Separation layer-forming composition and laminate

Abstract

The invention relates to a composition for forming a separation layer and a laminate. The present invention addresses the problem of providing: a composition for forming a separation layer, said composition being capable of forming a separation layer in which a support substrate can be separated from a laminate by irradiation with light and which has improved heat resistance; and a laminate provided with a separation layer formed from the composition. [Solution] The present invention uses a separation layer-forming composition for forming a separation layer (12) in a laminate (10) provided with the separation layer (12) between a first layer and a second layer. The first layer is a support substrate (11) that can transmit light, and the separation layer (12) is a layer that can be denatured by irradiation with light from the support substrate (11) side and separates the support substrate (11) from the laminate (10). The composition for forming the separation layer contains an epoxy resin (P), a light-absorbing agent having an absorption at a wavelength of 300-1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator, and the 1% weight loss temperature of a cured product of the composition for forming the separation layer is 200 DEG C or more.

Description

Technical Field

[0001] This invention relates to compositions for forming separation layers and laminates. Background Technology

[0002] In recent years, there has been a demand for further high integration, thinning, and miniaturization in semiconductor packages (electronic components) that contain semiconductor elements.

[0003] To achieve miniaturization of semiconductor packages, it is important to reduce the thickness of the substrate in the assembled components. However, reducing the thickness of the substrate reduces its strength, making it more susceptible to breakage during the manufacturing of semiconductor packages.

[0004] To address this, a laminate obtained by bonding a support substrate to a substrate, or a laminate obtained by directly forming a wiring layer on the support substrate, is employed. Finally, the support substrate is separated from the laminate to manufacture electronic components.

[0005] For example, a method has been proposed in the past to separate the aforementioned support substrate from a laminate formed by laminating a substrate and a support substrate that allows light to pass through, with a separation layer that can be deformed by irradiation of light in between (for example, see Patent Document 1).

[0006] Existing technical documents Patent documents Patent Document 1: Japanese Patent Application Publication No. 2017-170870 Summary of the Invention

[0007] The problem that the invention aims to solve In the manufacturing of a laminate formed by stacking a support substrate and a substrate with a release layer in between, when metal sputtering is performed on the release layer and then a redistribution layer (RDL) or insulating film is formed, a thermal process is performed on the release layer at a high temperature of 200°C or above for a long period of time, such as more than 3 hours.

[0008] However, due to the effects of this thermal process, there are problems such as the generation of gas from the separation layer, which reduces the yield.

[0009] The present invention was made in view of the above circumstances, and its object is to provide a composition for forming a separation layer and a laminate having a separation layer formed therefrom, wherein the composition for forming a separation layer is capable of forming a separation layer that can be separated from the laminate by light irradiation and whose heat resistance is improved.

[0010] Methods for solving problems To address the aforementioned issues, the present invention employs the following configuration.

[0011] That is, the first aspect of the present invention is a separation layer forming composition, which is a separation layer forming composition for forming the aforementioned separation layer in a laminate having a separation layer between a first layer and a second layer. The aforementioned first layer is a support substrate that allows light to pass through, and the aforementioned separation layer is a layer that can be denatured by irradiation from the aforementioned support substrate side, thereby separating the aforementioned support substrate from the aforementioned laminate. The aforementioned separation layer forming composition contains epoxy resin (P), a light absorber having absorption at a wavelength of 300 nm to 1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator. The 1% weight reduction temperature of the cured product of the aforementioned separation layer forming composition is 200°C or higher.

[0012] The second aspect of the present invention is a laminate, which is a laminate having a separation layer between a first layer and a second layer, wherein the first layer is a support substrate that allows light to pass through, and the separation layer is formed by curing a layer obtained by curing the separation layer forming composition involved in the first aspect.

[0013] Invention Effects According to the present invention, a separation layer forming composition and a laminate having a separation layer formed therefrom can be provided, wherein the separation layer forming composition is capable of forming a separation layer that can be separated from the laminate by light irradiation and has improved heat resistance. Attached Figure Description

[0014] [ Figure 1 [A diagram illustrating one embodiment of the laminate.]

