Laminate and method for producing electronic component

Abstract

To provide: a laminate, from which a support base can be separated by irradiation with light and which has a metal layer or a rewiring layer provided without intervention of an adhesive layer; and a method for producing an electronic component using the same.SOLUTION: A laminate 10 comprises: a support base 11 which transmits light; a separation layer 12 formed on the support base 11; and a metal layer 14 or a rewiring layer 16 formed above the separation layer 12 opposite to the support base 11. The separation layer 12 changes its nature by irradiation with light from the support base 11 side to make the support base 11 separable from the laminate 10. Further, the separation layer 12 is a layer comprising a light absorptive resin or a layer comprising a resin which does not have light absorptivity and a light absorber.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a laminate and a method for manufacturing an electronic component. [Background technology]

[0002] 2. Description of the Related Art In recent years, there has been a demand for higher integration, thinner size, and smaller size of semiconductor packages (electronic components) that include semiconductor elements. In order to miniaturize semiconductor packages, it is important to reduce the thickness of the substrate in which the elements are built in. However, when the substrate is made thinner, its strength decreases, and the substrate becomes more susceptible to breakage during the manufacture of the semiconductor package.

[0003] In response to this, a laminate in which a supporting base is bonded to a substrate is used. Finally, the supporting base is separated from this laminate to manufacture an electronic component. For example, a method has been proposed in the past in which a substrate and a light-transmitting supporting base are laminated via a separation layer and an adhesive layer that are altered by irradiation with light, in which the supporting base is separated from the laminate (see, for example, Patent Document 1).

[0004] 5A to 5C are diagrams showing an example of a method for producing a laminate, and Fig. 5D is a diagram illustrating an operation for separating the support base from the laminate. First, a separation layer 52, which has a property of being altered by irradiation with light, is formed on a light-transmitting support base 51 (FIG. 5A). Next, an adhesive layer 54 and a substrate 56 are laminated in this order on the separation layer 52, and the support base 51 and the substrate 56 are bonded together via the separation layer 52 and the adhesive layer 54 (FIG. 5B). Next, the substrate 56 is processed to obtain the laminate 50. Here, an encapsulant layer 58 is provided so as to cover the entire substrate 56 (FIG. 5C). 5C is then turned upside down, and separation layer 52 is irradiated with synchrotron radiation (arrow) from the supporting base 51 side (FIG. 5D). As a result, separation layer 52 is altered and decomposed, and processed substrate 56 and supporting base 51 are separated. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent No. 6681762 Summary of the Invention [Problem to be solved by the invention]

[0006] However, in a method using a conventional laminate, that is, a laminate formed by laminating a supporting base and a substrate via a separation layer and an adhesive layer, when metal sputtering is performed on the adhesive layer and then an attempt is made to form a redistribution layer (RDL), the adhesive layer may flow and deform when heated, making it impossible to stably laminate the metal sputtered layer (metal layer) or the redistribution layer.

[0007] The present invention has been made in consideration of the above circumstances, and has an objective of providing a laminate in which a supporting base can be separated by irradiation with light and which has a metal layer or a redistribution layer without an adhesive layer, and a method for manufacturing an electronic component using the same. [Means for solving the problem]

[0008] In order to solve the above problems, the present invention employs the following configuration.

[0009] A first aspect of the present invention is a laminate comprising a light-transmitting supporting base, a separation layer formed on the supporting base, and a metal layer or a redistribution layer formed directly on the separation layer on the side opposite the supporting base, wherein the separation layer is a layer that is altered by irradiation of light from the supporting base side to enable separation of the supporting base from the laminate, and the separation layer is a layer that contains a light-absorbing resin or a layer that contains a non-light-absorbing resin and a light-absorbing agent.

[0010] A second aspect of the present invention is a method for manufacturing an electronic component, comprising: a separation step of separating the supporting base from the laminate of the first aspect by irradiating the separation layer from the supporting base side with light to alter the separation layer, and a removal step of removing the separation layer adhering to the metal layer or redistribution layer after the separation step. Effect of the Invention

[0011] According to the present invention, it is possible to provide a laminate in which a supporting base can be separated by irradiation with light and which has a metal layer or a rewiring layer without an adhesive layer, and a method for manufacturing an electronic component using the same. [Brief description of the drawings]

[0012] [Figure 1] FIG. 1 illustrates one embodiment of a laminate. [Diagram 2] FIG. 13 is a diagram showing another embodiment of a laminate. [Figure 3A] 1A to 1C are diagrams illustrating a method for forming a separation layer. [Figure 3B] FIG. 2 is a diagram showing an example of a laminate prepared in the first embodiment. [Figure 3C] FIG. 2 is a diagram illustrating an operation for separating the support base from the laminate. [Figure 3D] FIG. 13 is a diagram showing the state after the separation step. [Figure 3E] FIG. 13 is a diagram showing a state after a removing step, illustrating an example of a semiconductor package (electronic component) manufactured in the first embodiment. [Figure 4A] 1A to 1C are diagrams illustrating a method for forming a separation layer. [Figure 4B] FIG. 11 is a diagram showing an example of a laminate prepared in the second embodiment. [Figure 4C] FIG. 2 is a diagram illustrating an operation for separating the support base from the laminate. [Figure 4D] FIG. 13 is a diagram showing the state after the separation step. [Figure 4E] 13 is a diagram showing a state after a removing step, illustrating an example of a semiconductor package (electronic component) manufactured in the second embodiment. FIG. [Figure 5A] 1A to 1C are diagrams illustrating a method for forming a separation layer. [Figure 5B] 1A to 1C are diagrams illustrating an example of a method for manufacturing a laminate. [Figure 5C] FIG. 2 is a diagram showing an example of a laminate; [Figure 5D] FIG. 2 is a diagram illustrating an operation of separating the support base from the laminate. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013] (First aspect: laminate) The laminate according to the first aspect of the present invention is a laminate comprising a light-transmitting supporting base, a separation layer formed on the supporting base, and a metal layer or a redistribution layer formed directly on the separation layer on the side opposite the supporting base. The separation layer is a layer that is altered by irradiation of light from the supporting base side, thereby enabling the supporting base to be separated from the laminate. The separation layer is a layer containing a light absorbing resin, or a layer containing a non-light absorbing resin and a light absorbing agent.

[0014] The laminate according to this embodiment is formed by stacking a support base, a separation layer, and a metal layer or a rewiring layer in this order. The metal layer or the rewiring layer is formed directly on the separation layer. "Formed directly on the separation layer" means that the metal layer or rewiring layer is in contact with the separation layer without any other layers, such as an adhesive layer, being present between the metal layer or rewiring layer and the separation layer.

[0015] Fig. 1 is a diagram showing one embodiment of a laminate, and Fig. 2 is a diagram showing another embodiment of a laminate. The laminate 10 shown in FIG. 1 is formed by stacking, in this order, a separation layer 12, a metal layer 14, a redistribution layer 16, and a sealing material layer 18 that seals the substrate on a supporting base 11. The laminate 20 shown in FIG. 2 is formed by laminating, in this order, a separation layer 22, a metal layer 24, a sealing material layer 28 that seals the substrate, and a rewiring layer 26 on a supporting base 21.

[0016] <Support base> The supporting base in the embodiment has a property of transmitting light. The supporting base is a member that supports the substrate, and is bonded to the substrate via a separation layer. Therefore, the supporting base preferably has a strength required to prevent damage or deformation of the substrate during thinning of the sealing body, transportation of the substrate, mounting on the substrate, etc. In addition, the supporting base preferably transmits light of a wavelength that can alter the separation layer. The material of the support base may be, for example, glass, silicon, acrylic resin, etc. The shape of the support base may be, for example, rectangular, circular, etc., but is not limited thereto. Furthermore, as the supporting base, in order to achieve higher density integration and improve production efficiency, a supporting base having a larger circular shape, or a large panel having a rectangular shape when viewed from above, can also be used.

[0017] <Separation layer> The separation layer in the embodiment is a layer that is altered by irradiation with light from the supporting substrate side, thereby enabling the supporting substrate to be separated from the laminate. The separation layer in the embodiment is a layer containing a light absorbing resin, or a layer containing a resin that does not have light absorbing properties and a light absorbent. The separation layer may be a layer containing a material that does not have a structure that absorbs light, as long as the essential properties are not impaired, but from the viewpoint of photoreactivity and separation, it is preferable that the separation layer is formed only from a material that absorbs light. The material (composition) constituting the separation layer will be described later.

[0018] The term "alteration" of the separation layer refers to a phenomenon in which the separation layer is in a state where it can be destroyed by an external force, or where the adhesive strength between the separation layer and a layer in contact with it is reduced. The separation layer becomes brittle by absorbing light, and loses the strength or adhesiveness it had before it was irradiated with light. The alteration of the separation layer occurs when the energy of the absorbed light causes decomposition, a change in configuration, or dissociation of functional groups, etc.

[0019] The thickness of the separation layer is, for example, preferably in the range of 0.05 μm to 50 μm, and more preferably in the range of 0.3 μm to 10 μm. If the thickness of the separation layer is within the range of 0.05 μm or more and 50 μm or less, the desired alteration can be caused in the separation layer by short-time light irradiation and low-energy light irradiation. Moreover, from the viewpoint of productivity, it is particularly preferable that the thickness of the separation layer is within the range of 1 μm or less.

