups of dicarboxylic acids, Si-O-bonded groups, or repeating structures of these bonded groups.

[0069] Examples of this type of bisphenol include bisphenol F, bisphenol A, bisphenol Z, biphenol, or their polymers.

[0070] Examples of such diols include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, naphthalene glycol (dihydroxynaphthalene), anthracene glycol (dihydroxyanthracene), 2,2-bis(4-hydroxyphenyl)propane, or polymers thereof.

[0071] Examples of dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid, and terephthalic acid.

[0072] Choose bisphenol ether bonding groups as L p1 In this case, it is easy to improve the flexibility of the (P) component film.

[0073] Diol-based ether bonding groups are selected as L. p1 In this case, the alkali solubility of component (P) can be easily adjusted. As the ether bonding group of the diol class, a linking group with a diol backbone is preferred. For example, a propylene glycol backbone can be cited as an example of a diol backbone.

[0074] Si-O bonding groups were selected as L p1 In this case, it is easy to achieve low dielectric properties in (P) component molded articles.

[0075] The following shows L in the aforementioned equation (p1) P1 Preferred specific examples of (divalent linking groups). In the following formula, * indicates a chemical bond with a methylene group (CH2). Chemical formula (L P1 -9) represents the number of repetitions of the propylene oxide group.

[0076] [Chemical Formula 3]

[0077]

[0078] In the aforementioned equation (p1), R P1 It is a fused polycyclic aromatic group that can have substituents.

[0079] R P1 The fused polycyclic aromatic group is a group obtained by removing one hydrogen atom from a fused polycyclic aromatic ring. This fused polycyclic aromatic ring can be a ring structure formed by the fusion of multiple aromatic rings, or a ring structure formed by the fusion of an aromatic ring and an aliphatic ring. In the ring structure formed by the fusion of aromatic and aliphatic rings, there can be multiple aromatic rings, multiple aliphatic rings, or one aromatic ring and one aliphatic ring.

[0080] The number of rings constituting the fused polycyclic aromatic ring is preferably 2 to 5, more preferably 2 to 3, and even more preferably 3.

[0081] In the aforementioned equation (p1), R is... P1 The fused polycyclic aromatic groups in the molecule may have substituents, such as hydroxyl, carboxyl, halogen atoms (fluorine, chlorine, bromine, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy carbonyl, oxo (=O), etc.

[0082] Additionally, R P1 In fused polycyclic aromatic groups, the hydrocarbon groups can have ether bonds in the middle of their hydrocarbon chains.

[0083] As R P1 For example, examples include naphthalene rings, azurite rings, anthracene rings, phenanthrene rings, pyrene rings, etc. A group obtained by removing one hydrogen atom from a ring, triphenylene ring, perylene ring, anthraquinone ring, or naphthoquinone ring.

[0084] Among them, as R P1 Preferably, it is a group obtained by removing one hydrogen atom from an anthraquinone ring or a naphthoquinone ring, more preferably a group obtained by removing one hydrogen atom from an anthraquinone ring.

[0085] The following shows a preferred example of the repeating unit (p1). In the chemical formula (p1-6), n1 represents the number of repetitions of the propylene oxide group.

[0086] [Chemical Formula 4]

[0087]

[0088] [Chemical Formula 5]

[0089]

[0090] The repeating unit (p1) of component (P) can be one type or two or more types.

[0091] The proportion of repeating units (p1) in component (P) is preferably 1 mol% or more relative to the total (100 mol%) of all repeating units constituting component (P), and may also be 1 to 100 mol%.

[0092] When the component (P) has other repeating units besides the repeating unit (p1), the proportion of the repeating unit (p1) in the component (P) is preferably 1 to 99 mol% relative to the total (100 mol%) of all repeating units constituting the component (P), more preferably 1 to 70 mol%, and even more preferably 1 to 50 mol%.

[0093] When the proportion of repeating units (p1) is above the lower limit of the aforementioned preferred range, laser reactivity is easily enhanced. On the other hand, when it is below the upper limit of the aforementioned preferred range, it is easier to achieve balance with other repeating units.

[0094] Other repeating units

[0095] (P) Components can be components that have other repeating units besides the repeating unit (p1) mentioned above.

[0096] Other repeating units include, for example, repeating units represented by the general formula (p2) described later.

[0097] Regarding the repeating unit represented by the general formula (p2):

[0098] (P) The preferred component is a resin that, in addition to the repeating unit (p1) described above, also has repeating units represented by the following general formula (p2) (hereinafter also referred to as "repeating unit (p2)").

[0099] [Chemical Formula 6]

[0100]

[0101] [In the formula, L] P2 This indicates a divalent linker. R P2 This indicates a monocyclic aromatic group that may have substituents.

[0102] In the aforementioned equation (p2), regarding L P2 The explanation is the same as L in the above formula (p1). P1 The same applies to the explanation regarding divalent linking groups.

[0103] As L P2 Preferred examples of (divalent linking groups) can be given by those derived from the above chemical formulas (L... P1 -1)~(L P1 -9) indicates the same linking group as the linking group.

[0104] In the aforementioned equation (p2), R P2 The monocyclic aromatic group in the formula is a hydrocarbon group having one aromatic ring. This aromatic ring can be a cyclic conjugated system with 4n+2 π electrons.

[0105] As a component of R P2 The aromatic rings containing monocyclic aromatic groups in the text, specifically, include benzene rings; pyridine rings, thiophene rings, pyrrole rings, imidazole rings, furan rings, thiazole rings, etc. Among them, as R... P2 Preferably, it is a group obtained by removing one hydrogen atom from the benzene ring.

[0106] The above RP2 When the indicated hydrocarbon group is substituted, examples of substituents include hydroxyl, carboxyl, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy carbonyl, etc.

[0107] The following shows a preferred example of the repeating unit (p2). In the chemical formula (p2-6), n2 represents the number of repeats of the propylene oxide group.

[0108] [Chemical Formula 7]

[0109]

[0110] When component (P) has repeating unit (p2), the repeating unit (p2) can be one type or two or more types.

[0111] When component (P) has repeating unit (p2), the proportion of repeating unit (p2) in component (P) relative to the total (100 mol%) of all repeating units constituting component (P) is preferably 1 to 99 mol%, more preferably 30 to 99 mol%, and even more preferably 50 to 99 mol%.

[0112] When the proportion of repeating units (p2) is above the lower limit of the aforementioned preferred range, photoreactivity is easily improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, it is easy to achieve balance with the repeating units (p1).

[0113] In the composition for forming the separation layer of this embodiment, component (P) is a resin having at least repeating units (p1).

[0114] (P) component can also be a resin formed solely from repeating units (p1).

[0115] As a preferred (P) component, a resin having repeating units (p1) and repeating units (p2) can be cited. In this case, the ratio (molar ratio) of repeating units (p1) to repeating units (p2) in the resin is preferably repeating unit (p1): repeating unit (p2) = 1:99 to 99:1, more preferably 1:99 to 70:30, and even more preferably 1:99 to 50:50.

[0116] Alternatively, component (P) may be a mixture of a resin having at least repeating units (p1) and a resin formed solely of repeating units (p2). In this case, the proportion of repeating units (p1) is preferably 1 to 99 mol% relative to the total (100 mol%) of all repeating units constituting the mixture, more preferably 1 to 70 mol%, and even more preferably 1 to 50 mol%. The molar ratio (molar ratio) of all repeating units (p1) to all repeating units (p2) constituting the mixture is preferably 1:99 to 99:1, more preferably 1:99 to 70:30, and even more preferably 1:99 to 50:50.

[0117] The (P) component has film-forming ability, and preferably has a molecular weight of 1000 or more. By making the molecular weight of the (P) component 1000 or more, the film-forming ability is improved. The molecular weight of the (P) component is more preferably 1000 to 30000, further preferably 1500 to 25000, particularly preferably 1500 to 20000, and most preferably 2000 to 15000.

[0118] By making the molecular weight of component (P) below the upper limit of the aforementioned preferred range, the solubility of the composition for separating the layer is improved in the solvent.