[0015] [ Figure 2 [A diagram illustrating other embodiments of the laminate.]

[0016] [ Figure 3A [Figure 1] illustrates the method for forming the separation layer.

[0017] [ Figure 3B [A diagram showing an example of a laminate prepared in the first embodiment.]

[0018] [ Figure 3C This is a diagram illustrating the operation of separating the support matrix from the laminate.

[0019] [ Figure 3D [This is a diagram showing the state after the separation process.]

[0020] [ Figure 3E This is a diagram showing the state after the removal process and an example of a semiconductor package (electronic component) manufactured in the first embodiment.

[0021] [ Figure 4A [Figure 1] illustrates the method for forming the separation layer.

[0022] [ Figure 4B [A diagram showing an example of a laminate prepared in the second embodiment.]

[0023] [ Figure 4C This is a diagram illustrating the operation of separating the support matrix from the laminate.

[0024] [ Figure 4D [This is a diagram showing the state after the separation process.]

[0025] [ Figure 4E This is a diagram showing the state after the removal process and an example of a semiconductor package (electronic component) manufactured in the second embodiment.

[0026] Explanation of reference numerals in the attached figures 10- and 20-layer stacks 11, 21 Supporting substrate 12, 22 Separation Layer 14, 24 metal layers 16, 26 Rerouting Layers 18, 28 Sealing material layers 100, 200 electronic components Detailed Implementation

[0027] In this specification and claims, "aliphatic" is a relative concept compared to aromatic, and is defined as non-aromatic groups, compounds, etc.

[0028] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0029] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0030] "Halogenated alkyl" is a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0031] "Fluoroalkyl" or "fluoroalkylene" refers to a group obtained by replacing some or all of the hydrogen atoms of an alkyl or alkylene group with fluorine atoms.

[0032] "Structural unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer).

[0033] The description of "may have substituents" or "may have substituents" includes both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH2-) is replaced by a divalent group.

[0034] "Exposure" is a concept that includes exposure to all forms of radiation.

[0035] The term "structural unit derived from styrene" refers to a structural unit formed by the breaking of the olefinic double bonds in styrene. The term "structural unit derived from styrene derivatives" refers to a structural unit formed by the breaking of the olefinic double bonds in styrene derivatives.

[0036] The term "styrene derivatives" refers to compounds obtained by substituting the α-hydrogen atom of styrene with alkyl, haloalkyl, or other substituents, as well as their derivatives. Examples of their derivatives include compounds obtained by replacing the hydrogen atom of the hydroxyl group in styrene where the α-hydrogen atom can be replaced by a substituent with an organic group; and compounds obtained by bonding a substituent other than the hydroxyl group to the benzene ring of styrene where the α-hydrogen atom can be replaced by a substituent. It should be noted that, unless otherwise specified, the α-position (α-carbon atom) refers to the carbon atom bonded to the benzene ring.

[0037] The alkyl group used as the α-substituent is preferably a straight-chain or branched alkyl group. Specifically, examples include alkyl groups with 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.).

[0038] Furthermore, the alkyl halogroup that serves as the α-substituent can be specifically a group obtained by replacing some or all of the hydrogen atoms of the aforementioned "alkyl group that serves as the α-substituent" with a halogen atom. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0039] Furthermore, the hydroxyalkyl group that serves as the α-substituent can be specifically a group obtained by replacing some or all of the hydrogen atoms of the aforementioned "alkyl group that serves as the α-substituent" with hydroxyl groups. The number of hydroxyl groups in this hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0040] (Composition for forming the separation layer) One embodiment of the separation layer forming composition is a separation layer forming composition for forming the aforementioned separation layer in a laminate having a separation layer between a first layer and a second layer, wherein the first layer is a support substrate that allows light to pass through, and the separation layer is a layer that can be deformed by irradiation from the support substrate side, thereby separating the support substrate from the laminate.