[0020] <Metal layer or rewiring layer> Examples of the metal layer include a layer mainly made of metal Ti and a layer mainly made of Cu, and each layer may further contain other metals, etc. The layer mainly made of Cu may be a seed layer for forming the wiring of the rewiring layer by a plating method. The metal layer can be formed by, for example, a sputtering method, and has a thickness in the range of, for example, 10 nm to 1000 nm.

[0021] The redistribution layer may be, for example, an insulating layer formed of a dielectric (such as silicon oxide (SiOx), photosensitive resin such as photosensitive epoxy, etc.), in which wiring is formed of a conductor (such as metals such as aluminum, copper, titanium, nickel, gold, silver, etc., and alloys such as silver-tin alloy).

[0022] <Others> The laminate according to this embodiment may further include layers other than the supporting base, the separating layer, the metal layer, and the rewiring layer (other layers). The laminates 10, 20 in the embodiments further include encapsulant layers 18, 28 that encapsulate the substrates. The substrate, while supported by a supporting base, is subjected to processes such as thinning, mounting, etc. Structures such as integrated circuits and metal bumps are mounted on the substrate. The substrate is typically a silicon wafer substrate, but is not limited thereto, and may be a ceramic substrate, a thin film substrate, a flexible substrate, or the like.

[0023] The laminate according to this aspect is not limited to the above-mentioned embodiment, and may be, for example, a laminate 10 shown in Fig. 1 that does not include the metal layer 14, that is, a laminate in which a separation layer 12, a redistribution layer 16, and a sealing material layer 18 that seals the substrate are stacked in this order on a support base 11. Also, for example, a laminate 20 shown in Fig. 2 may be a laminate in which bumps are formed on the redistribution layer 26 or an element is mounted on the redistribution layer 26.

[0024] In addition, as another embodiment of the laminate, an additional layer may be provided between the support base and the separation layer. In this case, the additional layer may be made of a material that transmits light. This allows a layer that imparts desirable properties to the laminate to be added as appropriate without preventing the light from entering the separation layer. The wavelength of light that can be used varies depending on the type of material that constitutes the separation layer. Therefore, the material that constitutes the additional layer does not need to transmit light of all wavelengths, and can be appropriately selected from materials that transmit light of a wavelength (e.g., 532 nm) that can alter the material that constitutes the separation layer.

[0025] The laminate according to this aspect does not necessarily require a so-called adhesive layer. In the laminate of the above-described embodiment, the supporting base is bonded to the substrate without an adhesive layer. An example of an optional adhesive layer is a layer mainly composed of one or more of a hydrocarbon resin such as a cycloolefin polymer, an acrylic-styrene resin, a maleimide resin, an elastomer resin, or a polysulfone resin. An example of an optional adhesive layer is a layer in which the content of one or more of a hydrocarbon resin such as a cycloolefin polymer, an acrylic-styrene resin, a maleimide resin, an elastomer resin, or a polysulfone resin is 10% by mass or more relative to the total (100% by mass) of the material forming the adhesive layer.

[0026] <Materials (compositions) constituting the separation layer> In the laminate according to the present embodiment, the material (composition) constituting the separation layer is intended to form a separation layer between a light-transmitting supporting base and a metal layer or a redistribution layer, the separation layer being altered by irradiation of light from the supporting base side to enable separation of the supporting base from the laminate. One embodiment of the material (composition) constituting the separation layer contains a resin component (P). The material of this embodiment is a composition containing a light-absorbing resin as the resin component (P), or a composition containing a resin that does not have light absorption properties as the resin component (P) and a light absorber.

[0027] ·Resin component (P) The resin component (P) (hereinafter also referred to as "component (P)") is either a light-absorbing resin or a resin that does not have light-absorbing properties. In this specification, the term "light absorbing resin" refers to a resin that has the property of absorbing light with a wavelength in the range of 190 to 1300 nm. The component (P) imparts to the separation layer the function of enabling the support base to be separated from the laminate, as well as the function of adhering to the support base and the function of adhering to the metal layer or rewiring layer.

[0028] The component (P) is preferably a resin having a 5% weight loss temperature of 250° C. or higher in thermogravimetry, more preferably a resin having a temperature of 280° C. or higher, and even more preferably a resin having a temperature of 300° C. or higher. From the viewpoint of heat resistance, the higher the 5% weight loss temperature, the more preferable, and the upper limit is substantially a resin of 500° C. or lower. When the temperature at which the weight of the component (P) decreases by 5% is equal to or higher than the lower limit of the above-mentioned preferred range, the heat resistance of the separation layer is improved, allowing the metal layer or rewiring layer to be laminated stably.

[0029] The "5% weight loss temperature" of the resin component (P) refers to the temperature measured as follows. Using TG-DTA (thermogravimetry-differential thermal analysis), the sample is heated in a nitrogen atmosphere from 50°C to 500°C at a constant heating rate (10°C / min), and the change in weight of the sample is measured. The temperature at which the remaining weight of the sample is 95% of the initial weight, i.e., the temperature at which a 5% weight loss is observed, is defined as the 5% weight loss temperature.

[0030] The component (P) is preferably a resin having a weight average molecular weight of 300 to 50,000, more preferably 500 to 40,000, and even more preferably 1,000 to 30,000. If the weight average molecular weight of the component (P) is equal to or greater than the lower limit of the preferred range, the heat resistance of the separation layer is improved, allowing the metal layer or the rewiring layer to be stably laminated, whereas if it is equal to or less than the upper limit of the preferred range, the solubility of the composition in a solvent is improved.

[0031] In this specification, the weight average molecular weight of the resin component (P) means the molecular weight calculated as polystyrene as measured by gel permeation chromatography (GPC).

[0032] The component (P) may be a resin having a glass transition point of 0° C. or higher, a resin having a glass transition point of 50° C. or higher, or a resin having a glass transition point of 100° C. or higher. From the viewpoint of heat resistance, the higher the glass transition point, the more preferable, and the upper limit is substantially 300° C. or lower for the resin. When the glass transition point of the component (P) is at least the lower limit of the above-mentioned preferred range, the heat resistance of the separating layer is improved, allowing the metal layer or rewiring layer to be laminated stably.

[0033] The glass transition point of the resin component (P) can be determined by known methods such as dynamic mechanical analysis and differential scanning calorimetry.

[0034] (P1) component The component (P) may be a resin component having a repeating unit represented by the following general formula (p1) (hereinafter also referred to as "component (P1)").

[0035] [ka] [In the formula, L P1 R represents a divalent linking group. P1 represents an organic group.

[0036] In the formula (p1), L P1 The divalent linking group in the formula (I) may contain an aromatic ring, may contain a plurality of kinds of aromatic rings, or may contain a ring structure in which an aromatic ring and an aliphatic ring are condensed. L P1 When the divalent linking group in the formula (I) contains an aromatic ring, the aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. The divalent linking group may contain one aromatic ring or two or more aromatic rings, and preferably contains two or more aromatic rings because this provides better photoreactivity.

[0037] Alternatively, in the formula (p1), L P1 The divalent linking group in L is preferably a divalent linking group containing a hetero atom. p1 Examples of the linking group include linking groups having various skeletons introduced therein in order to impart desired properties. Examples of the skeleton in the "linking group having various skeletons introduced therein" include a naphthalene skeleton, anthracene skeleton, xanthene skeleton, fluorene skeleton, and bisphenol A skeleton.

[0038] L p1 Examples of such bond groups include ether bond groups of bisphenols, ether bond groups of diols, ester bond groups of dicarboxylic acids, Si-O bond groups, and repeating structures of these bond groups.

[0039] Examples of the bisphenols include bisphenol F, bisphenol A, bisphenol Z, biphenol, and polymers thereof. Examples of the diols include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, naphthalenediol (dihydroxynaphthalene), anthracenediol (dihydroxyanthracene), 2,2-bis(4-hydroxyphenyl)propane, and polymers thereof. Examples of the dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid, and terephthalic acid. L p1In the above, the ether linking group of the diol is preferably a linking group having a glycol skeleton. An example of the glycol skeleton is a propylene glycol skeleton.

[0040] Hereinafter, L in the formula (p1) will be described. P1 Preferred specific examples of (divalent linking group) are shown below. In the following formula, * indicates a bond that bonds to a methylene group (CH2). P1 -9) n represents the number of repetitions of the oxypropylene group.

[0041] [ka]

[0042] In the formula (p1), R P1 The organic group in is not particularly limited, and examples thereof include hydrocarbon groups which may have a substituent. R P1 Examples of the hydrocarbon group in include linear or branched alkyl groups, linear or cyclic alkenyl groups, and cyclic hydrocarbon groups.

[0043] R P1 The linear alkyl group in R preferably has 1 to 5 carbon atoms. P1 Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. R P1 The branched alkyl group in R preferably has 3 to 10 carbon atoms, and more preferably has 3 to 5 carbon atoms. P1 Specific examples of the alkyl group include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group.

[0044] R P1 The chain or cyclic alkenyl group in is preferably an alkenyl group having 2 to 10 carbon atoms.

[0045] R P1 The cyclic hydrocarbon group in may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. The monocyclic aliphatic hydrocarbon group is preferably a group in which one hydrogen atom has been removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The aliphatic hydrocarbon group that is a polycyclic group is preferably a group in which one hydrogen atom has been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0046] R P1The aromatic hydrocarbon group in the above is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group); a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (such as biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (such as arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, and 2-naphthylethyl group). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0047] R P1 The aromatic hydrocarbon group in may be a condensed polycyclic aromatic group. The condensed polycyclic aromatic group is a group in which one hydrogen atom is removed from a condensed polycyclic aromatic ring. This condensed polycyclic aromatic ring may be a ring structure in which a plurality of aromatic rings are condensed, or a ring structure in which an aromatic ring and an aliphatic ring are condensed. In the ring structure in which an aromatic ring and an aliphatic ring are condensed, the number of aromatic rings may be multiple, the number of aliphatic rings may be multiple, or there may be one aromatic ring and one aliphatic ring. The number of rings constituting this condensed polycyclic aromatic ring is preferably 2 to 5, more preferably 2 to 3, and even more preferably 3.