[0119] It should be noted that the molecular weight of the resin component is the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0120] As a component (P), for example, the GSP series (manufactured by Kumiei Chemical Industry Co., Ltd.) with trade names such as GSP-112, GSP-113, and GSP-117 can be used.

[0121] Alternatively, as component (P), a resin can be used that is generated by reacting aminoanthraquinone or aminonaphthoquinone with aminophenols, aminonaphthoquinones or anilines, or with a compound having two epoxy groups in one molecule.

[0122] Examples of aminophenols include 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 2-amino-4-methylphenol, 3-amino-2-methylphenol, and 5-amino-2-methylphenol. Examples of aminonaphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, and 5-amino-1-naphthol.

[0123] 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 DENACOL EX-211, DENACOL EX-212, DENACOL EX-810, DENACOL EX-830, DENACOL EX-911, DENACOL EX-920, and DENACOL EX-930 (manufactured by Nagase Chemtex Corporation); and DENACOL EX-711 and DENACOL EX-721 (manufactured by Nagase Chemtex Corporation). Dicarboxylate epoxy resins such as Chemtex Corporation and JER191P (Mitsubishi Chemical Corporation); silicone epoxy resins such as X-22-163 and KF-105 (Shin-Etsu Chemical Industry Co., Ltd.).

[0124] The heating temperature during the above reaction is preferably set to 60°C or higher and 250°C or lower, and more preferably to 80°C or higher and 180°C or lower.

[0125] The (P) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types.

[0126] The content of component (P) in the composition for forming the separation layer in this embodiment can be adjusted according to the thickness of the separation layer to be formed.

[0127] Regarding the content of the (P) component in the composition for forming the separation layer, for example, it is preferably 1 to 100% by mass, more preferably 1 to 70% by mass, further preferably 5 to 50% by mass, and particularly preferably 10 to 50% by mass, relative to the composition (100% by mass).

[0128] When the content of component (P) is above the lower limit of the aforementioned preferred range, it is easier to improve the photoreactivity of the release layer. Furthermore, it is also easier to improve chemical resistance. On the other hand, when it is below the upper limit of the aforementioned preferred range, it is easier to improve photoreactivity and peelability.

[0129] <Other Ingredients>

[0130] The composition for forming the separation layer in this embodiment may also contain components other than the (P) component described above (optional components).

[0131] As optional components, examples include resins other than the (P) components shown below, thermal acid-producing components, photoacid-producing components, photosensitizer components, organic solvent components, surfactants, sensitizers, etc.

[0132] The composition for forming the separation layer in this embodiment may contain resin other than component (P) without impairing the effects of the present invention.

[0133] Examples of resins other than component (P) include Novolac-type phenolic resins, Resol-type phenolic resins, hydroxystyrene resins, hydroxyphenyl silsesquioxane resins, hydroxybenzyl silsesquioxane resins, and acrylic resins containing a phenolic skeleton.

[0134] By using Novolac-type phenolic resin, which is a resin other than component (P), in combination with component (P), the generation of voids caused by heating can also be easily suppressed.

[0135] Heat-generating acid agents

[0136] The composition for forming the separation layer in this embodiment preferably further contains a thermally generated acid agent (hereinafter also referred to as "(T) component").

[0137] By including the (T) component in the composition for forming the separation layer, the oxidation of the separation layer is promoted by the action of the acid generated by the (T) component under conditions such as heating during firing, thus making it easier to denature due to light irradiation (which can improve the photoreactivity of the separation layer).

[0138] As component (T), it can be suitably selected from known components, and the temperature at which it generates acid is preferably above the temperature at which the support substrate coated with the composition for forming the release layer is pre-baked, more preferably above 110°C, and even more preferably above 130°C.

[0139] Examples of components (T) include trifluoromethanesulfonate, hexafluorophosphate, perfluorobutyrate, boron trifluoride salt, and boron trifluoride ether complexes. Preferred components (T) include compounds formed from cationic and anionic portions as shown below.

[0140] [Chemical Formula 8]

[0141]

[0142] In formula (T-ca-1), R h01 ~R h04 Each is independently a group selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and aryl groups, R h01 ~R h04 At least one of them is an aryl group. The aforementioned alkyl or aryl group may have substituents. In formula (T-ca-2), R h05 ~R h07Each is independently a group selected from the group consisting of alkyl and aryl groups having 1 to 20 carbon atoms, R h05 ~R h07 At least one of them is an aryl group. The aforementioned alkyl or aryl groups may have substituents.

[0143] • Regarding the cationic portion of component (T)

[0144] In the aforementioned formula (T-ca-1), R h01 ~R h04 The alkyl group has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and even more preferably a straight-chain or branched alkyl group with 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., among which methyl and ethyl are preferred.

[0145] R h01 ~R h04 The alkyl group may have substituents. Examples of such substituents include alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups.

[0146] The alkoxy group that is a substituent for an alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0147] Examples of halogen atoms that can be used as substituents for alkyl groups include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0148] Haloalkyl groups that are substituents of alkyl groups include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms.

[0149] The carbonyl group that is a substituent for an alkyl group is a group that replaces the methylene group (-CH2-) that constitutes the alkyl group (>C=O).

[0150] Examples of cyclic groups that can be substituents for alkyl groups include aromatic hydrocarbon groups and alicyclic hydrocarbon groups (which can be polycyclic or monocyclic). Aromatic hydrocarbon groups mentioned here include those related to R described later. h01 ~R h04The same group as the aryl group. Among the alicyclic hydrocarbon groups here, as monocyclic alicyclic hydrocarbon groups, groups obtained by removing one or more hydrogen atoms from a monocyclic alkane are preferred. As the monocyclic alkane, monocyclic alkanes with 3 to 6 carbon atoms are preferred; specifically, cyclopentane, cyclohexane, etc., are examples. Furthermore, as polycyclic alicyclic hydrocarbon groups, groups obtained by removing one or more hydrogen atoms from a polycyclic alkane are preferred; as the polycyclic alkane, polycyclic alkanes with 7 to 30 carbon atoms are preferred. More preferably, as the polycyclic alkane, are polycyclic alkanes with a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or polycyclic alkanes with a fused ring system such as a cyclic group containing a steroidal skeleton.

[0151] In the aforementioned formula (T-ca-1), R h01 ~R h04 The aryl group in the figure is a hydrocarbon group having at least one aromatic ring.

[0152] The aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12.

[0153] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by the substitution of a portion of the carbon atoms in the aforementioned aromatic hydrocarbon rings by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0154] As R h01 ~R h04 Specifically, the aryl group in the aryl group can be exemplified by: a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); or a group obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1. More preferably, these are groups obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle, or groups obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group, and even more preferably groups obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or groups obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring with an alkylene group.

[0155] R h01 ~R h04 The aryl group may have substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, cyclic, alkylcarbonyloxy, etc.

[0156] The alkyl group used as a substituent for the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0157] The descriptions of alkoxy groups, halogen atoms, haloalkyl groups, carbonyl groups, and cyclic groups that are substituents for aryl groups are the same as those of alkoxy groups, halogen atoms, haloalkyl groups, carbonyl groups, and cyclic groups that are substituents for alkyl groups described above.

[0158] In the alkyl carbonyloxy group that is a substituent for aryl, the number of carbon atoms in the alkyl moiety is preferably 1 to 5, and examples of the alkyl moiety include methyl, ethyl, propyl, isopropyl, etc., among which methyl and ethyl are preferred, and methyl is more preferred.

[0159] In the aforementioned formula (T-ca-1), R h01 ~R h04 At least one of them is an aryl group that may have substituents.

[0160] The following are specific examples of cations represented by the aforementioned formula (T-ca-1).

[0161] [Chemical Formula 9]

[0162]

[0163] In the aforementioned equation (T-ca-2), regarding R h05 ~R h07 The descriptions of alkyl and aryl groups in the above are respectively related to the descriptions of R. h01 ~R h04 The explanations for alkyl and aryl groups are the same.

[0164] In the aforementioned formula (T-ca-2), R h05 ~R h07 At least one of them is an aryl group that may have substituents.

