Compositions for forming release layers, support substrates with release layers, laminates and methods for manufacturing the same, and methods for manufacturing electronic components.

Abstract

This invention provides a composition for forming a separation layer in a laminate having a separation layer between a support substrate and a substrate, which can further enhance photoreactivity and improve the separability of the support substrate from the laminate. The separation layer forming composition of this invention is used to form a separation layer in a laminate 10 having a separation layer 2 and an adhesive layer 3 between a light-transmitting support substrate 1 and a substrate 4. This separation layer can be denatured by irradiation from the support substrate side, thereby separating the support substrate from the laminate. The separation layer forming composition contains a resin component (P) having repeating units represented by the general formula (p1). In the general formula (p1), L P1 represents a divalent linker group. R P1 represents a condensed polycyclic aromatic group that may have substituents.

Description

Technical Field

[0001] This invention relates to a composition for forming a release layer, a support substrate with a release layer, a laminate, a method for manufacturing the same, and a method for manufacturing electronic components. Prior 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). 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 edge of the bare die are reconfigured within the die region. 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 die region.

[0003] 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.

[0004] To achieve miniaturization of semiconductor packaging, it is crucial to reduce the thickness of the substrate in the assembled components. However, reducing the substrate thickness decreases its strength, making it prone to breakage during semiconductor packaging manufacturing. To address this, a multilayer structure is used, which involves bonding a support substrate onto the substrate. 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 to the separation layer, causing the separation layer to denature and decompose. This separates the processed substrate from the support substrate, thereby manufacturing a laminate. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2004-64040 Summary of the Invention

[0006] [The problem the invention aims to solve]

[0007] As described in Patent Document 1, when miniaturization of semiconductor packaging is achieved by using a multilayer obtained by bonding a support substrate onto a substrate, the separability of the support substrate from the multilayer becomes a problem. The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a separation layer in a laminate having a separation layer between a support substrate and a substrate, wherein the separation layer of the separation layer is further improved to enhance the photoreactivity and thus improve the separation of the support substrate from the laminate; a support substrate with the separation layer thereon; a laminate; a method for manufacturing the same; and a method for manufacturing electronic components. [Technical means to solve the problem]

[0008] To address the aforementioned issues, the present invention employs the following configuration. That is, the first embodiment of the present invention is a composition for forming a separation layer, characterized in that it is used to form the separation layer in a laminate in which a separation layer is provided between a support substrate and a substrate that allows light to pass through. The separation layer can be deformed by irradiation from the support substrate side, thereby separating the support substrate 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).

[0009] [Chemistry 1] [In the formula, LP1 represents a divalent linker; RP1 represents a condensed polycyclic aromatic group that may have substituents.]

[0010] The second embodiment 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 of the first embodiment.

[0011] The third state of the present invention is a laminate, characterized in that it has a separation layer between the light-transmitting support substrate and the substrate, wherein the separation layer is a sintered body of the separation layer forming composition of the first state.

[0012] 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 includes the following steps: a separation layer forming step, in which 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, in which the aforementioned substrate and the aforementioned support substrate are laminated through the aforementioned separation layer.

[0013] The fifth aspect of the present invention is a method for manufacturing an electronic component, characterized by the following steps: a separation step, in which, after obtaining the laminate using the aforementioned fourth aspect of the laminate manufacturing method, light is irradiated onto the aforementioned separation layer through the aforementioned support substrate to denature the aforementioned 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. [Effects of the Invention]

[0014] According to the present invention, a composition for forming a separation layer in a laminate having a separation layer between a support substrate and a substrate, wherein the separation layer is further improved to enhance the photoreactivity and thus improve the separability of the support substrate from the laminate, a support substrate with the separation layer thereon, a laminate, a method for manufacturing the same, and a method for manufacturing electronic components are provided. Simple Explanation of the Diagram

[0015] Figure 1 is a schematic diagram illustrating one embodiment of the laminated body to which the present invention is applied. Figure 2 is a schematic diagram illustrating one embodiment of the method for manufacturing a laminate. Figure 2(a) illustrates the separation layer formation step, and Figure 2(b) illustrates the lamination step. Figure 3 is a schematic diagram illustrating another embodiment of the manufacturing method of the laminate. Figure 3(a) shows a laminate manufactured using the manufacturing method of the first embodiment, and Figure 3(b) illustrates the sealing step. Figure 4 is a schematic diagram illustrating another embodiment of the manufacturing method of the laminate. Figure 4(a) shows a seal manufactured using the manufacturing method of the second embodiment, Figure 4(b) illustrates the grinding step, and Figure 4(c) illustrates the rewiring step. Figure 5 is a schematic diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 5(a) shows a multilayer manufactured using the manufacturing method of the third embodiment, Figure 5(b) illustrates the separation step, and Figure 5(c) illustrates the removal step. Figure 6 is a schematic diagram illustrating other embodiments of the manufacturing method of semiconductor package (electronic component). Figure 6(a) is a schematic diagram showing another embodiment of the laminate to which the present invention is applied, Figure 6(b) is a diagram illustrating the separation step, and Figure 6(c) is a diagram illustrating the removal step. Implementation

[0016] In this specification and the scope of this patent application, the term "aliphatic" is a relative concept compared to aromatic compounds, and it is defined as a group or compound that does not possess aromaticity. Unless otherwise specified, "alkyl" includes monovalent saturated hydrocarbon groups that are straight-chain, branched, or cyclic. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups. "Halogenated alkyl" refers to a group in which one 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. "Fluorinated alkyl" refers to an alkyl group in which one or all of the hydrogen atoms are replaced by fluorine atoms. The term "repeating unit" refers to the monomer unit that makes up a polymer compound (resin, polymer, copolymer). When it is recorded as "may have substituents", it includes both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH 2-) is replaced by a divalent group.

[0017] The term "styrene" encompasses both styrene and styrene in which the hydrogen atom at the α-position is replaced by alkyl groups, alkyl halides, or other substituents. Furthermore, the term α-position (the carbon atom at the α-position), unless otherwise specified, refers to the carbon atom bonded to the benzene ring.

[0018] The alkyl group used as the α-position substituent 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, tributyl, pentyl, isopentyl, neopentyl, etc.). Furthermore, the alkyl halide that serves as the substituent at the α-position can be specifically a group formed by substituting one or all of the hydrogen atoms of the aforementioned alkyl halide at the α-position with a halogen atom. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0019] In this specification and the claims of this application, based on the structure shown in the chemical formula, chiral carbon may be present, as well as enantiomers and diastereomers. In such cases, a single chemical formula is used to represent each isomer. These isomers may be used alone or in mixtures.

[0020] (Composition for forming the separation layer) The first embodiment of the present invention provides a separation layer forming composition for forming the aforementioned separation layer in a laminate containing a separation layer between a light-transmitting support substrate and a substrate. The separation layer is 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).

[0021] Figure 1 illustrates one embodiment of the laminated body to which the present invention is applied. The laminate 10 shown in Figure 1 has a separation layer 2 and an adhesive layer 3 between the support substrate 1 and the substrate 4, and the separation layer 2, adhesive layer 3 and substrate 4 are sequentially laminated on the support substrate 1. The support substrate 1 is formed of a light-transmitting material. In the laminate 10, by irradiating the separation layer 2 with light from the support substrate 1 side, the separation layer 2 is denatured and decomposed, and thus the support substrate 1 separates from the laminate 10. The separation layer 2 in the laminate 10 can be formed using the separation layer forming composition of this embodiment.