[0048] R P1 Examples of the fused polycyclic aromatic group in the above formula include groups in which one hydrogen atom has been removed from a naphthalene ring, an azulene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, a chrysene ring, a triphenylene ring, a perylene ring, an anthraquinone ring, or a naphthoquinone ring. Among these, groups in which one hydrogen atom has been removed from an anthraquinone ring or a naphthoquinone ring are preferred, and groups in which one hydrogen atom has been removed from an anthraquinone ring are more preferred.

[0049] The above R P1 When the hydrocarbon group represented by the formula (I) is substituted, examples of the substituent include a hydroxy group, a carboxy group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, etc.), an alkoxy group (a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc.), an alkyloxycarbonyl group, etc. R P1 The hydrocarbon group represented by the following formula may have an ether bond in the middle of the hydrocarbon chain.

[0050] Specific examples of the repeating unit represented by formula (p1) are shown below, but the repeating unit is not limited to these.

[0051] [ka]

[0052] [ka]

[0053] [ka]

[0054] [ka]

[0055] The component (P1) has a film-forming ability and preferably has a molecular weight of at least 1000. The film-forming ability is improved by the molecular weight of the component (P1) being at least 1000. The molecular weight of the component (P1) is more preferably 1000 to 30000, further preferably 1500 to 25000, particularly preferably 1500 to 20000, and most preferably 2000 to 15000. By ensuring that the molecular weight of the component (P1) is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the material (composition) constituting the separation layer in a solvent is increased. The molecular weight of the resin component is determined by polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC).

[0056] As the component (P1), for example, the GSP series (manufactured by Gun-ei Chemical Industry Co., Ltd.) with the trade names GSP-01, GSP-02, GSP-03, GSP-106, GSP-112, GSP-113, GSP-117, and GSP-119 can be used.

[0057] Furthermore, as the component (P1), a resin produced by reacting an aminophenol, an aminonaphthol, or an aniline with a compound 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, 5-amino-2-methylphenol, etc. Examples of aminonaphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, 5-amino-1-naphthol, etc. Examples of compounds having two epoxy groups in one molecule include bisphenol-type epoxy resins with trade names of EPICLON850, EPICLON830 (manufactured by DIC Corporation), jERYX-4000 (manufactured by Mitsubishi Chemical Corporation), and the like; diol-type epoxy resins such as DENACOL EX-211, DENACOL EX-212, DENACOL EX-810, DENACOL EX-830, DENACOL EX-911, DENACOL EX-920, DENACOL EX-930 (manufactured by Nagase ChemteX Corporation); dicarboxylate-type epoxy resins such as DENACOL EX-711, DENACOL EX-721 (manufactured by Nagase ChemteX Corporation), jER191P (manufactured by Mitsubishi Chemical Corporation); and silicone-type epoxy resins such as X-22-163, KF-105 (manufactured by Shin-Etsu Chemical Co., Ltd.). The heat treatment temperature during this reaction is preferably 60°C or higher and 250°C or lower, and more preferably 80°C or higher and 180°C or lower.

[0058] The component (P1) may be used alone or in combination of two or more types.

[0059] ·(P2) component The component (P) may be a resin component other than the component (P1) (hereinafter, also referred to as "component (P2)"). Examples of the component (P2) include novolac-type phenolic resins, epoxy resins, maleimide resins, benzoxazine resins, resol-type phenolic resins, hydroxystyrene resins, hydroxyphenylsilsesquioxane resins, hydroxybenzylsilsesquioxane resins, and acrylic resins containing a phenol skeleton. Among these, novolac-type phenolic resins, epoxy resins, and maleimide resins are preferably used.

[0060] Novolac phenolic resin Suitable examples of novolac-type phenolic resins include resins having a structural unit represented by the following general formula (anv1).

[0061] [ka] [In the formula, R a22 and R a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.]

[0062] In the above formula (anv1), R a22 , R a23 The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched-chain, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the straight-chain or branched-chain alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclobutyl group, and a cyclopentyl group. R a22 , R a23 The halogen atom is preferably a chlorine atom or a bromine atom. Among them, R a22 , R a23 are each preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a linear alkyl group, and further preferably a hydrogen atom or a methyl group; a22 is a methyl group and R a23 is particularly preferably a hydrogen atom. That is, a preferred novolac type phenolic resin is a cresol novolac type phenolic resin.

[0063] Epoxy resin The epoxy resin may be a resin having a sufficient number of epoxy groups in one molecule to form a membrane for the separation layer. A preferred epoxy resin may be, for example, a resin represented by the following general formula (anv0).

[0064] [ka] [In formula (anv0), R p1 and R p2are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. p1 may be the same or different. p2 may be the same or different. n1 is an integer of 1 to 5. R EP is an epoxy group-containing group. EP may be the same or different.

[0065] In the above formula (anv0), R p1 , R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group, and examples of the cyclic alkyl group include a cyclobutyl group, and a cyclopentyl group. Among them, R p1 , R p2 As the alkyl group, a hydrogen atom or a linear or branched alkyl group is preferable, a hydrogen atom or a linear alkyl group is more preferable, and a hydrogen atom or a methyl group is particularly preferable. In the formula (anv0), multiple R p1 may be the same or different. p2 may be the same or different from each other.

[0066] In formula (anv0), n1 is an integer of 1 to 5, preferably 2 or 3, and more preferably 2.

[0067] In formula (anv0), R EP is an epoxy group-containing group. R EP The epoxy group-containing group is not particularly limited, and examples thereof include a group consisting of only epoxy groups; a group consisting of only alicyclic epoxy groups; and a group having an epoxy group or an alicyclic epoxy group and a divalent linking group. The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, is a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group that is the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. The hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable that the epoxy group or the alicyclic epoxy group is linked via the divalent linking group bonded to an oxygen atom (—O—) in the formula.

[0068] Here, the divalent linking group is not particularly limited, but suitable examples include a divalent hydrocarbon group which may have a substituent, and a divalent linking group containing a hetero atom.

[0069] Regarding the optionally substituted divalent hydrocarbon group: Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group in the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specifically, the aliphatic hydrocarbon group may be a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0070] The linear aliphatic hydrocarbon group preferably has a carbon number of 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], and the like. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, even more preferably 2 to 4 carbon atoms, and most preferably 2 or 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0071] Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is present in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same as those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms are removed from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group in which two hydrogen atoms have been removed from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, specific examples of which include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0072] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n+2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group in which two hydrogen atoms have been removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) has been substituted with an alkylene group (e.g., a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0073] The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group as the divalent hydrocarbon group may or may not have a substituent, which may include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0074] The alicyclic hydrocarbon group in the aliphatic hydrocarbon group containing a ring in the structure as the divalent hydrocarbon group may or may not have a substituent, such as an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, or a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include the alkyl groups in which some or all of the hydrogen atoms of the alkyl groups are substituted with the halogen atoms. In the alicyclic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom. Preferred examples of the substituent containing a heteroatom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0075] In the aromatic hydrocarbon group as a divalent hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the alicyclic hydrocarbon group.

[0076] Regarding divalent linking groups containing heteroatoms: The heteroatom in the divalent linking group containing a heteroatom is an atom other than a carbon atom or a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

[0077] In the divalent linking group containing a hetero atom, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H may be substituted by a substituent such as an alkyl group or an acyl group); -S-, -S(=O)2-, -S(=O)2-O-, and the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 , -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. Formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -or-Y 21 -OC(=O)-Y 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include the same ones as the "divalent hydrocarbon group which may have a substituent" listed above in the description of the divalent linking group. Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0078] Among them, R EP As the epoxy group-containing group in the formula (I), a glycidyl group is preferred.

[0079] Maleimide resin The maleimide resin may be a resin having a five-membered ring structure that can be opened by hydrolysis to produce an amide bond and a carboxyl group. A preferred maleimide resin is, for example, a resin represented by the following general formula (z-1).

[0080] [ka] [In the formula, R 1 and R 2 R each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Z 00 R represents a divalent organic group containing a linear, branched or cyclic aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. Z 01 and R Z 02 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. n1 and n2 each independently represent 0 or 1.]

[0081] In the formula (z-1), R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. The alkyl group having 1 to 5 carbon atoms is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group and an ethyl group are preferable, and a methyl group is more preferable.

[0082] In the formula (z-1), R Z 00 represents a divalent organic group containing a linear, branched or cyclic aliphatic hydrocarbon group and / or an aromatic hydrocarbon group. R Z 00 The aliphatic hydrocarbon group in may be saturated or unsaturated, and is preferably saturated. R Z 00 In the linear aliphatic hydrocarbon group, the carbon number is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As the straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferable, and specific examples thereof include a methylene group [-CH2-], an ethylene group [-(CH2)2-], a trimethylene group [-(CH2)3-], a tetramethylene group [-(CH2)4-], a pentamethylene group [-(CH2)5-], etc. R Z 00 In the above, the branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, further preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferable, and specific examples thereof include alkyl alkylene groups such as alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, etc.; alkyl ethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, -C(CH2CH3)2-CH2-, etc.; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

[0083] R Z 00 The linear or branched aliphatic hydrocarbon group in the formula (I) may or may not have a substituent, and examples of the substituent include a fluorine atom, a fluorinated alkyl group having 1 to 5 carbon atoms and substituted with a fluorine atom, and a carbonyl group.