[0165] The following are specific examples of cations represented by the aforementioned formula (T-ca-2).

[0166] [Chemical Formula 10]

[0167]

[0168] • Regarding the anionic portion of component (T)

[0169] Examples of anionic components of (T) include hexafluorophosphate anion, trifluoromethanesulfonic acid anion, perfluorobutyrate anion, and tetra(pentafluorophenyl)borate anion.

[0170] Among them, hexafluorophosphate anion, trifluoromethanesulfonic acid anion, and perfluorobutanesulfonic acid anion are preferred, and hexafluorophosphate anion and trifluoromethanesulfonic acid anion are more preferred.

[0171] In the composition for forming the separation layer in this embodiment, as component (T), for example, the following can be used: San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110, SI-110L, SI-145, SI-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 (all manufactured by San-Shin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66, CP-77 (manufactured by ADEKA Co., Ltd.); FC-520 (manufactured by 3M Corporation); K-PURE TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2 678, TAG-2681, TAG-2679, TAG-2689, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC- Commercially available products including CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60, and CXC-2689 (all manufactured by KING INDUSTRY).

[0172] The (T) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types.

[0173] In the composition for forming the separation layer of this embodiment, among the above-mentioned components, the preferred (T) component is hexafluorophosphate, trifluoromethanesulfonate, or perfluorobutanesulfonate, more preferably trifluoromethanesulfonate, and even more preferably a quaternary ammonium salt of trifluoromethanesulfonate.

[0174] When the composition for forming the separation layer in this embodiment contains component (T), the content of component (T) is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of component (P), more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass.

[0175] If the content of component (T) is within the aforementioned preferred range, it is easily denatured by light irradiation (which can improve the photoreactivity of the separation layer). For example, a sintered body capable of suitable absorption of light in the wavelength range below 600 nm can be easily formed by firing. Furthermore, chemical resistance is further improved.

[0176] Photo-acid generator

[0177] The composition for forming the separation layer in this embodiment may also contain a photoacid-generating agent.

[0178] The composition for forming the separation layer contains a photoacid-generating agent, and thus, similar to the case containing (T) component as described above, under conditions such as heating during firing, the oxidation of the separation layer is promoted by the acid generated by the photoacid-generating agent, and therefore it is easily denatured by light irradiation (which can improve the photoreactivity of the separation layer).

[0179] As photoacid generators, onium salt-based acid generators such as sulfonium salts are preferred examples.

[0180] Preferred cationic components among onium salt-based acid-producing agents include sulfonium cations and iodonium cations.

[0181] Preferred anionic groups among onium salt-based acid-producing agents include: tetratetra(pentafluorophenyl)borate ([B(C6F5)4]). - Tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4]) - ); Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - Tetrafluorophenyl)borate ([B(C6H3F2)4]) - In addition, anions represented by the following general formula (b0-2a) are also preferred.

[0182] [Chemical Formula 11]

[0183]

[0184] [In the formula, R] bf05 It is a fluoroalkyl group that can have substituents. 1 Integers from 1 to 5.

[0185] In the aforementioned equation (b0-2a), R bf05 The fluoroalkyl group in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Among them, as R... bf05 Preferably, it is a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferably trifluoromethyl or pentafluoroethyl.

[0186] In the aforementioned equation (b0-2a), nb 1 Preferably, it is an integer from 1 to 4, more preferably an integer from 2 to 4, and most preferably 3.

[0187] nb 1 When the value is 2 or higher, multiple R bf05 They can be the same, or they can be completely different.

[0188] The photoacid-generating agent contained in the separation layer formation composition of this embodiment may be one type or two or more types.

[0189] When the composition for forming the separation layer in this embodiment contains a photoacid generator, the content of the photoacid generator is preferably 0.01 to 20 parts by mass relative to 100 parts by mass of component (P), more preferably 1 to 15 parts by mass, and even more preferably 2 to 10 parts by mass.

[0190] If the content of the photoacid-generating agent is within the aforementioned preferred range, it is easily denatured by light irradiation (which can improve the photoreactivity of the separation layer). For example, a sintered body capable of suitable absorption of light in the wavelength range below 600 nm can be easily formed by firing. Furthermore, chemical resistance is also further improved.

[0191] Photosensitive Ingredients

[0192] As a photosensitizing component (hereinafter also referred to as "(C) component"), for example, the esterification product of a compound containing a phenolic hydroxyl group represented by the following chemical formula (C1) and a compound containing 1,2-diazidonaphthoquinone sulfonic acid (hereinafter also referred to as "(C1) component") is a preferred component.

[0193] [Chemical Formula 12]

[0194]

[0195] Examples of 1,2-diazidonaphthoquinone sulfonic acid compounds include 1,2-diazidonaphthoquinone-5-sulfonyl compounds and 1,2-diazidonaphthoquinone-4-sulfonyl compounds, with 1,2-diazidonaphthoquinone-5-sulfonyl compounds being preferred.

[0196] The following shows a preferred example of component (C1).

[0197] [Chemical Formula 13]

[0198]

[0199] In formula (c1-1), D 1 ~D 4 Each can be represented independently as a hydrogen atom or a 1,2-diazidonaphthoquinone-5-sulfonyl group. D 1 ~D 4 At least one of them represents 1,2-diazidonaphthoquinone-5-sulfonyl.

[0200] The esterification rate of the aforementioned (C1) component is preferably 50-70%, more preferably 55-65%. If the esterification rate is 50% or higher, film loss after alkaline development can be further suppressed, and the residual film rate can be increased. If the esterification rate is 70% or lower, the storage stability is further improved.

[0201] The term "esterification rate" here, for the compound represented by the aforementioned formula (c1-1), refers to D in formula (c1-1). 1 ~D 4 The proportion of 1,2-diazidonaphthoquinone-5-sulfonyl groups substituted.

[0202] The aforementioned (C1) component is also preferred from the perspective of being very inexpensive and capable of achieving high sensitivity.

[0203] In addition, other photosensitizing components besides the aforementioned component (C1) can be used as component (C2).

[0204] As a (C2) component, for example, the esterification reaction product of a compound containing a phenolic hydroxyl group ((C2-Phe) component) and a 1,2-diazidonaphthoquinone sulfonic acid compound (preferably a 1,2-diazidonaphthoquinone-5-sulfonyl compound or a 1,2-diazidonaphthoquinone-4-sulfonyl compound) is a preferred component.

[0205] Examples of the aforementioned (C2-Phe) components include, for instance, tris(4-hydroxyphenyl)methane, bis(4-hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3 ... (dimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3 ...3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxyphenylmethane)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxyphenylmethane)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxyphenylmethane)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxyphenylmethane)-3-hydroxyphenylmethane, bis( 1-[1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(2',4'-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4'-hydroxyphenyl)propane 2-(3-fluoro-4-hydroxyphenyl)-2-(3'-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl)propane, bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4'-hydroxyphenylmethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,4-bis[1-(4-hydroxyphenyl)isopropyl]-5-hydroxyphenol, etc.

[0206] The (C) component contained in the separation layer forming composition of this embodiment can be used alone or in combination of two or more.

[0207] In the composition for forming the separation layer of this embodiment, among the above-mentioned components (C), component (C1) is preferably used.

[0208] When the composition for forming the separation layer in this embodiment contains component (C), the content of component (C) is preferably 95 parts by mass or less, more preferably 50 to 95 parts by mass, and even more preferably 60 to 90 parts by mass, relative to 100 parts by mass of component (P).

[0209] If the content of component (C) is within the aforementioned preferred range, the photoreactivity of the separation layer can be further improved.

[0210] Organic Solvent Composition

[0211] The composition for forming the release layer in this embodiment may contain an organic solvent component (hereinafter also referred to as "(S) component") to adjust coating workability, etc.

[0212] Examples of (S) components include, for example: straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, and tridecane; branched hydrocarbons with 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; and p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, camphene, norbornene, pinane, thujone, carene, and longifene. Geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroterpinene acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, dipentene, and other terpene solvents; γ-butyrolactone and other lactones; acetone, methyl ethyl ketone, cyclohexanone (CH4) Ketones such as methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and derivatives of polyols such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., or monoalkyl ethers or monophenyl ethers, etc. (Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butylphenyl ether, etc.