[0022] <Resin Components (P)> Resin component (P) (hereinafter also referred to as "(P) component") is a resin component having repeating units represented by the general formula (p1). The (P) component has a condensed polycyclic aromatic group (RP1) that can have substituents in the repeating unit. Therefore, in the separation layer formed by the separation layer forming composition containing the (P) component, laser reactivity is enhanced, photoreactivity is further improved, and the separation of the support matrix from the laminate is improved. Furthermore, the (P) component has a divalent linker (LP1) in the repeating unit. Therefore, the (P) component is easily denatured (oxidized, etc.) by heating. In the separation layer formed by the separation layer forming composition containing the above-mentioned (P) component, the light absorption is improved and the photoreactivity is excellent.

[0023] In Figure 1, in a laminate 10 having a release layer 2 formed using a release layer forming composition containing component (P), the release layer 2 is deformed and easily peeled off from the substrate 4 by irradiation from the support substrate 1 side, thus separating the support substrate 1. Furthermore, when the release layer 2 containing component (P) is peeled off from the substrate 4, there is little residue adhering to the substrate 4, and its removability from the substrate 4 is also good. In addition, since the component (P) has a divalent linker (LP1) in the repeating unit, the heat resistance of the release layer 2 containing component (P) is improved, and furthermore, it has high chemical resistance. Furthermore, due to the strong laser reactivity of component (P), laser damage to the separation layer 2 containing component (P) is suppressed, and laser intensity can be increased, thereby shortening the process time.

[0024] The (P) component may also have other repeating units besides the repeating unit represented by the general formula (p1).

[0025] Repetitive Units Represented by General Formula (p1) (P) component has repeating units represented by the following general formula (p1) (hereinafter also referred to as "repeating unit (p1)").

[0026] [Chemistry 2] [In the formula, LP1 represents a divalent linker; RP1 represents a condensed polycyclic aromatic group that may have substituents.]

[0027] In the aforementioned formula (p1), the divalent linker in L P1 may include an aromatic ring, may include multiple aromatic rings, or may include a ring structure formed by the condensation of an aromatic ring and an aliphatic ring. When the divalent linker in L P1 contains an aromatic ring, there are no particular limitations 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, further preferably 6 to 15, and even more preferably 6 to 12. Aromatic rings include, specifically, 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. Heteratoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Aromatic heterocycles specifically include pyridine rings and thiophene rings. The divalent linkage may contain one or more aromatic rings, but from the perspective of superior photoreactivity, two or more rings are preferred.

[0028] Alternatively, in the aforementioned formula (p1), the divalent linker in L P1 is preferably a divalent linker containing heteroatoms. To impart the desired properties, various linkers with different frameworks can be introduced as L p1. As the framework mentioned above, which is "a linker base for various frameworks", examples include the naphthalene framework, the anthracene framework, and α-naphthalene. Skeleton, fusiform skeleton, bisphenol A skeleton, etc.

[0029] Examples of L p1 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 such groups.

[0030] Examples of bisphenols include bisphenol F, bisphenol A, bisphenol Z, biphenol, or polymers thereof. 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. Examples of dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid, and terephthalic acid.

[0031] When bisphenol ether linkages are selected as Lp1, the flexibility of the (P) component film is easily improved. When an ether-linked group of a diol is chosen as L p1, the alkali solubility of the (P) component can be easily adjusted. Preferably, the ether-linked group is a linker with a diol skeleton. For example, a propylene glycol skeleton can be used as a diol skeleton. When Si-O bonding groups are selected as Lp1, it is easy to achieve low dielectricization of (P) composition molded articles.

[0032] The following shows a preferred specific example of LP1 (divalent linkage) in the aforementioned formula (p1). In the following formula, * indicates a bond with a methylene (CH2) group. n in chemical formula (LP1-9) represents the repeating number of the oxypropyl group.

[0033] [Chemistry 3]

[0034] In the aforementioned formula (p1), R P1 is a condensed polycyclic aromatic group that may have substituents. The condensed polycyclic aromatic group in RP1 is a group obtained by removing one hydrogen atom from a condensed polycyclic aromatic ring. This condensed polycyclic aromatic ring can be a ring structure formed by the condensation of multiple aromatic rings, or it can be a ring structure formed by the condensation of an aromatic ring and an aliphatic ring. In the ring structure formed by the condensation of an aromatic ring and an aliphatic ring, the number of aromatic rings can be multiple, the number of aliphatic rings can also be multiple, and there can be one aromatic ring and one aliphatic ring. The number of rings constituting the condensed polycyclic aromatic ring is preferably 2 to 5, more preferably 2 to 3, and even more preferably 3.

[0035] In the aforementioned formula (p1), the substituents that the condensed polycyclic aromatic group in R P1 may have include, for example, hydroxyl, carboxyl, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy carbonyl, side oxygen (=O), etc. Furthermore, the hydrocarbon groups in the condensed polycyclic aromatic groups of RP1 can have ether bonds in the middle of their hydrocarbon chains.

[0036] As RP1, examples include those derived from naphthalene rings, azurite rings, anthracene rings, phenanthrene rings, pyrene rings, etc. A radical obtained by removing one hydrogen atom from a ring, a triphenylene ring, a perylene ring, an anthraquinone ring, or a naphthoquinone ring. Of these, R P1 is preferably a group obtained by removing one hydrogen atom from an anthraquinone ring or naphthoquinone ring, and more preferably a group obtained by removing one hydrogen atom from an anthraquinone ring.

[0037] The following is a preferred specific example regarding the repeating unit (p1). In the chemical formula (p1-6), n1 represents the number of repeats of the oxypropyl group.

[0038] [Chemistry 4]

[0039] [Chemistry 5]

[0040] The repeating unit (p1) of component (P) can be one type or two or more types. The proportion of repeating units (p1) in component (P) is preferably more than 1 mol% relative to the total of all repeating units constituting component (P) (100 mol%), or it can be 1 to 100 mol.

[0041] When component (P) has other repeating units besides repeating unit (p1), the proportion of repeating unit (p1) in component (P) is preferably 1 to 99 mol%, more preferably 1 to 70 mol%, and even more preferably 1 to 50 mol% relative to the total of all repeating units constituting component (P) (100 mol%). 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.

[0042] Other repeating units (P) Components may be components that have other repeating units besides the repeating unit (p1) mentioned above. Other repeating units include, for example, repeating units represented by the general formula (p2) described later.

[0043] Regarding the repeating unit represented by the general formula (p2): (P) is preferably a resin having repeating units represented by the following general formula (p2) in addition to the repeating unit (p1) mentioned above (hereinafter also referred to as "repeating unit (p2)").

[0044] [Chemistry 6] [In the formula, LP2 represents a divalent linker; RP2 represents a monocyclic aromatic group that may have substituents.]

[0045] In the aforementioned equation (p2), the explanation of L P2 is the same as the explanation of the divalent linkage in L P1 in the aforementioned equation (p1). As a preferred specific example of LP2 (divalent linker), a linker that is the same as the linker represented by the above chemical formulas (LP1-1) to (LP1-9) can be given.

[0046] In the aforementioned formula (p2), the monocyclic aromatic group in R P2 is a hydrocarbon group having one aromatic ring. This aromatic ring can be a cyclic conjugated system with 4n+2 π electrons. Specifically, the aromatic ring constituting the monocyclic aromatic group in RP2 can be a benzene ring; a pyridine ring; a thiophene ring; a pyrrole ring; an imidazole ring; a furan ring; a thiazole ring, etc. Among these, the group obtained by removing one hydrogen atom from the benzene ring is preferred as RP2.

[0047] When the hydrocarbon group represented by RP2 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.