[0084] R Z 00In the above, examples of the cyclic aliphatic hydrocarbon group include an alicyclic hydrocarbon group (a group in which two hydrogen atoms have been removed from an aliphatic hydrocarbon ring), a group in which an alicyclic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group, etc. Examples of such linear or branched aliphatic hydrocarbon groups include the same as the linear aliphatic hydrocarbon groups or the branched aliphatic hydrocarbon groups described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably has 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, specifically cycloalkane preferably has 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0085] R Z 00 The cyclic aliphatic hydrocarbon group in may or may not have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and most preferably a methoxy group or an ethoxy group. Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent include the alkyl groups in which some or all of the hydrogen atoms of the alkyl groups are substituted with the halogen atoms. In the cyclic aliphatic hydrocarbon group, some of the carbon atoms constituting the ring structure may be substituted with a substituent containing a heteroatom, and the heteroatom-containing substituent is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0086] R Z 00 The aromatic hydrocarbon group in the formula (I) is a hydrocarbon group having an aromatic ring. Such an aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this carbon number does not include the number of carbon atoms in the substituent. Specific examples of the aromatic ring contained in the aromatic hydrocarbon group include aromatic hydrocarbon rings such as benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is substituted with a heteroatom, etc. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic hydrocarbon group include a group in which two hydrogen atoms have been removed from the aromatic hydrocarbon ring (arylene group); a group in which one hydrogen atom of a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring (aryl group) has been substituted with an alkylene group (for example, a group in which one hydrogen atom has been further removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, or a 2-naphthylethyl group). The number of carbon atoms in the alkylene group (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0087] The aromatic hydrocarbon group may have a hydrogen atom substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, and a hydroxyl group. The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, or a tert-butyl group. Examples of the alkoxy group, halogen atom and halogenated alkyl group as the substituent include those exemplified as the substituent substituting a hydrogen atom of the cyclic aliphatic hydrocarbon group.

[0088] R Z 00 The organic group in may have a divalent linking group containing a hetero atom. Preferable examples of such a divalent linking group containing a hetero atom include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O)2-, -S(=O)2-O-, and a group represented by the general formula -Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -, wherein Y 21 and Y 22 each independently represents a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m″ is an integer of 0 to 3. When the divalent linking group containing a hetero atom is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H may be substituted with a substituent such as an alkyl group, acyl, etc. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5 carbon atoms. General formula-Y 21 -OY 22 -, -Y 21 -O-, -Y 21 -C(=O)-O-, -C(=O)-OY 21 -, -[Y 21 -C(=O)-O] m” -Y 22 -, -Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -Medium, Y 21 and Y 22 are each independently a divalent hydrocarbon group which may have a substituent. The divalent hydrocarbon group may be any of the above-mentioned R Z 00 Examples of the linear, branched or cyclic aliphatic hydrocarbon group and aromatic hydrocarbon group in the above formula (1) are the same as those in the above formula (1). Y 21 As the alkyl group, a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or ethylene group is particularly preferable. Y 22 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula − [Y 21 -C(=O)-O] m” -Y 22In the group represented by -, m" is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 The group represented by the formula -Y 21 -C(=O)-OY 22 Particularly preferred is a group represented by the formula -(CH2) a’ -C(=O)-O-(CH2) b’ In the formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, still more preferably 1 or 2, and most preferably 1.

[0089] R Z 00 is preferably a linear or branched alkylene group or a fluorinated alkyl group, an aromatic hydrocarbon group, a combination of a linear or branched alkylene group or a fluorinated alkyl group with an aromatic hydrocarbon group, or a combination of one or more selected from the group consisting of a linear or branched alkylene group or a fluorinated alkyl group, and an aromatic hydrocarbon group with one or more selected from the group consisting of -O-, -C(=O)-NH-, -S-, and -S(=O)-.

[0090] Below, R Z 00 Preferable specific examples are as follows: In the formula, "*" represents a bond bonded to N (nitrogen atom) in formula (z-1).

[0091] [ka]

[0092] [ka]

[0093] [ka]

[0094] [ka] [Formula(R Z 00 -38) medium, n z is an integer between 1 and 10.

[0095] Among the above examples, R Z 00 As the formula (R Z 00 -4), formula (R Z 00 -37) or formula (R Z 00 -38) is preferred.

[0096] In the formula (z-1), R Z 01 and R Z 02 each independently represents an alkyl group having 1 to 5 carbon atoms or an alkoxy group having 1 to 5 carbon atoms. As the alkyl group having 1 to 5 carbon atoms, a linear or branched alkyl group having 1 to 5 carbon atoms is preferred, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. A methyl group or an ethyl group is preferred, and a methyl group is more preferred. As the alkoxy group having 1 to 5 carbon atoms, a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, and a tert-butoxy group are preferred, and a methoxy group or an ethoxy group is more preferred.

[0097] In the above formula (z-1), n1 and n2 each independently represent 0 or 1, and preferably represent 0.

[0098] Preferred specific examples of the maleimide resin are given below.

[0099] [ka]

[0100] The maleimide resin may be used alone or in combination of two or more kinds. Among the above, as the maleimide resin, the compounds represented by the chemical formula (z-11), the compounds represented by the chemical formula (z-12), and the compounds represented by the chemical formula (z-13) are preferred because they are more likely to achieve the effects of the present invention. Among these, the compounds represented by the chemical formula (z-11) and the compounds represented by the chemical formula (z-12) are more preferred, and the compounds represented by the chemical formula (z-12) are particularly preferred.

[0101] The resin component (P) contained in the material (composition) constituting the separation layer is preferably at least one selected from the group consisting of a resin component (component (P1)) having a repeating unit represented by the above-mentioned general formula (p1), a novolac-type phenolic resin, an epoxy resin, and a maleimide resin. Alternatively, the resin component (P) contained in the material (composition) constituting the separation layer is preferably at least one selected from the group consisting of a resin component (component (P1)) having a repeating unit represented by the above-mentioned general formula (p1), a cresol novolac type phenolic resin having a structural unit represented by the general formula (anv1), an epoxy resin represented by the general formula (anv0), and a maleimide resin represented by the general formula (z-1).

[0102] Light absorbing resin The light absorbing resin is not particularly limited as long as it has the property of absorbing light in the wavelength range of 190 to 1300 nm. The light absorbing resin may be one that changes to a structure that absorbs light in the wavelength range of 190 to 1300 nm when cured (for example, at 200 to 300° C.). A preferred light absorbing resin is a resin that absorbs light with a wavelength of 532 nm. Such a light absorbing resin is one that changes in quality when the resin itself absorbs light. In the resin component (P) contained in the material (composition) constituting the separation layer, the light absorbing resin is preferably a resin containing an aromatic ring or a condensed polycyclic skeleton in the main chain or side chain. From the viewpoint of easily improving the process heat resistance, a resin containing a condensed polycyclic skeleton in the main chain or side chain is preferable. As the condensed polycyclic skeleton, a condensed ring structure of an aromatic ring and an aromatic ring, or a condensed ring structure of an aromatic ring and an aliphatic ring is preferable. As such a light absorbing resin, for example, a resin component (component (P1)) having a repeating unit represented by the above general formula (p1) is preferable.

[0103] Resin that does not absorb light In the material (composition) constituting the separation layer in this embodiment, the resin that does not have light absorbing properties is altered by the action of the light absorbing agent used in combination, which absorbs light. In the resin component (P) contained in the material (composition) constituting the separation layer, for example, as a resin that does not absorb laser light with a specific wavelength of 308 nm, 355 nm, or 532 nm, at least one selected from the group consisting of the above-mentioned novolac-type phenolic resin, epoxy resin, and maleimide resin is preferable. Suitable examples of the resin that does not absorb laser light of the specific wavelength of 308 nm, 355 nm, or 532 nm include at least one selected from the group consisting of a cresol novolac phenolic resin having a structural unit represented by general formula (anv1), an epoxy resin represented by general formula (anv0), and a maleimide resin represented by general formula (z-1).

[0104] In the material (composition) constituting the separation layer in this embodiment, the resin component (P) may be used alone or in combination of two or more kinds. The content of the resin component (P) in the material (composition) constituting the separation layer is preferably 1 to 100 mass%, more preferably 1 to 70 mass%, and even more preferably 5 to 50 mass%, relative to the total mass (100 mass%) of the composition. The content of the resin component (P) in the material (composition) constituting the separation layer is preferably 30 mass% or more, more preferably 30 to 100 mass%, and even more preferably 50 to 100 mass%, relative to the total mass (100 mass%) of the solid contents excluding the solvent (organic solvent component, water) of the composition. When the content of the resin component (P) is equal to or more than the lower limit of the above-mentioned preferred range, the photoreactivity of the separation layer is more likely to be increased. In addition, the adhesion is also more likely to be increased. On the other hand, when the content is equal to or less than the upper limit of the above-mentioned preferred range, it is easier to achieve a balance with other components.