[0213] The (S) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types.

[0214] In the separation layer forming composition of this embodiment, the amount of component (S) is not particularly limited, and can be appropriately set according to the coating film thickness and coatability within a concentration that allows it to be coated onto a support substrate, etc. Preferably, component (S) is used in such a way that the total amount of the above-mentioned component (P) in the separation layer forming composition is in the range of 70% by mass or less, more preferably 10 to 50% by mass, relative to the total mass (100% by mass) of the composition.

[0215] Surfactants

[0216] The composition for forming the release layer in this embodiment may contain a surfactant in order to adjust the coating workability, etc.

[0217] Examples of surfactants include, for example, silicone-based surfactants and fluorinated surfactants. Examples of silicone-based surfactants include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-322, BYK-323, BYK-325, BYK-330, BYK-331, and BYK-335. 3. BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355, BY K-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (the above is BYK Chemie Co., Ltd.), etc. Fluorinated surfactants such as F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F-445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484, F-486, F-487, F-172D, MCF-350SF, and T can be used. F-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF-1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (all manufactured by DIC Corporation); PolyFox series PF-636, PF-6320, PF-656, PF-6520 (all manufactured by Omnova Corporation), etc.

[0218] The composition for forming the separation layer in this embodiment may contain one or more surfactants.

[0219] When the composition for forming the separation layer in this embodiment contains a surfactant, the content of the surfactant is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of component (P), more preferably 0.02 to 2 parts by mass, and even more preferably 0.03 to 1 part by mass.

[0220] If the surfactant content is within the aforementioned preferred range, a highly flat separation layer can be easily formed when the separation layer forming composition is applied to the support substrate.

[0221] (Supporting substrate with separation layer)

[0222] The second aspect of the present invention relates to a support substrate with a separation layer comprising: a support substrate; and a separation layer formed on the support substrate using the separation layer forming composition of the first aspect.

[0223] In the support substrate with a separation layer of this embodiment, a separation layer formed using the separation layer forming composition of the above-described embodiment is provided on the support substrate. Therefore, in the support substrate with the separation layer, photoreactivity and chemical resistance are improved.

[0224] <Supporting Substrate>

[0225] The support substrate has the property of allowing light to pass through. The support substrate is a component that supports the substrate and is attached to the substrate through a release layer. Therefore, as a support substrate, it is preferable to have the strength required to prevent damage or deformation of the substrate during processes such as thinning of the sealant, handling of the substrate, and mounting onto the substrate. Furthermore, the support substrate is preferably designed to allow light of wavelengths capable of deforming the release layer to pass through.

[0226] Materials used as the supporting substrate can include, for example, glass, silicone, acrylic resin, etc. The shape of the supporting substrate can include, for example, rectangles, circles, etc., but is not limited to these.

[0227] In addition, as a support substrate, in order to further achieve high-density integration and improve production efficiency, a substrate obtained by increasing the size of a circular support substrate and a large panel with a quadrilateral shape when viewed from above can also be used.

[0228] <Separation Layer>

[0229] The release layer can be formed using the release layer forming composition of the above-described embodiments, and is a layer formed by firing a sintered body containing a resin component (P) of the release layer forming composition. This release layer adaptably modulates by absorbing light irradiated through the supporting substrate.

[0230] It should be noted that the separation layer can also be a layer obtained by combining a material that does not have a light-absorbing structure within the range that does not impair the essential characteristics of the present invention, but from the viewpoint of photoreactivity and separation, it is preferable to form it only by a light-absorbing material.

[0231] The term "fired body" as used here refers to the product obtained by firing a composition containing (P) component.

[0232] This sintered body is formed by sintering a composition containing (P) in an atmospheric environment, i.e., in the presence of oxygen, wherein at least a portion of the composition is carbonized. The sintered body constituting the separation layer in this embodiment is capable of absorbing light in the wavelength range below 600 nm, and preferably has high chemical resistance.

[0233] The term "deterioration" of the separation layer refers to the phenomenon where the separation layer becomes susceptible to damage under external forces, or where the adhesive strength between the separation layer and the layers in contact with it decreases. The separation layer becomes brittle by absorbing light, losing its strength or adhesiveness before exposure to light. This deterioration occurs through processes such as decomposition caused by the energy of the absorbed light, changes in its stereostructure, or dissociation of functional groups.

[0234] The thickness of the separation layer is preferably 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.

[0235] If the thickness of the separation layer is in the range of 0.05 μm or more and 50 μm or less, the desired denaturation can be achieved by short-term and low-energy light irradiation. Furthermore, from a productivity point of view, the thickness of the separation layer is particularly preferably in the range of 1 μm or less.

[0236] For example in Figure 1 In the laminate 10 shown, the side of the separation layer that is in contact with the adhesive layer is preferably flat (without any unevenness), thereby making it easy to form the adhesive layer and to easily attach the support substrate to the substrate uniformly.

[0237] The support substrate with the separation layer in this embodiment can be manufactured by performing the same operation as the [separation layer formation process] described later.

[0238] The support substrate with a separation layer in this embodiment exhibits enhanced laser reactivity and further improved photoreactivity due to the separation layer obtained by applying the separation layer forming composition of the above-described embodiment. Preferably, chemical resistance is also improved.

[0239] (Layered structure)

[0240] The laminate according to the third aspect of the present invention has a separation layer between a light-transmitting support substrate and a substrate. This separation layer is a sintered body of the separation layer forming composition of the above-described embodiments.

[0241] like Figure 1 As shown, in the laminate 10 of this embodiment, a separation layer 2, an adhesive layer 3, and a substrate 4 are sequentially laminated on a support substrate 1.

[0242] The description of support substrate 1 is the same as that in the above description of support substrate.

[0243] The description of separation layer 2 is the same as that in the above description of <Separation Layer>.

[0244] <Adhesive Layer>

[0245] The adhesive layer 3 is a layer used to bond the support substrate 1 to the substrate 4, and can be formed using an adhesive layer forming composition.

[0246] Examples of compositions for forming the adhesive layer include compositions containing, for example, thermoplastic resins, diluents, and additives. The thermoplastic resin, as long as it exhibits adhesive strength, can be one or more of the following: hydrocarbon resins (preferably cycloolefin polymers), acrylic-styrene resins, maleimide resins, elastomer resins, and polysulfone resins. The diluent can be the same as component (S) described above. Other components include additive resins for improving the performance of the adhesive layer, curable monomers, photopolymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors, and surfactants.

[0247] The thickness of the adhesive layer 3 is preferably in the range of 0.1 μm or more and 50 μm or less, and more preferably in the range of 1 μm or more and 10 μm or less.

[0248] If the thickness of the adhesive layer is in the range of 0.1 μm or more and 50 μm or less, the support substrate 1 and the substrate 4 can be bonded better. In addition, by making the thickness of the adhesive layer 1 μm or more, the substrate can be fully fixed to the support substrate, and by making the thickness of the adhesive layer 10 μm or less, the adhesive layer can be easily removed in the subsequent removal process.

[0249] <Substrate>

[0250] The substrate 4 is supplied for thinning, mounting, and other processes while supported by the support substrate 1. Structures such as integrated circuits and metal bumps are mounted on the substrate 4.

[0251] As substrate 4, a silicon wafer substrate can typically be used, but it is not limited to this; ceramic substrates, thin film substrates, flexible substrates, etc., can also be used.

[0252] In this embodiment, the component is a semiconductor component or other component, and may have a single-layer or multi-layer structure. It should be noted that when the component is a semiconductor component, the electronic component obtained by cutting the sealed substrate becomes a semiconductor device.

[0253] The laminate of the above-described embodiments has enhanced laser reactivity and further improved photoreactivity (appropriately denatured by light irradiation) because it is provided with a separation layer obtained by applying the separation layer forming composition of the above-described embodiments, thereby improving the separation of the support matrix from the laminate.