[0048] The following is a preferred specific example regarding the repeating unit (p2). In the chemical formula (p2-6), n2 represents the number of repeats of the oxypropyl group.

[0049] [Chemistry 7]

[0050] When component (P) has repeating units (p2), there may be one type of repeating unit (p2) or two or more types. When component (P) has repeating units (p2), the proportion of repeating units (p2) in component (P) is preferably 1 to 99 mol% relative to the total of all repeating units constituting component (P) (100 mol%), more preferably 30 to 99 mol%, and even more preferably 50 to 99 mol%. 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 repeating units (p1).

[0051] In the composition for forming the separation layer of this embodiment, component (P) is a resin having at least repeating units (p1). (P) component can also be a resin formed solely from repeating units (p1). As a preferred component (P), 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) = 1:99~99:1, more preferably 1:99~70:30, and even more preferably 1:99~50:50.

[0052] 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%, more preferably 1 to 70 mol%, and even more preferably 1 to 50 mol%, relative to the total (100 mol%) of all repeating units constituting the mixture. The 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.

[0053] The (P) component has film-forming ability, and its molecular weight is preferably 1000 or higher. By making the molecular weight of the (P) component 1000 or higher, the film-forming ability is improved. The molecular weight of the (P) component is more preferably 1000 to 30000, more preferably 1500 to 25000, especially 1500 to 20000, and most preferably 2000 to 15000. 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 in the solvent is improved. Furthermore, the molecular weight of the resin component is the weight-average molecular weight (Mw) obtained by GPC (gel permeation chromatography) converted to polystyrene.

[0054] As a component (P), for example, the GSP series (manufactured by Chung Jung Chemical Industry Co., Ltd.) with trade names such as GSP-112, GSP-113, and GSP-117 can be used.

[0055] Furthermore, as component (P), resins generated by reacting aminoanthraquinone or aminonaphthoquinone with aminophenols, aminonaphthophenols or anilines, or compounds having two epoxy groups in one molecule can also be used. 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. 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); dicarboxylic acid ester-type epoxy resins such as DENACOL EX-711, DENACOL EX-721 (manufactured by Nagase Chemtex Corporation) and jER191P (manufactured by Mitsubishi Chemical Corporation); and polysiloxane-type epoxy resins such as X-22-163 and KF-105 (manufactured by Shin-Etsu Chemical Industry Co., Ltd.). The heating temperature during the above reaction is preferably set to 60°C or higher and 250°C or lower, and more preferably 80°C or higher and 180°C or lower.

[0056] The composition for forming the separation layer in this embodiment may contain one or more (P) components. 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. Regarding the content of component (P) in the above-mentioned composition for forming the separation layer, for example, it is preferably 1 to 100% by mass, more preferably 1 to 70% by mass, and even more preferably 5 to 50% by mass, and particularly preferably 10 to 50% by mass, relative to the composition (100% by mass). 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. In addition, 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.

[0057] <Other Ingredients> The composition for forming the separation layer in this embodiment may further contain components other than the (P) component mentioned above (optional components). As optional components, examples include resins, thermal acid-generating agents, photo-acid-generating agents, photosensitizers, organic solvents, surfactants, sensitizers, etc., other than the components shown below (P).

[0058] 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. Examples of resins other than component (P) include phenolic varnish-type phenolic resin, soluble phenolic resin, hydroxystyrene resin, hydroxyphenyl silsesquioxane resin, hydroxybenzyl silsesquioxane resin, and acrylic resin containing a phenol backbone. By using phenolic resin, which is a resin other than component (P), in combination with component (P), it is also easy to suppress the formation of voids caused by heating.

[0059] Heat-generating acid agents 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"). By including the (T) component in the above-mentioned composition for forming the separation layer, the oxidation of the separation layer is promoted by the acid generated by the (T) component during heating during firing, and thus it is easily denatured by light irradiation (which can improve the photoreactivity of the separation layer).

[0060] 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 to which the composition for forming the release layer is coated is pre-baked, more preferably above 110°C, and even more preferably above 130°C. Examples of the aforementioned component (T) include trifluoromethanesulfonate, hexafluorophosphate, perfluorobutyrate, boron trifluoride salt, and boron trifluoride ether complexes. Preferred components (T) include compounds formed from the cationic and anionic portions as described below.

[0061] [Chemistry 8] [In formula (T-ca-1), Rh01 to Rh04 are each independently a group selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and aryl groups, and at least one of Rh01 to Rh04 is an aryl group; the aforementioned alkyl or aryl groups may have substituents; in formula (T-ca-2), Rh05 to Rh07 are each independently a group selected from the group consisting of alkyl groups having 1 to 20 carbon atoms and aryl groups, and at least one of Rh05 to Rh07 is an aryl group; the aforementioned alkyl or aryl groups may have substituents]

[0062] • Regarding the cationic portion of component (T) In the aforementioned formula (T-ca-1), the alkyl group in Rh01 to Rh04 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, tributyl, pentyl, isopentyl, neopentyl, etc., among which methyl and ethyl are preferred.

[0063] The alkyl group in R h01 to R h04 may have substituents. Examples of such substituents include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups.

[0064] The alkoxy group that is a substituent for the alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tributoxy, and even more preferably methoxy or ethoxy. Examples of halogen atoms that can be used as substituents for alkyl groups include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. Examples of alkyl halogen substituents include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tributyl, etc., in which one or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group that is a substituent of an alkyl group is a group that substitutes for the methylene group (-CH 2-) that constitutes the alkyl group (>C=O). Examples of cyclic groups substituting for alkyl groups include aromatic hydrocarbon groups and alicyclic hydrocarbon groups (which can be polycyclic or monocyclic). Aromatic hydrocarbon groups mentioned here can be the same as the aryl groups in Rh01 to Rh04 described later. Among the alicyclic hydrocarbon groups mentioned here, monocyclic alicyclic hydrocarbon groups are preferably those obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane and cyclohexane are examples. Furthermore, polycyclic alicyclic hydrocarbon groups are preferably those obtained by removing one or more hydrogen atoms from a polycyclic alkane; the polycyclic alkane is preferably a polycyclic alkane with 7 to 30 carbon atoms. Among them, the polycyclic alkane is preferably: adamantane, northane, isothane, tricyclodecane, tetracyclododecane, etc., which are polycyclic alkane with a cross-linked ring system; or polycyclic alkane with a condensed ring system such as a cyclic group containing a steroid skeleton.

[0065] In the aforementioned formula (T-ca-1), the aryl groups in R h01 to R h04 are hydrocarbon groups having at least one aromatic ring. 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, further preferably 6 to 15, and even more preferably 6 to 12. Aromatic rings include, specifically, 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. Heteratoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Aromatic heterocycles specifically include pyridine rings and thiophene rings. Specifically, the aryl group in Rh01 to Rh04 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, benzoylene, etc.); or a group obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkyl group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). The number of carbon atoms in the alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and especially preferably 1. Among these, it is more preferably a base obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle, or a base obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkyl group, and even more preferably a base obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring, or a base obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring with an alkyl group.

[0066] The aryl group in Rh01 to Rh04 may have substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, nitro, amino, cyclic, alkylcarbonyloxy, etc.

[0067] The alkyl group used as a substituent for the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and preferably methyl, ethyl, propyl, n-butyl, or tributyl. The descriptions of alkoxy groups, halogen atoms, halogenated alkyl groups, carbonyl groups, and cyclic groups that are substituents of aryl groups are the same as those of alkoxy groups, halogen atoms, halogenated alkyl groups, carbonyl groups, and cyclic groups that are substituents of alkyl groups. 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 even more preferred.