[0105] Light absorber The light absorbent is not particularly limited as long as it is a substance that has light absorbing ability. The light absorbent can be one that can absorb light of the wavelength depending on the wavelength of light irradiated when separating the support base from the laminate. By containing the light absorbent, the separation layer can be altered by being irradiated with light from the support base side. For example, the light absorbent can be one capable of absorbing light in a wavelength range of 300 to 800 nm. The light absorbent can be one capable of absorbing light in a wavelength range of 400 to 700 nm, more preferably one capable of absorbing light in a wavelength range of 450 to 600 nm, and even more preferably one capable of absorbing light in a wavelength range of 500 to 550 nm. Examples of the light absorbing agent include pigments and dyes.

[0106] Pigments The pigment may be an organic pigment or an inorganic pigment. The pigment may be either a black pigment or a color pigment.

[0107] Examples of black organic pigments include perylene black (perylene-based black pigments), cyanine black, aniline black, and lactam black. Examples of black inorganic pigments include carbon black (lamp black, acetylene black, thermal black, channel black, furnace black, etc.), chromium oxide, iron oxide, titanium black, titanium oxynitride, titanium nitride, strontium titanate, chromium oxide, and ceria.

[0108] Examples of color pigments include compounds classified as pigments in the Color Index (CI; published by The Society of Dyers and Colourists), specifically, compounds having the following Color Index (CI) numbers:

[0109] CI Pigment Yellow 1 (hereinafter referred to as "CI Pigment Yellow" in the same manner, only the numbers will be stated), 3, 11, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 55, 60, 61, 65, 71, 73, 74, 81, 83, 86, 93, 95, 97, 98, 99, 100, 101, 104 , 106, 108, 109, 110, 113, 114, 116, 117, 119, 120, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 166, 167, 168, 175, 180, 185; CI Pigment Orange 1 (hereinafter referred to as "CI Pigment Orange" in the same way, only the numbers will be stated), 5, 13, 14, 16, 17, 24, 34, 36, 38, 40, 43, 46, 49, 51, 55, 59, 61, 63, 64, 71, 73; CI Pigment Violet 1 (hereinafter, "CI Pigment Violet" will be referred to as the same, and only the numbers will be stated), 19, 23, 29, 30, 32, 36, 37, 38, 39, 40, 50; CI Pigment Red 1 (hereinafter, "CI Pigment Red" will be the same, and only the numbers will be listed), 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 19, 21, 22, 23, 30, 31, 32, 37, 38, 40, 41, 42, 48:1, 48:2, 48:3, 48:4, 49:1, 49:2, 50:1, 52:1, 53:1, 57, 57:1, 57:2, 58:2, 58:4, 60:1, 63:1, 63:2, 64:1, 81:1, 83, 88, 90:1, 97, 101, 102, 104, 105, 106, 108, 112, 113, 114, 122, 123, 144, 146, 149, 150, 151, 155, 166, 168, 170, 171, 172, 174, 175, 176, 177, 178, 179, 180, 185, 187, 188, 190, 192, 193, 194, 202, 206, 207, 208, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 242, 243, 245, 254, 255, 264, 265; CI Pigment Blue 1 (hereinafter referred to as "CI Pigment Blue" in the same way, only the numbers will be stated), 2, 15, 15:3, 15:4, 15:6, 16, 22, 60, 64, 66; CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 37; CI Pigment Brown 23, CI Pigment Brown 25, CI Pigment Brown 26, CI Pigment Brown 28; CI Pigment Black 1, Pigment Black 7.

[0110] The particle size of the pigment can be appropriately set, but for example, the volume average particle size is 10 nm or more and 1000 nm or less, preferably 10 nm or more and 500 nm or less, and more preferably 10 nm or more and 300 nm or less. The volume average particle size can be determined by a dynamic light scattering method.

[0111] The pigment may be used alone or in combination of two or more kinds. In addition, a plurality of pigments that absorb light in different wavelength ranges may be used in combination, for example, a black pigment may be used in combination with one or more color pigments.

[0112] ··dye Examples of dyes include azo dyes (monoazo and polyazo dyes, metal complex azo dyes, pyrazolone azo dyes, stilbene azo dyes, thiazole azo dyes), anthraquinone dyes (anthraquinone derivatives, anthrone derivatives), indigoid dyes (indigoid derivatives, thioindigoid derivatives), phthalocyanine dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes), quinoneimine dyes (azine dyes, oxazine dyes, thiazine dyes), methine dyes (cyanine dyes, azomethine dyes), quinoline dyes, nitroso dyes, benzoquinone and naphthoquinone dyes, naphthalimide dyes, and perinone dyes.

[0113] The dye may be a commercially available dye, for example, PC-5857 (manufactured by Orient Industries Co., Ltd.).

[0114] The dye may be used alone or in combination of two or more kinds. Also, a plurality of dyes that absorb light in different wavelength ranges may be used in combination.

[0115] In the material (composition) constituting the separation layer of this embodiment, the light absorbing agent may be used alone or in combination of two or more. Among the light absorbing agents, it is preferable to use a black inorganic pigment, and it is more preferable to use carbon black. The content of the light absorber in the material (composition) constituting the separation layer is preferably 0.1 to 30 mass %, more preferably 0.5 to 20 mass %, and even more preferably 1 to 10 mass %, relative to the total mass (100 mass %) of the composition. Alternatively, the content of the light absorbent in the material (composition) constituting the separation layer is preferably 1 to 70 parts by mass, more preferably 1 to 60 parts by mass, and even more preferably 1 to 50 parts by mass, per 100 parts by mass of the resin component (P). When the content of the light absorbent is equal to or greater than the lower limit of the above-mentioned preferred range, the light absorption efficiency in the separation layer is improved, making it easier to alter the separation layer.When the content of the light absorbent is equal to or less than the upper limit of the above-mentioned preferred range, the solubility of the composition in a solvent is improved.

[0116] Other ingredients In this embodiment, the material (composition) constituting the separation layer may contain other components as necessary, in addition to the above-mentioned component (P) and light absorbing agent. Such other components include fluorocarbons, thermal acid generator components, photoacid generator components, photosensitizer components, organic solvent components, surfactants, sensitizers, and the like.

[0117] Fluorocarbon In this embodiment, the material (composition) constituting the separation layer may contain a fluorocarbon. Fluorocarbons absorb light having a wavelength in a specific range depending on the type of fluorocarbon. By irradiating the separation layer with light having a wavelength in the range absorbed by the fluorocarbon, the fluorocarbon can be suitably altered. The fluorocarbon constituting the separation layer can be suitably formed into a film by plasma CVD (chemical vapor deposition).

[0118] Thermal acid generator component In this embodiment, the material (composition) constituting the separation layer may contain a thermal acid generator component (hereinafter also referred to as "component (T)").

[0119] The component (T) can be appropriately selected from known ones and used. The component (T) is preferably one that generates an acid at a temperature equal to or higher than the temperature at which the supporting substrate coated with the material (composition) constituting the separation layer is prebaked, more preferably 110°C or higher, and even more preferably 130°C or higher. Examples of such component (T) include trifluoromethanesulfonate, hexafluorophosphate, perfluorobutanesulfonate, boron trifluoride salt, boron trifluoride ether complex, etc. Preferred examples of the component (T) include compounds consisting of a cation moiety and an anion moiety shown below.

[0120] [ka] [In formula (T-ca-1), R h01 ~R h04 are each independently a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group; R h01 ~R h04 At least one of R is an aryl group. The alkyl group or aryl group may have a substituent. h05 ~R h07 are each independently a group selected from the group consisting of alkyl groups and aryl groups having 1 to 20 carbon atoms, R h05 ~R h07 At least one of the alkyl groups is an aryl group. The alkyl group or the aryl group may have a substituent.]

[0121] Regarding the cationic portion of the (T) component In the above formula (T-ca-1), R h01 ~R h04 The alkyl group in the formula (I) has 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and further preferably a linear or branched alkyl group having 1 to 5 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Of these, a methyl group and an ethyl group are preferred.

[0122] R h01 ~R h04The alkyl group in may have a substituent, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group, etc.

[0123] The alkoxy group as a substituent of the alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group, and further preferably a methoxy group or an ethoxy group. Examples of the halogen atom as a substituent of the alkyl group include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, with a fluorine atom being preferred. Examples of the halogenated alkyl group as the substituent of the alkyl group include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, in which some or all of the hydrogen atoms have been substituted with the above-mentioned halogen atoms. A carbonyl group as a substituent of an alkyl group is a group (>C=O) that replaces a methylene group (-CH2-) that constitutes the alkyl group. Examples of the cyclic group as a substituent of the alkyl group include an aromatic hydrocarbon group and an alicyclic hydrocarbon group (which may be polycyclic or monocyclic). The aromatic hydrocarbon group here is the same as R h01 ~R h04Examples of the aryl group in the above are the same as those in the above. In the alicyclic hydrocarbon group, the monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane. The monocycloalkane is preferably one having 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. In addition, the polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane is preferably one having 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycycloalkane having a polycyclic skeleton of a condensed ring system such as a cyclic group having a steroid skeleton.

[0124] In the above formula (T-ca-1), R h01 ~R h04 The aryl group in the formula (I) is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a part of the carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom. Examples of the heteroatom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. R h01 ~R h04Specific examples of the aryl group in the above include a group in which one hydrogen atom has been removed from the aromatic hydrocarbon ring or aromatic heterocycle; a group in which one hydrogen atom has been removed from an aromatic compound containing two or more aromatic rings (such as biphenyl, fluorene, etc.); and a group in which one hydrogen atom of the aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group (such as arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. Among these, a group in which one hydrogen atom has been removed from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle, or a group in which one hydrogen atom of the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle has been substituted with an alkylene group, is more preferred, and a group in which one hydrogen atom has been removed from the above-mentioned aromatic hydrocarbon ring, or a group in which one hydrogen atom of the above-mentioned aromatic hydrocarbon ring has been substituted with an alkylene group is even more preferred.