[0254] Furthermore, the laminate of the embodiment has improved chemical resistance because it is provided with a separation layer obtained by applying the separation layer forming composition of the above-described embodiment. Therefore, the laminate of the embodiment is less susceptible to damage from chemicals used in etching processes, photolithography processes, etc.

[0255] In the laminated body of the above-described embodiment, the support substrate 1 and the separation layer 2 are adjacent, but this is not a limitation; other layers may be further formed between the support substrate 1 and the separation layer 2. In this case, the other layers can be made of a material that allows light to pass through. Accordingly, layers that impart preferred properties to the laminated body 10 can be suitably added without hindering the incidence of light into the separation layer 2. Depending on the type of material constituting the separation layer 2, different wavelengths of light can be used. Therefore, the materials constituting the other layers do not need to allow all wavelengths of light to pass through; they can be suitably selected from materials that allow light of wavelengths that can modify the material constituting the separation layer 2 to pass through.

[0256] Furthermore, the laminate of the above-described embodiment includes an adhesive layer 3 for bonding the support substrate 1 to the substrate 4, but it is not limited to this; a separation layer 2 may also be provided between the support substrate 1 and the substrate 4. In this case, for example, a separation layer that also functions as an adhesive layer may be used.

[0257] (Manufacturing method of laminated bodies)

[0258] The fourth aspect of the present invention is a method for manufacturing a laminate having a separation layer between a support substrate and a substrate that allows light to pass through, comprising a separation layer forming step and a lamination step.

[0259] <First Implementation>

[0260] Figure 2 This is a schematic process diagram illustrating one embodiment of a method for manufacturing a laminate. Figure 2 (a) is a diagram illustrating the separation layer formation process. Figure 2 (b) is a diagram illustrating the lamination process.

[0261] In the method for manufacturing the laminate in this embodiment, a composition for forming a release layer is used, which is obtained by dissolving a resin component ((P) component) having repeating units represented by the above general formula (p1) in an organic solvent component ((S) component). Additionally, a composition for forming an adhesive layer is used, which is obtained by dissolving a hydrocarbon resin in the (S) component.

[0262] [Separation Layer Formation Process]

[0263] The separation layer forming process in the embodiment is as follows: the separation layer forming composition of the above embodiment is applied to one side of the support substrate, and then fired to form the separation layer.

[0264] Figure 2 In (a), the separation layer forming composition of the above embodiment is applied to the support substrate 1 and then fired to form the separation layer 2 (i.e., a support substrate with a separation layer is formed).

[0265] The method of coating the composition for forming the release layer onto the support substrate 1 is not particularly limited. For example, spin coating, dip coating, roller coating, spray coating, slot coating, etc. can be mentioned.

[0266] In the release layer formation process, the (S) component is removed from the coating layer of the release layer forming composition applied to the support substrate 1 under a heated or reduced pressure environment to form a film. The removal of the (S) component can be performed, for example, by baking at a temperature of 80–150°C for 120–360 seconds.

[0267] Then, in an atmospheric environment, the film obtained by removing the (S) component from the aforementioned coating layer is fired to form a separation layer 2 formed by the fired body.

[0268] The firing temperature of the film obtained by removing the (S) component from the aforementioned coating layer can be appropriately set according to the type of (P) component, for example, preferably set to 200°C or higher, more preferably set to 250°C or higher. If the firing temperature is above or at the lower limit of the aforementioned preferred range, a separation layer capable of absorbing light in the wavelength range of 600 nm or lower can be formed more stably.

[0269] There is no particular limit to the upper limit of the firing temperature, but it is preferred to set it to 800°C or below, and more preferably to 600°C or below.

[0270] The firing time is preferably set to 3 minutes or more and 3 hours or less, more preferably 3 minutes or more and 30 minutes or less. This allows for the reliable formation of a separation layer capable of absorbing light in the wavelength range below 600 nm.

[0271] [Lamination process]

[0272] The lamination process in the embodiment is as follows: the aforementioned support substrate with the aforementioned separation layer formed is laminated with the aforementioned substrate without the aforementioned separation layer formed, separated by the aforementioned separation layer and the aforementioned adhesive layer.

[0273] Figure 2In (b), the support substrate 1 with the separation layer 2 is stacked with the substrate 4 without the separation layer 2 through the separation layer 2 and the adhesive layer 3, resulting in a laminate 10 formed by the sequential stacking of the support substrate 1, the separation layer 2, the adhesive layer 3 and the substrate 4.

[0274] As a specific method for the lamination process, the following method can be cited: the adhesive layer forming composition is applied to the release layer 2 and heated to form the adhesive layer 3, and then the support substrate 1 is bonded to the substrate 4.

[0275] The method of applying the adhesive layer forming composition to the release layer 2 is not particularly limited, and can be carried out in the same way as the method of applying the release layer forming composition to the support substrate 1 described above.

[0276] The baking process for forming adhesive layer 3 is performed, for example, by heating in stages while raising the temperature, thereby removing the (S) component from the adhesive layer forming composition to form adhesive layer 3.

[0277] The method for bonding the support substrate 1 to the substrate 4 is as follows: the substrate 4 is placed at a specified position on the adhesive layer 3, and the support substrate 1 and the substrate 4 are pressed together using a die bonder while being heated under vacuum (e.g., around 100°C).

[0278] According to the method for manufacturing a laminate according to the first embodiment, the separation layer is formed using the separation layer composition of the above-described embodiment. Therefore, laser reactivity is enhanced, photoreactivity is further improved, and the separability of the support matrix from the laminate is improved. Preferably, a laminate with high chemical resistance can be manufactured.

[0279] In the manufacturing method of the laminate of the present embodiment described above, the separation layer 2 is formed on the support substrate 1, but it is not limited to this, and the separation layer 2 may also be formed on the substrate 4.

[0280] In the above-described method for manufacturing the laminate, the adhesive layer 3 is formed on the separation layer 2, but it is not limited to this; the adhesive layer 3 may also be formed on the substrate 4.

[0281] Alternatively, the separation layer 2 can be formed on both the support substrate 1 and the substrate 4. In this case, the support substrate 1 and the substrate 4 are bonded together through the separation layer 2, the adhesive layer 3, and the separation layer 2.

[0282] <Second Implementation Method>

[0283] Figure 3 A schematic process diagram illustrating other embodiments of the manufacturing method of the laminate. Figure 3 (a) A diagram illustrating a laminate manufactured using the manufacturing method of the first embodiment. Figure 3 (b) is a diagram illustrating the sealing process.

[0284] In addition to the separation layer formation process and the lamination process described above, the manufacturing method of the laminate in other embodiments also includes a sealing process.

[0285] [Sealing process]

[0286] The sealing process in the embodiment is as follows: after the aforementioned lamination process, the aforementioned substrate, which is bonded to the aforementioned support substrate through the aforementioned adhesive layer, is sealed with a sealing material to create a sealing body.

[0287] Figure 3 In (b), a sealing body 20 (laminated body) was obtained by sealing the substrate 4 disposed on the adhesive layer 3 with a sealing material.

[0288] In the sealing process, for example, sealing material heated to 130-170°C is supplied to adhesive layer 3 while maintaining a high viscosity, and then compressed and molded to produce a sealing body 20 (laminated body) with sealing material layer 5 disposed on adhesive layer 3.

[0289] As a sealing material, for example, a composition containing epoxy resin or silicone resin can be used. The sealing material layer 5 is preferably not disposed separately on each substrate 4, but rather covers all substrates 4 on the adhesive layer 3.

[0290] According to the manufacturing method of the laminate according to the second embodiment, a sealing substrate having a substrate (wiring layer) on the separation layer and the adhesive layer can be suitably formed by using the separation layer forming composition of the above embodiment.

[0291] <Third Implementation Method>

[0292] Figure 4 A schematic process diagram illustrating other embodiments of the manufacturing method of the laminate. Figure 4 (a) A diagram showing a sealing body manufactured using the manufacturing method of the second embodiment. Figure 4 (b) is a diagram illustrating the grinding process. Figure 4 (c) is a diagram illustrating the rewiring process.