[0068] In the aforementioned formula (T-ca-1), at least one of Rh01 to Rh04 is an aryl group that may have substituents. The following shows specific examples of cations represented by the aforementioned formula (T-ca-1).

[0069] [Chemistry 9]

[0070] In the aforementioned formula (T-ca-2), the descriptions of the alkyl and aryl groups in Rh05 to Rh07 are the same as those of the alkyl and aryl groups in Rh01 to Rh04 mentioned above.

[0071] In the aforementioned formula (T-ca-2), at least one of Rh05 to Rh07 is an aryl group that may have substituents. The following shows specific examples of cations represented by the aforementioned formula (T-ca-2).

[0072] [Chemistry 10]

[0073] Regarding the anionic portion of component (T) Examples of anionic components of (T) include hexafluorophosphate anion, trifluoromethanesulfonic acid anion, perfluorobutyrate anion, and tetra(pentafluorophenyl)borate anion. Among these, hexafluorophosphate anion, trifluoromethanesulfonic acid anion, and perfluorobutanesulfonic acid anion are preferred, and hexafluorophosphate anion and trifluoromethanesulfonic acid anion are even more preferred.

[0074] In the composition for forming the separation layer of 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-Aid 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).

[0075] The (T) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types. In the composition for forming the separation layer of this embodiment, among the above-mentioned components, the preferred component (T) is hexafluorophosphate, trifluoromethanesulfonate, perfluorobutanesulfonate, more preferably trifluoromethanesulfonate, and even more preferably a quaternary ammonium salt of trifluoromethanesulfonic acid. 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. 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 that can appropriately absorb light in the wavelength range below 600 nm can be easily formed by firing. In addition, chemical resistance is further improved.

[0076] Photo-acid generator The composition for forming the separation layer in this embodiment may further contain a photoacid-generating agent. The above-mentioned composition for forming the separation layer contains a photoacid-generating agent, and thus, similar to the case containing (T) component as described above, during heating during firing, the oxidation of the separation layer is promoted by the acid generated by the photoacid-generating agent, and therefore it is easy to denature due to light irradiation (which can improve the photoreactivity of the separation layer). As photoacid generators, for example, onium salt-based acid generators such as strontium salts are preferred examples.

[0077] Examples of preferred cationic components among onium salt-based acid-producing agents include strontium cations and monium cations.

[0078] Examples of preferred anionic moieties for onium salt-based acid-producing agents include: tetra(pentafluorophenyl)borate ([B(C6F5)4]-); tetra(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4]-); difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2]-); trifluoro(pentafluorophenyl)borate ([(C6F5)BF3]-); tetra(difluorophenyl)borate ([B(C6H3F2)4]-), etc. Furthermore, anions represented by the following general formula (b0-2a) are also preferred.

[0079] [Chemistry 11] [In the formula, Rbf05 is a fluorinated alkyl group that may have substituents; nb1 is an integer from 1 to 5]

[0080] In the aforementioned formula (b0-2a), the fluorinated alkyl group in Rbf05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Specifically, Rbf05 is preferably a fluorinated alkyl group with 1 to 5 carbon atoms, more preferably a perfluoroalkyl group with 1 to 5 carbon atoms, and even more preferably trifluoromethyl or pentafluoroethyl. In the aforementioned formula (b0-2a), nb 1 is preferably an integer from 1 to 4, more preferably an integer from 2 to 4, and most preferably 3. When nb 1 is 2 or more, multiple R bf05s can be the same or different.

[0081] The photoacid-generating agent contained in the composition for forming the separation layer in this embodiment may be one type or two or more types. 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. If the content of the photoacid generator 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 that can appropriately absorb light in the wavelength range below 600 nm can be easily formed by firing. In addition, chemical resistance is further improved.

[0082] Photosensitive Agent Ingredients As a photosensitizer 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.

[0083] [Chemistry 12]

[0084] Examples of 1,2-diazidonaphthoquinone sulfonic acid compounds include 1,2-diazidonaphthoquinone-5-sulfonylurea compounds and 1,2-diazidonaphthoquinone-4-sulfonylurea compounds, with 1,2-diazidonaphthoquinone-5-sulfonylurea compounds being more preferred.

[0085] The following shows a preferred example of component (C1).

[0086] [Chemistry 13] [In formula (c1-1), D1 to D4 each independently represent a hydrogen atom or a 1,2-diazidonaphthoquinone-5-sulfonyl group; at least one of D1 to D4 represents a 1,2-diazidonaphthoquinone-5-sulfonyl group.]

[0087] The esterification rate of the aforementioned (C1) component is preferably 50-70%, more preferably 55-65%. If the esterification rate is above 50%, film loss after alkaline development can be further suppressed, and the residual film rate can be improved. If the esterification rate is below 70%, the storage stability is further improved. The term "esterification rate" here refers to the proportion of D1 to D4 in formula (c1-1) that are replaced by 1,2-diazidonaphthoquinone-5-sulfonylutriates for the compound represented by the aforementioned formula (c1-1). The aforementioned (C1) component is also better from the perspective of being very inexpensive and enabling high sensitivity.

[0088] Furthermore, as component (C), other photosensitizing components besides the aforementioned component (C1) may be used (hereinafter also referred to as "component (C2)"). As a (C2) component, for example, the esterification 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-sulfonylurea compound or a 1,2-diazidonaphthoquinone-4-sulfonylurea compound) can be cited as a preferred component.

[0089] 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.

[0090] The (C) component contained in the composition for forming the separation layer in this embodiment can be used alone or in combination of two or more. In the composition for forming the separation layer of this embodiment, among the above-mentioned components (C), component (C1) is preferably used. 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). If the content of component (C) is within the aforementioned preferred range, the photoreactivity of the separation layer can be further improved.

[0091] Organic Solvent Composition The composition for forming the release layer in this embodiment may contain an organic solvent component (hereinafter also referred to as "(S) component") in order to adjust the coating workability, etc. 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, sine, nor-sine, pinane, thujane, carene, and long-chain hydrocarbons. Terpenes, geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroterpineol acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, dipentene and other terpene solvents; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexane... Ketones such as hexanone (CH), 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; the aforementioned polyols or compounds containing ester bonds such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., monoalkyl ethers, or monophenyl ethers, etc., containing ether bonds. Derivatives (preferably propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME)); cyclic ethers such as dialkyl, 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. The (S) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types.

[0092] 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 manner that the total amount of the above-mentioned component (P) in the separation layer forming composition is 70% by mass or less, and more preferably 10 to 50% by mass, relative to the total mass (100% by mass) of the composition.

[0093] Surfactants The composition for forming the release layer in this embodiment may contain a surfactant in order to adjust the coating workability, etc. Examples of surfactants include polysiloxane-based surfactants and fluorinated surfactants. Examples of polysiloxane-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 TF-1 can be used as surfactants. 025SF, 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.

[0094] The surfactant contained in the composition for forming the separation layer in this embodiment may be one type or two or more types. 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. If the content of the surfactant is within the aforementioned preferred range, a release layer with high flatness can be easily formed when the release layer forming composition is applied to the support substrate.

[0095] (Supporting substrate for the separation layer) The second state sample of the present invention includes 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 state sample. In the support substrate with a release layer in this embodiment, a release layer formed using the release layer forming composition of the above embodiment is provided on the support substrate. Therefore, in the support substrate with the release layer, photoreactivity and chemical resistance are improved.