[0125] R h01 ~R h04 The aryl group in may have a substituent, for example, an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group, an alkylcarbonyloxy group, and the like.

[0126] The alkyl group as a substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group. The explanations about the alkoxy group, halogen atom, halogenated alkyl group, carbonyl group and cyclic group as the substituent of the aryl group are the same as the explanations about the alkoxy group, halogen atom, halogenated alkyl group, carbonyl group and cyclic group as the substituent of the alkyl group described above. In the alkylcarbonyloxy group as a substituent of an aryl group, the alkyl portion preferably has 1 to 5 carbon atoms, and examples of the alkyl portion include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Among these, a methyl group and an ethyl group are preferable, and a methyl group is more preferable.

[0127] However, in the above formula (T-ca-1), R h01 ~R h04 At least one of the groups is an aryl group which may have a substituent. Specific examples of the cation represented by the formula (T-ca-1) are shown below.

[0128] [ka]

[0129] In the above formula (T-ca-2), R h05 ~R h07 The alkyl group and aryl group in R h01 ~R h04 This is the same as the explanation for the alkyl group and aryl group in the above.

[0130] However, in the above formula (T-ca-2), R h05 ~R h07 At least one of the groups is an aryl group which may have a substituent. Specific examples of the cation represented by the formula (T-ca-2) are shown below.

[0131] [ka]

[0132] Regarding the anion part of the (T) component Examples of the anion moiety of the component (T) include a hexafluorophosphate anion, a trifluoromethanesulfonate anion, a perfluorobutanesulfonate anion, and a tetrakis(pentafluorophenyl)borate anion. Among these, hexafluorophosphate anion, trifluoromethanesulfonate anion, and perfluorobutanesulfonate anion are preferred, and hexafluorophosphate anion and trifluoromethanesulfonate anion are more preferred.

[0133] In the material (composition) constituting the separation layer in this embodiment, examples of the (T) component include trade names such as San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110, SI-110L, SI-145, I-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, and SI-300 (all manufactured by Sanshin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, and CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66 and CP-77 (manufactured by ADEKA Corporation); FC-520 (manufactured by 3M); and 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- 1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CXC-1739, CX C-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60, CXC-2689 (and above, KING Commercially available products such as INDUSTRY) can be used.

[0134] Photoacid generator component In the present embodiment, the material (composition) constituting the separation layer may contain a photoacid generator component. Suitable examples of the photoacid generator component include onium salt-based acid generators such as sulfonium salts.

[0135] In the onium salt acid generator, preferred cationic moieties include a sulfonium cation and an iodonium cation.

[0136] A preferred anion moiety in the onium salt acid generator is tetrakis(pentafluorophenyl)borate ([B(C6F5)4] - );Tetrakis[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - );Difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - );Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - );Tetrakis(difluorophenyl)borate ([B(C6H3F2)4] - In addition, anions represented by the following general formula (b0-2a) are also preferred.

[0137] [ka] [In the formula, R bf05 is a fluorinated alkyl group which may have a substituent. 1 is an integer from 1 to 5.

[0138] In the above formula (b0-2a), R bf05 The fluorinated alkyl group in R preferably has 1 to 10 carbon atoms, more preferably has 1 to 8 carbon atoms, and even more preferably has 1 to 5 carbon atoms. bf05 As the alkyl group, a fluorinated alkyl group having 1 to 5 carbon atoms is preferable, a perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, and a trifluoromethyl group or a pentafluoroethyl group is even more preferable. In the above formula (b0-2a), nb 1 is preferably an integer of 1 to 4, more preferably an integer of 2 to 4, and most preferably 3. nb 1 If is 2 or more, multiple R bf05 may be the same or different from each other.

[0139] Photosensitizer component In this embodiment, the material (composition) constituting the separation layer may contain a photosensitizer component. A suitable example of the photosensitizer component (hereinafter also referred to as "component (C)") is an esterification reaction product (hereinafter also referred to as "component (C1)") between a phenolic hydroxyl group-containing compound represented by the following chemical formula (c1) and a 1,2-naphthoquinone diazide sulfonic acid compound.

[0140] [ka]

[0141] Examples of the 1,2-naphthoquinone diazide sulfonic acid compound include a 1,2-naphthoquinone diazide-5-sulfonyl compound and a 1,2-naphthoquinone diazide-4-sulfonyl compound, and the like, with the 1,2-naphthoquinone diazide-5-sulfonyl compound being preferred.

[0142] Specific examples of suitable components (C1) are given below.

[0143] [ka] [In formula (c1-1), D 1 ~D 4 each independently represents a hydrogen atom or a 1,2-naphthoquinonediazide-5-sulfonyl group. D 1 ~D 4 At least one of the groups represents a 1,2-naphthoquinonediazide-5-sulfonyl group.

[0144] The esterification rate of the (C1) component is preferably from 50 to 70%, and more preferably from 55 to 65%. The "esterification rate" here means, for the compound represented by formula (c1-1), D 1 ~D 4 is substituted with 1,2-naphthoquinonediazide-5-sulfonyl groups. The component (C1) is also preferred because it is very inexpensive and yet can achieve high sensitivity.

[0145] As the component (C), a photosensitizer component other than the component (C1) (hereinafter also referred to as "component (C2)") can be used. A suitable example of the (C2) component is an esterification reaction product of a phenolic hydroxyl group-containing compound ((C2-Phe) component) shown below with a 1,2-naphthoquinone diazide sulfonic acid compound (preferably a 1,2-naphthoquinone diazide-5-sulfonyl compound or a 1,2-naphthoquinone diazide-4-sulfonyl compound).

[0146] Examples of the (c2-phe) component include 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-hydroxyphenylmethane, Bis(4-hydroxy-2,5-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-dihydroxy Phenylmethane, 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)-3,4-dihydroxyphenylmethane, bis(2 ,3,5-trimethyl-4-hydroxyphenyl)-2-hydroxyphenylmethane, 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-di(4-hydroxyphenyl)cyclohexane, 2,4-bis[1-(4-hydroxyphenyl)isopropyl]-5-hydroxyphenol, and the like.

[0147] Organic solvent components In this embodiment, the material (composition) constituting the separation layer may contain an organic solvent component (hereinafter also referred to as "component (S)") in order to adjust the coating workability and the like. Examples of the (S) component include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, norbornane, pinane, thujane, carane, longifolene, geraniol, nerol, Terpene solvents such as linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinen-1-ol, terpinen-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, and dipentene; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl ketones such as isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol; compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate and dipropylene glycol monoacetate, derivatives of polyhydric alcohols such as monoalkyl ethers of the polyhydric alcohols or compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether and monobutyl ether, or compounds having an ether bond such as monophenyl ether (among these, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, and esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate;Examples of aromatic organic solvents include anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, and butyl phenyl ether. In this embodiment, the material (composition) constituting the separation layer may contain one type of component (S), or two or more types of components.

[0148] In the material (composition) constituting the separation layer of this embodiment, the amount of the (S) component used is not particularly limited, and is appropriately set according to the coating film thickness and coatability at a concentration that can be applied to a support substrate, etc. Preferably, the (S) component is used so that the total amount of the (P) component in the material (composition) constituting the separation layer is preferably 70 mass % or less, more preferably in the range of 5 to 50 mass %, and even more preferably in the range of 10 to 50 mass %, based on the total mass (100 mass %) of the composition.

[0149] Surfactants In the present embodiment, the material (composition) constituting the separation layer may contain a surfactant in order to adjust the coating workability, etc. Examples of the surfactant include silicone-based surfactants and fluorine-based surfactants.

[0150] In this embodiment, examples of the material (composition) constituting the separation layer include a composition containing a light-absorbing resin and an organic solvent component; and a composition containing a non-light-absorbing resin, a light absorber, and an organic solvent component. Alternatively, in this embodiment, examples of the material (composition) constituting the separation layer include a composition containing a resin having an aromatic ring or a fused polycyclic skeleton in its main chain or side chain, and an organic solvent component; a composition containing a resin having an aromatic ring or a fused polycyclic skeleton in its main chain or side chain, a light absorber, and an organic solvent component; a composition containing a resin component (component (P1)) having a repeating unit represented by the above-mentioned general formula (p1), and an organic solvent component; and a composition containing component (P1), a light absorber, and an organic solvent component. Alternatively, in this embodiment, examples of the material (composition) constituting the separation layer include a composition containing at least one selected from the group consisting of the above-mentioned novolac-type phenolic resin, epoxy resin, and maleimide resin, a light absorber, and an organic solvent component; a composition containing a cresol novolac-type phenolic resin having a structural unit represented by the above-mentioned general formula (anv1), a light absorber, and an organic solvent component; a composition containing an epoxy resin represented by the above-mentioned general formula (anv0), a light absorber, and an organic solvent component; and a composition containing a maleimide resin represented by the above-mentioned general formula (z-1), a light absorber, and an organic solvent component.