[0293] In addition to the separation layer formation process, the stacking process, and the sealing process described above, the manufacturing method of the laminate in other embodiments also includes a grinding process and a rewiring formation process.

[0294] [Grinding process]

[0295] The grinding process in the embodiment is as follows: after the aforementioned sealing process, the sealing material portion (sealing material layer 5) in the sealing body 20 is ground to expose a portion of the substrate 4.

[0296] Grinding of the sealing material portion, for example Figure 4 As shown in (b), the sealing material layer 5 is ground to a thickness approximately equal to that of the substrate 4.

[0297] [Rewiring process]

[0298] The redistribution process in the embodiment is as follows: after the aforementioned grinding process, a redistribution layer 6 is formed on the aforementioned exposed substrate 4.

[0299] A redistribution layer, also known as an RDL (Redistribution Layer), is a thin film that forms the wiring for connecting components. It can have a single-layer or multi-layer structure. For example, a redistribution layer can utilize a conductor (metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) on a dielectric (silicon oxide (SiO2)). x A layer obtained by forming wiring on a photosensitive resin such as photosensitive epoxy resin, but not limited to this.

[0300] As a method for forming the redistribution layer 6, firstly, silicon oxide (SiO2) is formed on the sealing material layer 5. x The dielectric layer consists of a photosensitive resin and other dielectric layers. The dielectric layer formed from silicon oxide can be formed using methods such as sputtering or vacuum evaporation. The dielectric layer formed from photosensitive resin can be formed by coating the sealing material layer 5 with the photosensitive resin using methods such as spin coating, dipping, roller coating, spraying, or slot coating.

[0301] Next, conductive materials such as metals are used to form wiring on the dielectric layer.

[0302] As a method for forming wiring, known semiconductor processes such as photolithography (resist photolithography) and etching can be used. Examples of such photolithography include photolithography using a positive resist material and photolithography using a negative resist material.

[0303] During photolithography and etching processes as described above, the release layer 2 is exposed to acids such as hydrofluoric acid, bases such as tetramethylammonium hydroxide (TMAH), or resist solvents used to dissolve the resist material. Particularly in fan-out techniques, PGMEA, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), or cyclohexanone can be used as resist solvents.

[0304] However, by using the separation layer forming composition of the above-described embodiments, the separation layer possesses high chemical resistance. Therefore, the separation layer is not easily dissolved or peeled off even when exposed not only to acids and alkalis but also to resist solvents.

[0305] As described above, a redistribution layer 6 can be suitably formed on the sealing material layer 5.

[0306] According to the manufacturing method of the laminate according to the third embodiment, a laminate 30 consisting of a support substrate 1, a separation layer 2, an adhesive layer 3, a sealing material layer 5 covering the substrate 4, and a redistribution layer 6 can be stably manufactured.

[0307] The stack 30 is a stack fabricated in the process of mounting terminals disposed on the substrate 4 to the redistribution layer 6 that extends beyond the chip area, based on fan-out technology.

[0308] In the manufacturing method of the laminate of this embodiment, bumps can be formed or components can be mounted on the redistribution layer 6. Component mounting on the redistribution layer 6 can be performed, for example, using a pick-and-place machine.

[0309] (Manufacturing methods for electronic components)

[0310] In the fifth aspect of the present invention, the method for manufacturing an electronic component includes a separation step and a removal step after obtaining the laminate using the method for manufacturing the laminate according to the fourth aspect.

[0311] Figure 5 This is a schematic process diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 5 (a) A diagram showing a laminate manufactured using the manufacturing method of the third embodiment. Figure 5 (b) is a diagram illustrating the separation process. Figure 5 (c) is a diagram illustrating the removal process.

[0312] [Separation Process]

[0313] The separation process in the embodiment is as follows: light is irradiated onto the separation layer 2 through the support substrate 1 (arrow), causing the separation layer 2 to deform, thereby separating the support substrate 1 from the laminate 30.

[0314] like Figure 5 As shown in (a), during the separation process, light (arrow) is irradiated onto the separation layer 2 through the support substrate 1, thereby causing the separation layer 2 to deform.

[0315] For example, wavelengths below 600 nm can be used to modify the separation layer 2.

[0316] The type and wavelength of the irradiated light can be appropriately selected based on the transmittance of the support substrate 1 and the material of the separation layer 2. For example, solid-state lasers such as YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers; liquid lasers such as pigment lasers; gas lasers such as CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers; semiconductor lasers; free-electron lasers; and non-laser light can be used. This allows the separation layer 2 to be modified, thus achieving a state where the support substrate 1 can be easily separated from the substrate 4.

[0317] As an example of laser irradiation conditions, the following conditions can be cited.

[0318] The average output value of the laser is preferably 1.0W or more and 5.0W or less, more preferably 3.0W or more and 4.0W or less. The repetition frequency of the laser is preferably 20kHz or more and 60kHz or less, more preferably 30kHz or more and 50kHz or less. The scanning speed of the laser is preferably 100mm / s or more and 10000mm / s or less.

[0319] After irradiating the separation layer 2 with light (arrow) to denature the separation layer 2, as... Figure 5 As shown in (b), the support substrate 1 is separated from the laminate 30.

[0320] For example, by applying force along the direction in which the support substrate 1 and the substrate 4 separate from each other, the support substrate 1 and the substrate 4 can be separated. Specifically, with one of the support substrate 1 or the substrate 4 (rewiring layer 6) fixed to the worktable, the other is held in place by a separation plate equipped with a bellows pad or similar suction cup while being lifted, thereby separating the support substrate 1 and the substrate 4.

[0321] The force applied to the laminate 30 can be adjusted appropriately according to the size of the laminate 30, and there is no limitation. For example, if the laminate has a diameter of about 300 mm, the support substrate 1 and the substrate 4 can be appropriately separated by applying a force of about 0.1 to 5 kgf (0.98 to 49 N).

[0322] [Removal process]

[0323] The removal process in the embodiment is as follows: after the aforementioned separation process, the adhesive layer 3 and the separation layer 2 attached to the substrate 4 are removed.

[0324] Figure 5 In (b), after the separation process, an adhesive layer 3 and a separation layer 2 are attached to the substrate 4. In this embodiment, during the removal process, the adhesive layer 3 and the separation layer 2 attached to the substrate 4 are removed, thereby obtaining... Figure 5(c) shows the electronic component 40.

[0325] As a method for removing the adhesive layer 3 and the like attached to the substrate 4, for example, a method of removing the residue of the adhesive layer 3 and the separation layer 2 using a cleaning solution, or a method of irradiating with plasma.

[0326] As a cleaning solution, a cleaning solution containing an organic solvent is preferred. As an organic solvent, organic solvents formulated in the composition for forming the release layer and organic solvents formulated in the composition for forming the adhesive layer are preferred.

[0327] <Other Implementation Methods>

[0328] Figure 6 A schematic process diagram illustrating other embodiments of a semiconductor package (electronic component) manufacturing method. Figure 6 (a) A schematic diagram illustrating other embodiments of the laminate to which the present invention is applied. Figure 6 (b) is a diagram illustrating the separation process. Figure 6 (c) is a diagram illustrating the removal process.

[0329] Figure 6 In the laminate 50 of the embodiment shown in (a), starting from the outermost surface 51s side, a support substrate 51, a separation layer 52, a wiring layer 57, a substrate 54, and a sealing material layer 55 are sequentially laminated.

[0330] The description of the support substrate 51 is the same as that in the above description of the support substrate.

[0331] The description of separation layer 52 is the same as that in the above description of <Separation Layer>.

[0332] Wiring layer 57 can be exemplified by using a conductor (metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) in a dielectric (silicon oxide (SiO2)). x A layer is obtained by forming wiring on a photosensitive resin such as photosensitive epoxy resin.

[0333] The description of substrate 54 is the same as that in the above description of substrate.

[0334] Sealing material layer 55 can be, for example, formed using a composition containing an epoxy resin or a silicone resin.

[0335] The laminate 50 can be manufactured, for example, by operating as described below.