[0096] <Supporting Substrate> The support substrate has the property of allowing light to pass through. The support substrate system is a component that supports the substrate and is attached to the substrate through a release layer. Therefore, the support substrate preferably has 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 preferably allows light of wavelengths that can deform the release layer to pass through. Materials used as the supporting substrate include, for example, glass, silicone, and acrylic resins. The shape of the supporting substrate can be, for example, rectangular or circular, but is not limited to these. Furthermore, as a support substrate, in order to further increase the density of the integrated substrate and improve production efficiency, a large panel with a quadrilateral shape when viewed from above can also be used to obtain a substrate that is larger in size than a circular support substrate.

[0097] <Separation Layer> The release layer can be formed using the release layer forming composition of the above embodiments, and is a layer formed by firing a sintered body containing the resin component (P) of the release layer forming composition. The release layer is suitably modified by absorbing light irradiated through the supporting substrate. Furthermore, the separation layer can also be a layer obtained by blending materials that do not have a light-absorbing structure within the scope of not impairing the essential characteristics of the present invention. However, from the viewpoint of photoreactivity and separation, it is preferable to form a layer that is only formed by light-absorbing materials.

[0098] The term "fired body" as used here refers to the product obtained by firing a composition containing (P) component. This calcination system is formed by calcining a composition containing (P) in an atmospheric environment, i.e., in the presence of oxygen, wherein at least a portion of the composition undergoes carbonization. The calcined 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.

[0099] The term "deterioration" of the delamination layer refers to the phenomenon where the delamination layer becomes susceptible to damage from external forces, or where the adhesion between the delamination layer and the adjacent layers decreases. The delamination layer becomes brittle by absorbing light, losing its strength or adhesion before exposure to light. This deterioration occurs through processes such as decomposition caused by the energy of the absorbed light, changes in its three-dimensional configuration, or dissociation of functional groups.

[0100] 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. If the thickness of the separation layer is between 0.05 μm and 50 μm, the desired denaturation can be achieved by short-duration and low-energy light irradiation. Furthermore, from a productivity perspective, the thickness of the separation layer is preferably below 1 μm.

[0101] For example, in the laminate 10 shown in Figure 1, the side of the release 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 and the substrate uniformly.

[0102] The support substrate with the separation layer in this embodiment can be manufactured by performing the same operation as the [separation layer formation step] described later.

[0103] The support substrate with the release layer in this embodiment has enhanced laser reactivity and further improved photoreactivity because it is provided with the release layer obtained by applying the release layer forming composition of the above embodiment. Preferably, it also improves chemical resistance.

[0104] (Laminated body) The third embodiment 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 embodiments. As shown in Figure 1, in the laminate 10 of this embodiment, a separation layer 2, an adhesive layer 3, and a substrate 4 are sequentially laminated on the support substrate 1.

[0105] The description of support substrate 1 is the same as that in the description of support substrate above. The description of separation layer 2 is the same as that in the above description of <Separation Layer>.

[0106] <Next layer> The adhesive layer 3 is used to bond the support substrate 1 to the substrate 4, and can be formed using an adhesive layer forming composition. Examples of the adhesive layer forming compositions include compositions containing, for example, thermoplastic resins, diluents, and additives. The thermoplastic resin, as long as it exhibits adhesion, can be one or more of the following: hydrocarbon resins (preferably cycloolefin polymers), acrylic-styrene resins, maleimide resins, elastomer resins, and polyurethane resins. The diluent can be the same as component (S) described above. Other components include additive resins for improving the properties of the adhesive layer, curing monomers, photopolymerization initiators, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors, and surfactants.

[0107] The thickness of 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. 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. Furthermore, 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 step.

[0108] <Substrate> 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. As substrate 4, silicon wafer substrate can be used in a typical manner, but it is not limited to this. Ceramic substrate, thin film substrate, flexible substrate, etc. can also be used.

[0109] In this embodiment, the component is a semiconductor component or other component, and may have a single-layer or multi-layer structure. Furthermore, when the component is a semiconductor component, the electronic part obtained by cutting the sealed substrate becomes a semiconductor device.

[0110] The laminate of the above 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 embodiments, thereby improving the separation of the support substrate from the laminate. Furthermore, the laminate of the embodiment has improved chemical resistance because it is provided with a release layer obtained by applying the release layer forming composition of the above embodiment. Therefore, the laminate of the embodiment is less susceptible to damage from chemicals used in etching processes, photolithography processes, etc.

[0111] In the laminated body described above, the supporting substrate 1 and the separating layer 2 are adjacent, but this is not a limitation; other layers may also be formed between the supporting substrate 1 and the separating layer 2. In this case, the other layers can be made of a light-transmitting material. Accordingly, layers that impart better properties to the laminated body 10 can be appropriately added without hindering the incidence of light onto the separating layer 2. Depending on the type of material constituting the separating layer 2, different wavelengths of light can be used. Therefore, the materials constituting the other layers do not need to transmit all wavelengths of light; they can be appropriately selected from materials that transmit wavelengths of light that can alter the properties of the material constituting the separating layer 2.

[0112] Furthermore, the laminate described in the above 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 such cases, for example, a separation layer that also functions as an adhesive layer may be used.

[0113] (Manufacturing method of laminated bodies) The fourth aspect of the present invention is a method for manufacturing a laminate having a separation layer between a light-transmitting support substrate and a substrate, comprising a separation layer formation step and a lamination step.

[0114] <First Implementation> Figure 2 is a schematic diagram illustrating one embodiment of the method for manufacturing a laminate. Figure 2(a) illustrates the separation layer formation step, and Figure 2(b) illustrates the lamination step. 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). Furthermore, a composition for forming an adhesive layer is used, which is obtained by dissolving a hydrocarbon resin in the (S) component.

[0115] [Separation Layer Formation Steps] The separation layer formation step in the embodiment is as follows: the separation layer formation composition of the above embodiment is applied to one side of the support substrate, and then fired to form the separation layer. In Figure 2(a), the composition for forming the separation layer according to 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).

[0116] The method of coating the composition for forming the separation 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 cited.

[0117] In the separation layer formation step, the (S) component is removed from the coating layer of the separation layer forming composition applied to the support substrate 1 under a heated environment or a 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 to 150°C for 120 to 360 seconds. Then, under atmospheric conditions, 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.

[0118] 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 above the lower limit of the aforementioned preferred range, a separation layer capable of absorbing light in the wavelength range below 600 nm can be formed more stably. There is no particular limit to the upper limit of the firing temperature, but it is preferable to set it below 800°C, and even more preferably below 600°C.

[0119] The firing time is preferably set to 3 minutes or more but less than 3 hours, and more preferably 3 minutes or more but less than 30 minutes. In this way, a separation layer capable of absorbing light in the wavelength range below 600 nm can be reliably formed.

[0120] [Layering Steps] The lamination step in the embodiment is as follows: laminating the aforementioned support substrate with the aforementioned separation layer and the aforementioned substrate without the aforementioned separation layer through the aforementioned separation layer and the aforementioned adhesive layer. In Figure 2(b), a support substrate 1 with a separation layer 2 and a substrate 4 without a separation layer 2 are laminated through the separation layer 2 and the adhesive layer 3 to obtain a laminate 10 formed by sequentially stacking the support substrate 1, the separation layer 2, the adhesive layer 3 and the substrate 4.

[0121] As a specific method for the lamination step, 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.

[0122] The method of coating the next layer forming composition onto the release layer 2 is not particularly limited, and can be carried out in the same way as the method of coating the release layer forming composition onto the support substrate 1 described above. The baking process for forming the adhesive layer 3 is carried out, for example, by heating in stages while raising the temperature, thereby removing the (S) component from the adhesive layer forming composition to form the adhesive layer 3.