[0151] As described above, the laminates 10 and 20 of the present embodiment include the specific separation layers 12 and 22, and a metal layer or a rewiring layer is formed directly on the separation layers 12 and 22. The specific separation layers 12 and 22 contain a light absorbing resin, or a resin that does not absorb light and a light absorbing agent, and are altered by irradiation with light from the support base 11 and 21 side, losing the film strength before irradiation with light and the adhesive strength with adjacent layers, making it possible to separate the support base 11 and 21 from the laminates 10 and 20. Since the laminates 10 and 20 include the specific separation layers 12 and 22, the support bases 11 and 21 can be separated from the laminates 10 and 20 by irradiation with light. In addition, since the laminates 10 and 20 include a metal layer or a rewiring layer without an adhesive layer, no flow deformation occurs due to heating, and the metal sputter layer (metal layer) or the rewiring layer can be stably laminated.

[0152] (Second aspect: Manufacturing method of electronic components) A method for producing an electronic component according to a second aspect of the present invention is a method for producing an electronic component, comprising: a separation step of separating the supporting base from the laminate according to the above-mentioned first aspect by irradiating the separation layer from the supporting base side with light to alter the separation layer, and a removal step of removing the separation layer adhering to the metal layer or redistribution layer after the separation step. The method for producing an electronic component according to the second aspect is preferably exemplified by the following first and second embodiments, each of which will be described with reference to the drawings. In the drawings, components may be shown diagrammatically to make them easier to see, and some components may be shown on different scales.

[0153] First Embodiment One embodiment of the method for manufacturing an electronic component includes a step (1-1) of preparing a laminate, a separation step (1-2) of separating a supporting base from the laminate, and a removal step (1-3) of removing a separation layer adhering to a metal layer or a redistribution layer. FIG. 3A is a diagram illustrating a method for forming a separation layer. FIG. 3B is a diagram showing an example of a laminate prepared in the first embodiment. FIG. 3C is a diagram illustrating an operation for separating the support base from the laminate. FIG. 3D shows the state after the separation step. FIG. 3E illustrates a state after the removing step, showing an example of a semiconductor package (electronic component) manufactured in the first embodiment. In the first embodiment, the laminate 10 has a configuration in which a metal layer 14 is provided directly on a separation layer 12, and a redistribution layer 16 and a sealing material layer 18 are laminated in this order on the metal layer 14.

[0154] [Step (1-1) of preparing a laminate] The step (1-1) includes, for example, an operation of forming a separation layer on a supporting substrate, and an operation of forming a metal layer or a rewiring layer on the separation layer.

[0155] - Forming a separation layer on a support substrate In FIG. 3A, a separation layer 12 is formed on a supporting substrate 11 . The separation layer 12 can be formed by applying the above-mentioned <<material (composition) constituting the separation layer>> to one surface of the support base 11 and curing it.

[0156] Forming a metal layer or a rewiring layer on the separation layer Next, the metal layer 14 and the rewiring layer 16 are formed on the separation layer 12 formed on the support base 11 by using, for example, a sputtering method or a plating method. As described above, the rewiring layer 16 can be fabricated as a wiring layer having an insulating layer and wiring formed in the insulating layer by repeatedly forming an insulating layer, a seed layer, and wiring formed by a dielectric material. As a method for forming the wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resist lithography) or an etching process can be used. By carrying out the operations up to this point, a supporting substrate with a metal thin film is produced.

[0157] In the laminate 10 shown in FIG. 3B, a sealing material layer 18 that seals the substrate is further provided on the redistribution layer 16. The encapsulant layer 18 can be formed by molding using a composition containing, for example, an epoxy resin or a silicone resin. The encapsulant layer 18 here is preferably one that encapsulates all of the substrates below the encapsulant layer 18, rather than encapsulating each individual substrate.

[0158] [Separation step (1-2) of separating the support base from the laminate] In the separation step (1-2), the separation layer is irradiated with light from the supporting base side to alter the properties of the separation layer, thereby separating the supporting base from the laminate. As shown in FIG. 3C, in this step (1-2), separation layer 12 is irradiated with light (arrow) through support base 11, thereby altering separation layer 12.

[0159] Wavelengths that can alter the separation layer 12 include those in the wavelength range of 600 nm or less (for example, 532 nm). The type and wavelength of the light to be irradiated may be appropriately selected depending on the transparency of the support base 11 and the material constituting the separation layer 12. For example, laser light such as a solid laser such as a YAG laser, a ruby ​​laser, a glass laser, a YVO4 laser, an LD laser, or a fiber laser, a liquid laser such as a dye laser, a gas laser such as a CO2 laser, an excimer laser, an Ar laser, or a He-Ne laser, a semiconductor laser, or a free electron laser, or a non-laser light may be used.

[0160] In the case of irradiating with a laser beam, the following conditions can be given as an example of the laser beam irradiation conditions. The average output value of the laser beam is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser beam is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10,000 mm / s or less.

[0161] Next, separation layer 12 is irradiated with light (arrow) to cause it to change in quality, and then supporting base 11 is separated from laminate 10. Fig. 3D shows the state after supporting base 11 has been separated from laminate 10. The operation of separating the supporting base 11 from the laminate 10 may be performed by applying a force in a direction in which the supporting base 11 and the metal layer 14 or the rewiring layer 16 are separated from each other. For example, the supporting base 11 and the metal layer 14 or the rewiring layer 16 can be separated from each other by fixing one of the supporting base 11 side and the metal layer 14 or the rewiring layer 16 side to a stage and lifting the other side while vacuum adsorbing it with a separation plate equipped with an adsorption pad such as a bellows pad. At that time, a fluid may be sprayed into a gap formed between the supporting base 11 and the metal layer 14 or the rewiring layer 16, and the supporting base 11 and the metal layer 14 or the rewiring layer 16 may be separated by the pressure of the sprayed fluid.

[0162] Examples of the fluid to be sprayed include gas, liquid, and a mixed fluid containing gas and liquid, and it is preferable to use a gas, which may be at least one selected from the group consisting of air, dry air, nitrogen, and argon.

[0163] [Removal process (1-3) for removing the separation layer attached to the metal layer or the rewiring layer] In the removal step (1-3), after the separation step (1-2), the separation layer adhering to the metal layer or the rewiring layer is removed. In Fig. 3D, after the separation step (1-2), the separation layer 12 is attached to the metal layer 14. In the main removal step (1-3), the separation layer 12 attached to the metal layer 14 is removed. Methods for removing the separation layer 12 adhering to the metal layer 14 include, for example, a method for removing the residue of the separation layer 12 using a cleaning liquid, or a method for irradiating with plasma. The cleaning liquid preferably contains an organic solvent, and it is preferable to use the organic solvent contained in the separation layer forming composition.

[0164] In FIG. 3E, electronic component 100 having a laminated structure of redistribution layer 16 and encapsulant layer 18 is finally obtained. As described above, according to the method for manufacturing an electronic component of the first embodiment that employs the laminate 10, it is possible to suitably form the encapsulant layer 18 that encapsulates the substrate (wiring layer) on the separation layer 12. The method for producing an electronic component according to the first embodiment may further include, after the above-mentioned removing step (1-3), a step of performing processing such as forming solder balls, dicing, or forming an oxide film.

[0165] <Second embodiment> Another embodiment of the method for manufacturing an electronic component is a manufacturing method including a step (2-1) of preparing a laminate, a separation step (2-2) of separating a supporting base from the laminate, and a removal step (2-3) of removing a separation layer adhering to a metal layer or a redistribution layer. FIG. 4A is a diagram illustrating a method for forming a separation layer. FIG. 4B is a diagram showing an example of a laminate prepared in the second embodiment. FIG. 4C is a diagram illustrating an operation for separating the support base from the laminate. FIG. 4D shows the state after the separation step. FIG. 4E illustrates a state after the removing step, showing an example of a semiconductor package (electronic component) manufactured in the second embodiment. In the second embodiment, the laminate 20 has a metal layer 24 directly on the separation layer 22, and a sealant layer 28 and a rewiring layer 26 are stacked in this order on the metal layer 24. The laminate 20 may have the sealant layer 28 ground to expose a portion of the substrate, and the rewiring layer 26 formed on the exposed substrate.

[0166] [Step (2-1) of preparing a laminate] The step (2-1) includes, for example, an operation of forming a separation layer on a supporting substrate, and an operation of forming a metal layer and a rewiring layer on the separation layer.

[0167] - Forming a separation layer on a support substrate In FIG. 4A, a separation layer 22 is formed on a supporting substrate 21. The separation layer 22 can be formed by applying the above-mentioned <<material (composition) constituting the separation layer>> to one surface of the support base 21 and curing it.

[0168] - Forming a metal layer and a rewiring layer on the separation layer Next, a metal layer 24 is formed on the separation layer 22 formed on the support base 21 by using, for example, a sputtering method or a plating method.

[0169] In the laminate 20 shown in FIG. 4B, a sealant layer 28 that seals the substrate is provided on the metal layer 24, and a redistribution layer 26 is provided on the sealant layer 28. The encapsulant layer 28 can be formed by molding using a composition containing, for example, an epoxy resin or a silicone resin. The encapsulant layer 28 here is preferably one that encapsulates all of the substrates below the encapsulant layer 28, rather than encapsulating each individual substrate.

[0170] As described above, the rewiring layer 26 can be fabricated as a wiring layer having an insulating layer and wiring formed in the insulating layer by repeatedly forming an insulating layer, a seed layer, and wiring formed by a dielectric material. As a method for forming the wiring, for example, a known semiconductor process such as a lithography process such as photolithography (resist lithography) or an etching process can be used.