[0336] First, a separation layer 52 is formed on the surface of the support substrate 51 opposite to the outermost surface 51s. The formation of the separation layer 52 is performed in the same manner as the [separation layer formation process] described above.

[0337] Next, a wiring layer 57 is formed on the side of the separation layer 52 opposite to the support substrate 51. The formation of the wiring layer 57 is performed in the same manner as the [rewiring formation process] described above.

[0338] Next, on the side of the wiring layer 57 opposite to the separation layer 52, the substrate 54 is attached, for example, with a bump in between.

[0339] Next, a sealing material is used to seal the substrate 54, which is bonded to the wiring layer 57, to form a sealing material layer 55. The formation of the sealing material layer 55 can be performed in the same manner as the [sealing process] described above. Thus, a laminate 50 is manufactured.

[0340] like Figure 6 As shown in (a), in the separation process of the embodiment, light (arrow) is irradiated onto the separation layer 52 through the support substrate 51 to deform the separation layer 52.

[0341] After the separation layer 52 is irradiated with light (arrow) to denature it, as... Figure 6 As shown in (b), the support substrate 51 is separated from the laminate 50. The operation in the separation process is the same as the operation in the [separation process] described above.

[0342] like Figure 6 As shown in (c), in the removal process of the embodiment, after the aforementioned separation process, the separation layer 52 attached to the wiring layer 57 is removed, thereby obtaining the electronic component 60.

[0343] As a method for removing the separation layer 52 attached to the wiring layer 57, examples include irradiating with plasma or removing residue from the separation layer 52 using a cleaning solution. As the aforementioned plasma, oxygen plasma is preferably used.

[0344] In the manufacturing method of the electronic component of this embodiment, after the above-mentioned removal process, the electronic component can be further processed by forming solder balls, cutting, or forming an oxide film.

[0345] [Example]

[0346] The present invention will now be described in more detail by way of examples, but the present invention is not limited to these examples.

[0347] <Resin Composition>

[0348] As resin components, the following resins (P-1), (P-2), (P-3), (Q-1), and (Q-2) are used.

[0349] Resin (P-1): A resin having repeating units (p12) represented by the following chemical formula (p1-2) and repeating units (p22) represented by the following chemical formula (p2-2). The weight-average molecular weight (Mw) converted to standard polystyrene by GPC determination is 6000, and the molecular weight dispersion (Mw / Mn) is 1.62. 13 The copolymer composition ratio (the proportion (molar ratio) of each repeating unit in the structural formula) obtained by C-NMR is repeating unit (p12) / repeating unit (p22) = 10 / 90.

[0350] Resin (P-2): A resin having repeating units (p12) represented by the following chemical formula (p1-2) and repeating units (p22) represented by the following chemical formula (p2-2). The weight-average molecular weight (Mw) converted to standard polystyrene by GPC determination is 5500, and the molecular weight dispersion (Mw / Mn) is 1.60. 13 The copolymer composition ratio (the proportion (molar ratio) of each repeating unit in the structural formula) obtained by C-NMR is repeating unit (p12) / repeating unit (p22) = 5 / 95.

[0351] [Chemical Formula 14]

[0352]

[0353] Resin (P-3): A resin having repeating units (p16) represented by the following chemical formulas (p1-6) and repeating units (p26) represented by the following chemical formulas (p2-6). In chemical formula (p1-6), n1 = 3, and in chemical formula (p2-6), n2 = 3. The weight-average molecular weight (Mw) converted to standard polystyrene by GPC determination is 2000, and the molecular weight dispersion (Mw / Mn) is 2.10. 13 The copolymer composition ratio (the proportion (molar ratio) of each repeating unit in the structural formula) obtained by C-NMR is repeating unit (p16) / repeating unit (p26) = 50 / 50.

[0354] [Chemical Formula 15]

[0355]

[0356] Resin (Q-1): A resin having a repeating unit (p21) represented by the following chemical formula (p2-1). The weight-average molecular weight (Mw) converted to standard polystyrene by GPC determination is 12000, and the molecular weight dispersion (Mw / Mn) is 2.10. The polymerization ratio (the proportion (molar ratio) of repeating units in the structural formula) is repeating unit (p21) = 100.

[0357] [Chemical Formula 16]

[0358]

[0359] Resin (Q-2): A resin having the repeating unit (p26) represented by the above chemical formula (p2-6). The weight-average molecular weight (Mw) converted to standard polystyrene by GPC determination is 2300, and the molecular weight dispersion (Mw / Mn) is 2.00. The polymerization ratio (the proportion (molar ratio) of the repeating units in the structural formula) is repeating unit (p26) = 100.

[0360] <Preparation of the composition for separating layer formation>

[0361] (Examples 1-5, Comparative Examples 1-2)

[0362] The components shown in Table 1 were mixed and dissolved to prepare separate layer formation compositions for each example (resin component concentration was 20% by mass).

[0363] [Table 1]

[0364]

[0365] In Table 1, each abbreviation has the following meaning. The value in [] is the amount of the mixture (parts by mass).

[0366] (P)-1: Resin (P-1)

[0367] (P)-2: Resin (P-2)

[0368] (P)-3: Resin (P-3)

[0369] (P)-4: Resin (Q-1)

[0370] (P)-5: Resin (Q-2)

[0371] (T)-1: A thermal acid-producing agent formed from a compound represented by the following chemical formula (T-1).

[0372] (S)-1: Propylene glycol monomethyl ether (PGME)

[0373] [Chemical Formula 17]

[0374]

[0375] <Formation of the Separation Layer>

[0376] The respective separation layer formation compositions were spin-coated onto a bare glass support substrate (12 inches, 0.7 mm thick), and heated at 100°C for 300 seconds, followed by heating at 150°C for 300 seconds, thereby removing the solvent and forming a film with a thickness of 1 μm.

[0377] Next, the formed film was fired at 300°C for 20 minutes in an atmospheric environment to form a separation layer with a film thickness of 0.3 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer.

[0378] [Evaluation of light transmittance in the separation layer]

[0379] For the films (separation layers) formed using the separation layer forming compositions described above, both before and after firing, a UV-3600 spectrophotometer (manufactured by Shimadzu Corporation) was used to irradiate them with light of wavelengths from 380 to 780 nm. The transmittance (%) of light at a wavelength of 532 nm in each film formed on the bare glass support substrate was evaluated. The evaluation results are shown in Table 2.

[0380] [Evaluation of laser reactivity in the separation layer]

[0381] For the separation layer formed using the separation layer forming compositions of each example, the laser reactivity was evaluated by irradiating it with a laser with a wavelength of 532 nm under the conditions of a scanning speed of 7200 mm / s, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation spacing of 140 μm.

[0382] The evaluation of laser reactivity was conducted as follows: using a VHX-600 microscope (manufactured by Keyence), the state of the laser traces irradiated onto the separation layer was observed, and the size of the laser traces on the surface of the separation layer (laser indentation diameter / μm) was determined. The evaluation criteria were set as described below. The evaluation results are shown in Table 2.

[0383] Evaluation Criteria

[0384] ◎: The diameter of the laser indentation is 160μm or more.

[0385] 〇: The diameter of the laser indentation is greater than 150μm and less than 160μm.

[0386] △: The diameter of the laser indentation is greater than 100μm and less than 150μm.

[0387] ×: Laser indentation diameter is less than 100μm.

[0388] [Table 2]

[0389]

[0390] As shown in Table 2, compared with the separation layers formed using the separation layer forming compositions of Comparative Examples 1-2, the light transmittance of the separation layers formed using the separation layer forming compositions of Examples 1-5 is lower and the laser indentation diameter is significantly larger.

[0391] That is, it has been confirmed that, according to the separation layer forming composition of the present invention, a separation layer with further improved photoreactivity and improved separation of the support matrix from the laminate can be formed.

[0392] <Fabrication of Layered Structures>

[0393] Using the same method as described above for the formation of the separation layer, the separation layer formation compositions of each embodiment were spin-coated onto a bare glass support substrate (12 inches, 0.7 mm thick). The substrate was then heated at 100°C for 300 seconds, followed by heating at 150°C for 300 seconds to remove the solvent and form a film. Next, the formed film was fired at 300°C for 20 minutes under atmospheric conditions to form a 0.5 μm thick separation layer on the bare glass support substrate (separation layer formation step).