[0123] The method for bonding the support substrate 1 and 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).

[0124] According to the method for manufacturing a laminate according to the first embodiment, the separation layer is formed using the separation layer formation composition of the above embodiment. Therefore, laser reactivity is enhanced, photoreactivity is further improved, and the separation of the support substrate from the laminate is improved. Preferably, it is possible to manufacture a laminate with high chemical resistance.

[0125] In the manufacturing method of the laminate described in this embodiment, the separation layer 2 is formed on the support substrate 1, but it is not limited to this; the separation layer 2 may also be formed on the substrate 4. In the manufacturing method of the laminate in the above embodiment, the bonding layer 3 is formed on the separation layer 2, but it is not limited to this. The bonding layer 3 may also be formed on the substrate 4. Alternatively, the separation layer 2 can also 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 bonding layer 3, and the separation layer 2.

[0126] <Second Implementation Method> Figure 3 is a schematic diagram illustrating another embodiment of the manufacturing method of the laminate. Figure 3(a) shows a laminate manufactured using the manufacturing method of the first embodiment, and Figure 3(b) illustrates the sealing step. In addition to the separation layer formation step and the lamination step described above, the manufacturing method of the laminate in other embodiments of the above-described embodiments also includes a sealing step.

[0127] [Sealing Steps] The sealing step in the embodiment is as follows: after the aforementioned lamination step, 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. In Figure 3(b), a sealing body 20 (laminated body) is obtained by sealing the substrate 4 disposed on the adhesive layer 3 with a sealing material.

[0128] In the sealing step, for example, sealing material heated to 130~170°C is supplied to the adhesive layer 3 while maintaining a high viscosity and covering the substrate 4, and then compressed and molded to form a sealing body 20 (laminated body) with a sealing material layer 5 disposed on the adhesive layer 3.

[0129] As a sealing material, for example, a composition containing epoxy resin or polysiloxane resin can be used. The sealing material layer 5 is preferably provided in such a way that it covers all the substrates 4 on the bonding layer 3, rather than being provided separately on each substrate 4.

[0130] According to the manufacturing method of the laminate according to the second embodiment, a sealing substrate having a substrate (wiring layer) on the release layer and the bonding layer can be suitably formed by applying the release layer forming composition of the above embodiment.

[0131] <Third Implementation Method> Figure 4 is a schematic diagram illustrating another embodiment of the manufacturing method of the laminate. Figure 4(a) shows a seal manufactured using the manufacturing method of the second embodiment, Figure 4(b) illustrates the grinding step, and Figure 4(c) illustrates the rewiring step. In addition to the separation layer formation step, the lamination step, and the sealing step described above, the manufacturing method of the laminate in other embodiments of the above-described embodiments further includes a grinding step and a rewiring formation step.

[0132] [Grinding Steps] The grinding step in the embodiment is as follows: after the aforementioned sealing step, the sealing material portion (sealing material layer 5) in the sealing body 20 is ground to expose a portion of the substrate 4. The grinding of the sealing material portion is shown in Figure 4(b) for example, by grinding the sealing material layer 5 to a thickness approximately equal to that of the substrate 4.

[0133] [Rewiring Steps] The redistribution forming step in the implementation method is as follows: after the aforementioned grinding step, a redistribution layer 6 is formed on the aforementioned exposed substrate 4. A redistribution layer, also known as an RDL, is a thin film of wiring that forms the wiring for connecting components. It can have a single layer or multiple layers. For example, a redistribution layer can be a layer formed by using a conductive material (metals such as aluminum, copper, titanium, nickel, gold, and silver, and alloys such as silver-tin alloys) on a dielectric material (silicon oxide (SiO₂), photosensitive resins such as photosensitive epoxy resins, etc.), but it is not limited to this.

[0134] As a method for forming the redistribution layer 6, firstly, a dielectric layer such as silicon oxide (SiO₂x) or a photosensitive resin is formed on the sealing material layer 5. The dielectric layer formed by silicon oxide can be formed using methods such as sputtering or vacuum evaporation. The dielectric layer formed by photosensitive resin can be formed by coating the sealing material layer 5 with the photosensitive resin using methods such as spin coating, dip coating, roller coating, spraying, or slot coating.

[0135] Subsequently, conductive materials such as metals are used to form wiring on the dielectric layer. As a method for forming wiring, known semiconductor manufacturing processes such as photolithography (resist lithography) and etching can be used. Examples of such photolithography include photolithography using positive resist materials and photolithography using negative resist materials.

[0136] When photolithography and etching are performed, the separation 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. Especially in fan-out technology, PGMEA, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), or cyclohexanone can be used as resist solvents. However, by using the separation layer forming composition of the above-described embodiments to form the separation layer, 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. In this way, a redistribution layer 6 can be appropriately formed on the sealing material layer 5.

[0137] According to the manufacturing method of the laminate according to the third embodiment, a laminate 30 can be stably manufactured by sequentially stacking a support substrate 1, a release layer 2, an adhesive layer 3, a sealing material layer 5 covering a substrate 4, and a redistribution layer 6. The aforementioned stack 30 is a stack fabricated in the process of mounting terminals disposed on the substrate 4 to the redistribution layer 6 extending beyond the chip area, based on fan-out technology.

[0138] In the manufacturing method of the multilayer in this embodiment, bumps can be formed or components can be mounted on the redistribution layer 6. The mounting of components onto the redistribution layer 6 can be performed, for example, using a pick-and-place machine.

[0139] (Manufacturing methods for electronic components) In the manufacturing method of the electronic component of the fifth state of the present invention, after obtaining the laminate using the manufacturing method of the laminate of the fourth state described above, there are a separation step and a removal step.

[0140] Figure 5 is a schematic diagram illustrating one embodiment of a method for manufacturing a semiconductor package (electronic component). Figure 5(a) shows a multilayer manufactured using the manufacturing method of the third embodiment, Figure 5(b) illustrates the separation step, and Figure 5(c) illustrates the removal step.

[0141] [Separation Steps] The separation step 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.

[0142] As shown in Figure 5(a), during the separation step, light (arrow) is irradiated onto the separation layer 2 through the support substrate 1, thereby causing the separation layer 2 to deform. For example, wavelengths below 600 nm can be used to modify the separation layer 2. 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 laser, ruby ​​laser, glass laser, YVO4 laser, LD laser, and fiber laser, liquid lasers such as pigment lasers, gas lasers such as CO2 laser, excimer laser, Ar laser, and He-Ne laser, semiconductor lasers, free electron lasers, and non-laser light can be used. In this way, the separation layer 2 can be modified, thereby achieving a state in which the support substrate 1 can be easily separated from the substrate 4.

[0143] When laser light is applied, the following conditions can be cited as an example of laser light application conditions. The average output value of the laser light is preferably above 1.0 W and below 5.0 W, more preferably above 3.0 W and below 4.0 W. The repetition frequency of the laser light is preferably above 20 kHz and below 60 kHz, more preferably above 30 kHz and below 50 kHz. The scanning speed of the laser light is preferably above 100 mm / s and below 10000 mm / s.

[0144] After the separation layer 2 is irradiated with light (arrow) to deform it, as shown in Figure 5(b), the support substrate 1 is separated from the laminate 30. 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. 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 0.1~5 kgf (0.98~49 N).

[0145] [Remove steps] The removal step in the implementation method is as follows: after the aforementioned separation step, the adhesive layer 3 and the separation layer 2 attached to the substrate 4 are removed. In Figure 5(b), after the separation step, an adhesive layer 3 and a separation layer 2 are attached to the substrate 4. In this embodiment, in the removal step, by removing the adhesive layer 3 and the separation layer 2 attached to the substrate 4, the electronic component 40 shown in Figure 5(c) is obtained.