[0171] [Separation step (2-2) of separating the support base from the laminate] In the separation step (2-2), the separation layer is irradiated with light from the supporting base side to alter the properties of the separation layer, thereby separating the supporting base from the laminate. As shown in FIG. 4C, in this step (2-2), separation layer 22 is irradiated with light (arrow) through support base 21, thereby altering separation layer 22. The method for separating the support base 21 from the laminate 20 may be the same as the operation in the above-mentioned separation step (1-2).

[0172] [Removal process (2-3) for removing the separation layer attached to the metal layer or rewiring layer] In the removal step (2-3), the separation layer adhering to the metal layer after the separation step (2-2) is removed. In Fig. 4D, after the separation step (2-2), the separation layer 22 is attached to the metal layer 24. In the main removal step (2-3), the separation layer 22 attached to the metal layer 24 is removed. The separation layer 22 adhering to the metal layer 24 may be removed in the same manner as in the above-mentioned removing step (1-3).

[0173] In FIG. 4E, electronic component 200 having a laminated structure of encapsulant layer 28 and rewiring layer 26 is finally obtained. As described above, according to the second embodiment of the method for manufacturing an electronic component that employs the laminate 20, it is possible to form the encapsulant layer 28 that encapsulates the substrate (wiring layer) on the separation layer 22, and further to suitably form the rewiring layer 26 on the encapsulant layer 28. In the method for manufacturing an electronic component according to the second embodiment, it is further possible to form bumps or mount elements on the rewiring layer. Mounting elements on the rewiring layer can be performed using, for example, a chip mounter. EXAMPLES

[0174] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0175] <Preparation of separation layer forming composition> The components shown in Table 1 were mixed and dissolved to prepare separation layer-forming compositions (1) to (8).

[0176] [Table 1]

[0177] In Table 1, the abbreviations have the following meanings: The numbers in brackets [ ] indicate the blend amount (parts by mass). Resin components (P)-1: A resin containing a condensed ring in the main chain and having a repeating unit represented by the following chemical formula (p1-9). Glass transition point: 120°C, 5% weight loss temperature: 250°C, weight average molecular weight: 5380 (P)-2: Cresol novolac resin represented by the following chemical formula (p-2). Glass transition point: 160°C, 5% weight loss temperature: 350°C, weight average molecular weight: 13,000 (P)-3: Aminophenol resin having a repeating unit represented by the following chemical formula (p1-13). Glass transition point: 130°C, 5% weight loss temperature: 280°C, weight average molecular weight: 6000 (P)-4: Epoxy resin represented by the following chemical formula (p-4). Glass transition point: 70°C, 5% weight loss temperature: 320°C, weight average molecular weight: 3200 (P)-5: Maleimide resin represented by the following chemical formula (p-5). Glass transition point: 308°C, 5% weight loss temperature: 437°C, weight average molecular weight: 509 (P)-6: Aminophenol resin having a repeating unit represented by the following chemical formula (p1-1). Glass transition point: 120°C, 5% weight loss temperature: 285°C, weight average molecular weight: 11600

[0178] Glass transition temperature measurement The glass transition temperature was measured by DSC. Specifically, the glass transition temperature was determined based on the results of measurement using 1 mg of a sample, which was heated at a rate of 10° C. / min in an air atmosphere.

[0179] Measurement of temperature for 5% weight loss Using TG-DTA (thermogravimetry-differential thermal analysis), the sample was heated in a nitrogen atmosphere from 50°C to 500°C at a constant heating rate (10°C / min) and the weight change of the sample was measured. The temperature at which the remaining weight of the sample was 95% of the initial weight, i.e., the temperature at which a 5% weight loss was observed, was defined as the 5% weight loss temperature.

[0180] Measurement of weight average molecular weight The values ​​were measured by gel permeation chromatography (GPC) and are expressed in terms of polystyrene.

[0181] [ka]

[0182] [ka]

[0183] [ka]

[0184] Light absorber (U)-1: Carbon black Organic solvent components (S)-1: Propylene glycol monomethyl ether acetate

[0185] <Manufacture of Laminate> (Examples 1 to 7, Comparative Example 2) Each of the separation layer-forming compositions (1) to (8) was used to form a film on a glass substrate by spin coating. The coating was heated on a hot plate at 90° C. for 3 minutes and then at 250° C. for 10 minutes to form a separation layer with a thickness of 0.5 μm on the glass substrate.

[0186] Next, a Ti layer (thickness 50 nm) and a Cu-containing seed layer (thickness 300 nm) were formed on the separation layer formed on the glass substrate using a sputtering device, thereby obtaining a supporting base with a metal thin film as a laminate.

[0187] Comparative Example 1 A film was formed on a glass substrate by spin coating using the separation layer forming composition (4). The coating film was heated on a hot plate at 90°C for 3 minutes and then at 250°C for 10 minutes to form a separation layer with a thickness of 0.5 μm on the glass substrate.

[0188] As the adhesive layer-forming composition, TZNR (registered trademark)-A4017 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was used. A film was formed on the separation layer formed on the glass substrate by spin coating using the adhesive layer forming composition. The coating film was heated on a hot plate at 90°C, 160°C, and 220°C for 4 minutes each, to form an adhesive layer with a thickness of 50 μm on the separation layer.

[0189] Next, the adhesive layer formed on the separation layer was heated at 100°C for 5 minutes using a sputtering device to form a Ti layer (thickness 50 nm) and a seed layer (thickness 300 nm) containing Cu, thereby obtaining a supporting base with a metal thin film as a laminate.

[0190] <Evaluation> The obtained laminate was evaluated for laser separability and process heat resistance by the methods described below. The results are shown in Table 2.

[0191] [Laser reactivity] The glass substrate on which a separation layer having a thickness of 0.5 μm was formed using the above-mentioned method was irradiated with a laser beam having a wavelength of 532 nm from the glass substrate side to evaluate the laser reactivity. The laser beam irradiation conditions were set to a frequency of 50 kHz, 6.5 W, a scanning speed of 7200 mm / s, and an irradiation pitch of 160 μm. The evaluation of the laser reactivity was performed by observing the state of traces of the laser light irradiated on the separation layer using a microscope VHX-600 (manufactured by Keyence Corporation) and according to the following evaluation criteria. Evaluation criteria A: The diameter of the impact mark caused by the laser beam was 100 μm or more. C: The diameter of the impact mark caused by the laser beam was less than 100 μm.

[0192] [Process heat resistance] The resulting support substrate with the metal thin film was heated in an inert gas oven at 230° C. for 3 hours under a nitrogen atmosphere. The process heat resistance was evaluated by visually observing the state of peeling between the metal thin film and the glass substrate, according to the following evaluation criteria. Evaluation criteria A: No peeling was observed between the metal thin film and the glass substrate, and the metal thin film was maintained on the glass substrate. B: Although slight peeling was observed between the metal thin film and the glass substrate, the metal thin film was maintained on the glass substrate. C: Significant peeling was observed between the metal thin film and the glass substrate, and the metal thin film could not be held on the glass substrate.

[0193] [Table 2]

[0194] From the results shown in Table 2, it can be confirmed that the supporting base with the metal thin film of Examples 1 to 7 can be separated by irradiation with light, and is a laminate in which the metal layer is held without an adhesive layer.

[0195] In contrast, in the supporting base with metal thin film of Comparative Example 1, which had an adhesive layer, the adhesive layer underwent flow deformation due to heating, and was evaluated as having poor process heat resistance. The supporting base with the metal thin film of Comparative Example 2, which was provided with a separation layer that did not contain a light absorbent, was evaluated as having a poor laser reactivity.

[0196] Comparing Examples 1 to 6 and Example 7, which have different compositions constituting the separation layer, it can be seen that from the viewpoint of process heat resistance, the supporting substrates with metal thin films of Examples 1 to 6 have a metal layer laminated more stably without an adhesive layer than the supporting substrate with metal thin film of Example 7.

[0197] Although the preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Addition, omission, substitution, and other modifications of the configuration are possible without departing from the spirit of the present invention. The present invention is not limited by the above description, but is limited only by the scope of the attached claims. [Explanation of symbols]

[0198] 10,20,50 laminate 11,21,51 Supporting base 12,22,52 separation layer 14,24 metal layer 54 Adhesive layer 16,26 Redistribution layer 56 Substrate 18,28,58 Encapsulant layer 100,200 Electronic Components

Claims

1. A light-transmitting supporting base; A separation layer formed on the supporting substrate; a metal layer or a rewiring layer formed directly on the separation layer on the side opposite to the support base; A laminate comprising: the separation layer is a layer that is altered by irradiation of light from the supporting base side to enable separation of the supporting base from the laminate, The separation layer is a layer containing a light-absorbing resin, or a layer containing a non-light-absorbing resin and a light-absorbing agent.

2. 2. The laminate according to claim 1, wherein the resin contained in the separation layer has a temperature at which it loses 5% weight in thermogravimetry of 250°C or higher.

3. 2. The laminate according to claim 1, wherein the resin contained in the separation layer has a weight average molecular weight of 300 to 50,000.

4. The laminate according to claim 1 , wherein the light absorbing resin is a resin containing an aromatic ring or a condensed polycyclic skeleton in a main chain or a side chain.

5. A separation step of irradiating the separation layer from the supporting base side with light to alter the separation layer of the laminate according to any one of claims 1 to 4, thereby separating the supporting base from the laminate; a removing step of removing the separation layer attached to the metal layer or the rewiring layer after the separating step; The method for manufacturing an electronic component includes the steps of:

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