[0394] On the other hand, an adhesive composition TZNR (registered trademark)-A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated onto a semiconductor wafer substrate (12-inch, silicon) and baked at 90°C, 160°C, and 220°C for 4 minutes each to form an adhesive layer with a film thickness of 50 μm.

[0395] Next, the bare glass support substrate with the separation layer and the semiconductor wafer substrate with the adhesive layer are stacked in the order of semiconductor wafer substrate, adhesive layer, separation layer, and bare glass support substrate. Under vacuum (5 Pa) and at 215°C, an adhesion pressure of 4000 kgf (approximately 39.2 kN) is applied for 2 minutes. Thus, the bare glass support substrate and the semiconductor wafer substrate are stacked with the separation layer and adhesive layer in between, resulting in a laminate (lamination process).

[0396] After obtaining the laminate, the separation layer is irradiated with a laser of wavelength 532 nm from the support substrate side of the laminate under the conditions of scanning speed of 3000 mm / s, frequency of 40 kHz, output (current value) of 24 A, and irradiation spacing of 140 μm (separation process). Subsequently, the adhesive layer is removed by cleaning with menthol (removal process).

[0397] It has been confirmed that, through the above operations, the support substrate is separated from the semiconductor wafer substrate of the laminate.

[0398] <Example of Electronic Component Manufacturing (1)>

[0399] Using the same method as described above for the formation of the separation layer, the separation layer forming compositions of each embodiment were spin-coated onto a bare glass support substrate (12 inches, 0.7 mm thick). The substrate was then heated at 100°C for 300 seconds, followed by heating at 150°C for 300 seconds to remove the solvent and form a film. Next, the formed film was fired at 300°C for 20 minutes under atmospheric conditions to form a 0.5 μm thick separation layer on the bare glass support substrate, thereby obtaining a support substrate with a separation layer (separation layer formation process).

[0400] Then, the adhesive composition TZNR (registered trademark)-A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated onto the separation layer and baked at 90°C, 160°C and 220°C for 4 minutes each to form an adhesive layer with a film thickness of 50 μm.

[0401] Next, using a die bonder (manufactured by TRESKY), the die bonder board is heated to 150°C, and a 2mm square silicon bare die is pressed onto the aforementioned bonding layer for 1 second with a pressure of 35N. After the silicon bare die is placed, it is heated at 200°C for 1 hour under a nitrogen atmosphere to obtain the laminate (lamination process).

[0402] The resulting laminate was placed on a plate heated to 50°C. 12g of a sealant containing epoxy resin was applied to cover the bare die. Under reduced pressure (below 10 Pa), using an attachment device, a pressure of 1 ton was applied using an extrusion plate heated to 130°C, and the mixture was compressed for 5 minutes. This process was repeated to seal the bare die disposed on the adhesive layer using the sealant, thus creating a sealed body (sealing process).

[0403] After fabricating the sealing body, the separation layer is irradiated with a 532nm laser from the support substrate side of the sealing body under the conditions of a scanning speed of 3000mm / s, a frequency of 40kHz, an output (current value) of 24A, and an irradiation spacing of 140μm (separation process). Subsequently, the adhesive layer is removed by cleaning with menthol (removal process).

[0404] It has been confirmed that, through the above operations, the support substrate has been separated from the seal. The electronic component is obtained by operating as described above.

[0405] <Example of Electronic Component Manufacturing (2)>

[0406] Using the same method as described above for the formation of the separation layer, the separation layer formation compositions of each embodiment were spin-coated onto a bare glass support substrate (12 inches, 0.7 mm thick). The substrate was heated at 90°C for 180 seconds to remove the solvent, thus forming a film. Next, the formed film was fired at 300°C for 10 minutes under atmospheric conditions to form a 0.35 μm thick separation layer on the bare glass support substrate, thereby obtaining a support substrate with a separation layer (separation layer formation process).

[0407] Next, a wiring layer forming material (trade name TMMR S2000) is coated on the aforementioned separation layer, and the layer is fired at 90°C for 3 minutes in an atmospheric environment, thereby forming a wiring layer with a thickness of 10 μm on the separation layer, resulting in a laminate.

[0408] After the wiring layer is formed, from the bare glass support substrate side of the laminate, at an irradiation dose of 200 mJ / cm 2 The separation layer was irradiated with a 532nm laser at an output current of 22A and an irradiation spacing of 80μm. Next, it was immersed in propylene glycol monomethyl ether acetate (PGMEA) as a cleaning solution and then baked at 90°C for 5 minutes. Following this, the firing process was repeated three times at 200°C for 60 minutes under a nitrogen atmosphere, thereby separating the support substrate from the laminate (separation process). Then, oxygen plasma (2000W power, 2000sccm oxygen flow rate, 75Pa pressure, 50°C temperature, 5 minutes) was irradiated onto the separation layer side of the wiring layer to remove the separation layer adhering to the wiring layer (removal process).

[0409] It has been confirmed that, through the above operations, the support substrate is separated from the laminate. The electronic component is obtained by operating as described above.

Claims

1. A composition for forming a separation layer, used to form the separation layer in a laminate having a separation layer between a light-transmitting support substrate and a base plate, the separation layer being denatured by irradiation from the support substrate side, thereby causing the support substrate to separate from the laminate. The composition for forming the separation layer contains a resin component (P) having repeating units represented by the following general formula (p1). [Chemical Formula 1] In equation (p1), L P1 Indicates a divalent linker; R P1 This indicates a fused polycyclic aromatic group that may have substituents.

2. The composition for forming a release layer as claimed in claim 1, wherein the release layer is formed in a laminate having a release layer and an adhesive layer between a light-transmitting support substrate and a substrate, the release layer being denatured by irradiation from the support substrate side thereby causing the support substrate to separate from the laminate, the composition for forming the release layer containing a resin component (P) having repeating units represented by the following general formula (p1). [Chemical Formula 2] In equation (p1), L P1 Indicates a divalent linker; R P1 This indicates a fused polycyclic aromatic group that may have substituents.

3. The composition for forming a separation layer as described in claim 1 or 2, wherein, The resin component (P) also has repeating units represented by the following general formula (p2). [Chemical Formula 3] In equation (p2), L P2 Indicates a divalent linker; R P2 This indicates a monocyclic aromatic group that may have substituents.

4. The composition for forming a separation layer according to any one of claims 1 to 3, further comprising a thermally generated acid agent.

5. A support substrate with a separation layer, which has the following characteristics: Supporting matrix; and A separation layer is formed on the support substrate using the separation layer forming composition according to any one of claims 1 to 4.

6. A laminate, which is a laminate having a separation layer between a light-transmitting support substrate and a base plate. The separation layer is a sintered body of the separation layer forming composition according to any one of claims 1 to 4.

7. A method for manufacturing a laminate, wherein a separation layer is provided between a light-transmitting support substrate and a base plate, the manufacturing method comprising the following steps: The separation layer forming process involves applying the separation layer forming composition according to any one of claims 1 to 4 to at least one of the substrate or the support substrate, followed by firing to form the separation layer; and In the lamination process, the substrate and the support substrate are laminated in a manner that separates them through the separation layer.

8. The method for manufacturing a laminate as claimed in claim 7, further comprising the following sealing step: after the lamination step, sealing the substrate bonded to the support substrate through the separation layer using a sealing material to create a sealed body.

9. The method for manufacturing a laminate as described in claim 8, further comprising the following steps: A grinding process, following the sealing process, involves grinding the sealing material portion of the sealing body to expose a portion of the substrate; and The rewiring process involves forming rewiring on the exposed substrate after the grinding process.

10. A method for manufacturing electronic components, comprising the following steps: In the separation process, after obtaining the laminate using the manufacturing method of any one of claims 7 to 9, light is irradiated onto the separation layer through the support substrate to denature the separation layer, thereby separating the support substrate from the laminate; and The removal process involves removing the separation layer attached to the substrate after the separation process.

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