[0146] 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 plasma. As a cleaning solution, it is preferable to use a cleaning solution containing an organic solvent. As an organic solvent, it is preferable to use an organic solvent formulated in the composition for forming the separation layer or an organic solvent formulated in the composition for forming the adhesion layer.

[0147] <Other Implementation Methods> Figure 6 is a schematic diagram illustrating other embodiments of the manufacturing method of semiconductor package (electronic component). Figure 6(a) is a schematic diagram showing another embodiment of the laminate to which the present invention is applied, Figure 6(b) is a diagram illustrating the separation step, and Figure 6(c) is a diagram illustrating the removal step.

[0148] In the laminate 50 of the embodiment shown in Figure 6(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.

[0149] The description of the support substrate 51 is the same as that in the description of the support substrate above. The description of the separation layer 52 is the same as that in the above description of the separation layer.

[0150] Wiring layer 57 can be, for example, a layer obtained by forming wiring on a dielectric material (silicon oxide (SiO x), photosensitive resin such as photosensitive epoxy resin, etc.) using a conductive material (metals such as aluminum, copper, titanium, nickel, gold, silver, and alloys such as silver-tin alloys). The description of substrate 54 is the same as that in the above description of substrate. Sealing material layer 55 may be, for example, a layer formed using a composition containing epoxy resin or polysiloxane resin.

[0151] The laminate 50 can be manufactured, for example, by operating as described below. First, a separation layer 52 is formed on the side of the supporting 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 step] described above. 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 step] described above. Secondly, on the side of the wiring layer 57 opposite to the separation layer 52, the substrate 54 is attached, for example, through a bump. 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 is performed in the same manner as the [sealing step] described above. In this way, the laminate 50 is manufactured.

[0152] As shown in Figure 6(a), in the separation step of the embodiment, light (arrow) is irradiated onto the separation layer 52 through the support substrate 51 to deform the separation layer 52. After the separation layer 52 is irradiated with light (arrow) to deform it, as shown in Figure 6(b), the support substrate 51 is separated from the laminate 50. The operations in the separation step described above are performed in the same way as those in the [separation step] described above.

[0153] As shown in Figure 6(c), in the removal step of the embodiment, after the aforementioned separation step, the separation layer 52 attached to the wiring layer 57 is removed, thereby obtaining the electronic component 60. As a method for removing the release layer 52 attached to the wiring layer 57, examples include irradiating plasma or using a cleaning solution to remove residue from the release layer 52. Oxygen plasma is preferred as the aforementioned plasma.

[0154] In the manufacturing method of electronic components according to this embodiment, after the above-mentioned removal steps, the electronic components can be further processed by forming solder balls, cutting, or forming an oxide film. [Example]

[0155] The present invention will now be described in more detail by way of examples, but the present invention is not limited to these examples.

[0156] <Resin Composition> As resin components, resins (P-1), (P-2), (P-3), (Q-1), and (Q-2) as shown below are used.

[0157] 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. The copolymer composition ratio (the proportion of each repeating unit in the structural formula (molar ratio)) determined by 13C-NMR is repeating unit (p12) / repeating unit (p22) = 10 / 90.

[0158] 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. The copolymer composition ratio (the proportion of each repeating unit in the structural formula (molar ratio)) determined by 13C-NMR is repeating unit (p12) / repeating unit (p22) = 5 / 95.

[0159] [Chemistry 14]

[0160] 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. The copolymer composition ratio (the proportion of each repeating unit in the structural formula (molar ratio)) determined by 13C-NMR is repeating unit (p16) / repeating unit (p26) = 50 / 50.

[0161] [Chemistry 15]

[0162] 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 of repeating units in the structural formula (molar ratio)) is repeating unit (p21) = 100.

[0163] [Chemistry 16]

[0164] 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 of repeating units in the structural formula (molar ratio)) is repeating unit (p26) = 100.

[0165] <Preparation of Compositions for Separation Layer Formation> (Examples 1-5, Comparative Examples 1-2) 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).

[0166] [Table 1] Resin components Thermal acid-producing agents (T) Organic solvent components (S) Example 1 (P)-1

[0100] - (T)-1

[10] (S)-1

[0440] Example 2 (P)-2

[0100] - (T)-1

[10] (S)-1

[0440] Example 3 (P)-3

[0100] - (T)-1

[10] (S)-1

[0440] Example 4 (P)-3

[70] (P)-4

[30] (T)-1

[10] (S)-1

[0440] Example 5 (P)-3

[40] (P)-4

[60] (T)-1

[10] (S)-1

[0440] Comparative Example 1 - (P)-4

[0100] (T)-1

[10] (S)-1

[0440] Comparative Example 2 - (P)-5

[0100] (T)-1

[10] (S)-1

[0440]

[0167] In Table 1, each abbreviation has the following meaning. The value in [ ] is the amount to be mixed (parts by mass). (P)-1: Resin (P-1) (P)-2: Resin (P-2) (P)-3: Resin (P-3) (P)-4: Resin (Q-1) (P)-5: Resin (Q-2) (T)-1: A thermally generated acid-producing agent formed from compounds represented by the following chemical formula (T-1). (S)-1: Propylene glycol monomethyl ether (PGME)

[0168] [Chemistry 17]

[0169] <Formation of the Separation Layer> The separation layer formation composition of each example was spin-coated onto a bare glass support substrate (12 inches, 0.7 mm thick), and heated at 100°C for 300 seconds, and then heated at 150°C for 300 seconds to remove the solvent, thereby forming a film with a thickness of 1 μm. Secondly, the film is fired at 300°C for 20 minutes in an atmospheric environment to form a separation layer with a thickness of 0.3 μm on the bare glass support substrate, thereby obtaining a support substrate with a separation layer.

[0170] [Evaluation of light transmittance in the separation layer] 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 for each film formed on the bare glass support substrate was evaluated. The evaluation results are shown in Table 2.

[0171] [Evaluation of laser reactivity in the separation layer] For the separation layers formed using the separation layer forming compositions of each example, the laser reactivity was evaluated by irradiating them with laser light of wavelength 532 nm under the conditions of scanning speed of 7200 mm / s, frequency of 40 kHz, output (current value) of 24 A, and irradiation spacing of 140 μm. The evaluation of the aforementioned laser reactivity was conducted as follows: using a VHX-600 microscope (manufactured by Keyence), the state of the laser light traces irradiated onto the separation layer was observed, and the size of the laser light traces on the surface of the separation layer (laser indentation diameter / μm) was determined. Evaluation criteria were established as described below. The evaluation results are shown in Table 2. Evaluation Criteria ◎: The laser indentation diameter is 160 μm or more. ○: The diameter of the laser indentation is greater than 150 μm but less than 160 μm. △: Laser indentation diameter is greater than 100 μm but less than 150 μm. ×: Laser indentation diameter did not reach 100 μm.

[0172] [Table 2] Composition for forming separation layer Resin composition (mixing mass ratio) Separation layer Light transmittance (%) Laser reactivity Laser indentation diameter (μm) laser evaluate Example 1 Resin (P-1) 100% 34.9 176.9 ◎ Example 2 Resin (P-2) 100% 30.0 184.7 ◎ Example 3 Resin (P-3) 100% 33.2 195.3 ◎ Example 4 Resin (P-3) / Resin (Q-1) = 70 / 30 30.9 185.6 ◎ Example 5 Resin (P-3) / Resin (Q-1) = 40 / 60 32.8 178.4 ◎ Comparative Example 1 Resin (Q-1) 100% 48.6 107.6 △ Comparative Example 2 Resin (Q-2) 100% 35.0 120.5 △

[0173] 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. That is, it has been confirmed that, according to the composition for forming a separation layer using the present invention, a separation layer with further improved photoreactivity and improved separation of the support substrate from the laminate can be formed.

[0174] <Manufacturing of Laminated Materials> 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 (separation layer formation step). 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 temperatures of 90°C, 160°C, and 220°C for 4 minutes each to form an adhesive layer with a film thickness of 50 μm. Next, the bare glass support substrate with the release layer and the semiconductor wafer substrate with the adhesive layer are stacked in the order of semiconductor wafer substrate, adhesive layer, release 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. In this way, the bare glass support substrate and the semiconductor wafer substrate are deposited with the release layer and adhesive layer in between, resulting in a laminate (lamination step).

[0175] After obtaining the laminate, the separation layer was irradiated with laser light at a wavelength of 532 nm from the substrate side of the laminate under the conditions of a scan speed of 3000 mm / s, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation spacing of 140 μm (separation step). Subsequently, the menthol was removed by cleaning the adhesion layer (removal step). It has been confirmed that the above operations support the separation of the substrate from the semiconductor wafer substrate of the laminate.

[0176] <Example of Electronic Component Manufacturing (1)> Using the same method as described above for the formation of the release layer, the release 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 release layer with a thickness of 0.5 μm on the bare glass support substrate, thereby obtaining a support substrate with a release layer (release layer formation step). Then, an adhesive composition TZNR (registered trademark)-A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was 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. Next, using a die bonder (manufactured by TRESKY Corporation), the die bonder plate is heated to 150°C, and a 2 mm square silicon bare wafer is pressed onto the aforementioned bonding layer for 1 second with a pressure of 35 N. After the silicon bare wafer is placed, it is heated at 200°C for 1 hour under a nitrogen atmosphere to obtain the laminate (laminarization step).

[0177] The resulting laminate was placed on a plate heated to 50°C. 12 g of a sealant containing epoxy resin was then placed on top, covering the bare wafer. Under reduced pressure (below 10 Pa), a pressure of 1 ton was applied using an attachment device and a pressing plate heated to 130°C for 5 minutes. This process sealed the bare wafer disposed on the adhesive layer, creating a sealant (sealing step).

[0178] After fabricating the sealing body, the separation layer was irradiated with laser light at a wavelength of 532 nm from the support substrate side of the sealing body under the conditions of a scanning speed of 3000 mm / s, a frequency of 40 kHz, an output (current value) of 24 A, and an irradiation spacing of 140 μm (separation step). Subsequently, the menthol adhesive layer was removed by cleaning (removal step). It has been confirmed that the above operations support the separation of the substrate from the seal. Electronic components are obtained by operating as described above.

[0179] <Example of Electronic Component Manufacturing (2)> Using the same method as described above for the formation of the release layer, the release 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 release layer with a thickness of 0.35 μm on the bare glass support substrate, thereby obtaining a support substrate with a release layer (release layer formation step). Next, a wiring layer forming material (trade name TMMR S2000) is coated on the aforementioned separation layer and fired at 90°C for 3 minutes in an atmospheric environment to form a wiring layer with a thickness of 10 μm on the separation layer, thereby obtaining a laminate.

[0180] After the wiring layer is formed, the separation layer is irradiated with 532 nm laser light from the bare glass support substrate side of the laminate under the conditions of irradiation dose of 200 mJ / cm2, output (current value) of 22 A, and irradiation spacing of 80 μm. Next, after immersion in propylene glycol monomethyl ether acetate (PGMEA) as a cleaning solution, it is baked at 90°C for 5 minutes. Next, the firing is repeated 3 times under a nitrogen atmosphere at 200°C for 60 minutes to separate the support substrate from the laminate (separation step). Then, the separation layer side of the wiring layer is irradiated with oxygen plasma (power of 2000 W, oxygen flow rate of 2000 sccm, pressure of 75 Pa, temperature of 50°C, and irradiation time of 5 minutes) to remove the separation layer adhering to the wiring layer (removal step). It has been confirmed that the above operations support the separation of the substrate from the laminate. Electronic components are obtained by operating as described above.

[0181] 1: Supporting substrate 2: Separation layer 3: Next layer 4:Substrate 5: Sealing material layer 6: Rerouting layer 10: Laminated body 20: Sealing body 30: Laminated body 40: Electronic Components 50: Laminated body 51: Supporting substrate 51S: The outermost surface 52: Separation layer 54:Substrate 55: Sealing material layer 57: Wiring Layer 60: Electronic Components

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 substrate, wherein the separation layer can be denatured by irradiation from the support substrate side, thereby separating the support substrate from the laminate, the composition for forming the separation layer containing a resin component (P) having a repeating unit represented by the following general formula (p1), [Chemical 1] [wherein, LP1 represents a divalent linker; RP1 represents a condensed polycyclic aromatic group that may have substituents].

2. The separation layer forming composition of claim 1, used to form the separation layer in a laminate having a separation layer and an adhesive layer between a light-transmitting support substrate and a substrate, wherein the separation layer can be deformed by irradiation from the support substrate side, thereby separating the support substrate from the laminate, wherein the separation layer forming composition contains a resin component (P) having a repeating unit represented by the following general formula (p1), [Chemical 2] [wherein, LP1 represents a divalent linker; RP1 represents a condensed polycyclic aromatic group that may have substituents].

3. The composition for forming a release layer as claimed in claim 1, wherein the resin component (P) further has a repeating unit represented by the following general formula (p2), [Chemical 3] [wherein, LP2 represents a divalent linker; RP2 represents a monocyclic aromatic group that may have substituents].

4. The composition for forming a release layer as claimed in claim 2, wherein the resin component (P) further has a repeating unit represented by the following general formula (p2), [Chemical 3] [wherein, LP2 represents a divalent linker; RP2 represents a monocyclic aromatic group that may have substituents].

5. The composition for forming a separation layer as claimed in any of claims 1 to 4, further comprising a thermally generated acid agent.

6. A support substrate with a release layer, comprising: a support substrate; and a release layer formed on the support substrate using a release layer forming composition as claimed in any one of claims 1 to 5.

7. A laminate having a separation layer between a light-transmitting support substrate and a base plate, wherein the separation layer is a sintered body of a separation layer forming composition as claimed in any one of claims 1 to 5.

8. A method for manufacturing a laminate, comprising the method of manufacturing a laminate having a separation layer between a light-transmitting support substrate and a substrate, the method comprising the following steps: a separation layer forming step, wherein a separation layer forming composition as claimed in any one of claims 1 to 5 is applied to at least one of the substrate or the support substrate, and then fired to form the separation layer; and a lamination step, wherein the substrate and the support substrate are laminated through the separation layer.

9. The method for manufacturing the laminate as claimed in claim 8 further includes the following sealing step: after the above-mentioned lamination step, the substrate that is bonded to the support substrate through the above-mentioned separation layer is sealed with a sealing material to create a sealing body.

10. The method for manufacturing a multilayer as claimed in claim 9 further comprises the following steps: a grinding step, which, after the sealing step, grinds a portion of the sealing material in the sealing body to expose a portion of the substrate; and a rewiring step, which, after the grinding step, forms rewiring on the exposed substrate.

11. A method for manufacturing an electronic component, comprising the following steps: a separation step, wherein after obtaining a laminate using the laminate manufacturing method of any one of claims 8 to 10, 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 a removal step, wherein after the separation step, the separation layer attached to the substrate is removed.

Images