[0041] The composition for forming the separation layer in this embodiment contains an epoxy resin (P), a light absorber having absorption at wavelengths of 300 nm to 1300 nm, and at least one acid-generating agent selected from the group consisting of thermal acid-generating agents and photo-acid-generating agents.

[0042] Furthermore, the curing temperature of the composition for forming the separation layer in this embodiment is 200°C or higher, which reduces the weight of the cured product by 1%.

[0043] Figure 1 A diagram illustrating one embodiment of the laminate. Figure 2 The figure illustrates other embodiments of the laminate.

[0044] Figure 1 In the stack 10 shown, a separation layer 12, a metal layer 14, a redistribution layer 16, and a sealing material layer 18 that seals the substrate are sequentially stacked on the support substrate 11.

[0045] Figure 2 In the stack 20 shown, a separation layer 22, a metal layer 24, a sealing material layer 28 that seals the substrate, and a redistribution layer 26 are sequentially stacked on the support substrate 21.

[0046] Supporting substrate 11 and supporting substrate 21 are supporting substrates that allow light to pass through, equivalent to the aforementioned first layer.

[0047] Separation layer 12 is a layer that can be denatured by irradiation from the support substrate 11 side, thereby separating the support substrate 11 from the laminate 10. Separation layer 22 is a layer that can be denatured by irradiation from the support substrate 21 side, thereby separating the support substrate 21 from the laminate 20.

[0048] Separation layer 12 and separation layer 22 are respectively formed by the separation layer forming composition involved in this method.

[0049] Regarding the release layer forming composition of this embodiment, the 1% weight reduction temperature of its cured product is 200°C or higher. If the 1% weight reduction temperature of the cured product of the release layer forming composition is at or above the lower limit of the aforementioned range, the heat resistance of the release layer formed by the release layer forming composition is improved.

[0050] For the composition for forming the release layer in this embodiment, the temperature at which the cured product loses 1% of its weight is 200°C or higher, preferably higher than 260°C, and the higher the temperature, the more preferred.

[0051] Method for determining the 1% weight reduction temperature of cured material: For compositions used to form a release layer, the 1% weight reduction temperature of the cured product is determined as follows.

[0052] In thermogravimetric analysis (TGA), for samples of 3–5 mg, heating is performed under a nitrogen atmosphere from 25 °C at a heating rate of 10 °C / min, and the weight change of the sample is measured. The temperature at which the sample weight decreases by 1% relative to the time point at 25 °C is taken as the 1% weight reduction temperature.

[0053] Regarding the composition for forming the separation layer in this embodiment, the transmittance of the cured product at a wavelength of 532 nm is preferably 30% or less, more preferably 20% or less, and the lower the value, the more preferred.

[0054] Methods for determining the transmittance of cured materials: For the composition for forming the release layer, the transmittance of the cured product was measured using a UV-Vis spectrophotometer when light with a wavelength of 532 nm was irradiated onto a cured film with a thickness of 1.0 μm formed on a glass substrate.

[0055] The composition for forming the separation layer in this embodiment contains an epoxy resin (P), a light absorber having absorption at wavelengths of 300 nm to 1300 nm, and at least one acid-generating agent selected from the group consisting of thermal acid-generating agents and photo-acid-generating agents.

[0056] <Epoxy Resin (P)> The composition for forming the release layer in this embodiment contains epoxy resin (P) (hereinafter also referred to as "(P) component").

[0057] (P) The separation layer is given the function of separating the support substrate from the laminate, and in addition, it is given the function of bonding with the support substrate and bonding with the metal layer or redistribution layer.

[0058] As a (P) component, a compound having sufficient epoxy groups in 1 molecule for forming a negative pattern by exposure can be used.

[0059] (P) The component preferably contains epoxy resin (PO) which is solid at 25°C. If the component contains epoxy resin (PO), it is less likely to leave marks on the surface of the coating film formed by the release layer forming composition, and it can prevent the deterioration of surface uniformity during operation.

[0060] The proportion of epoxy resin (PO) in the (P) component relative to the total mass (100% by mass) of the aforementioned (P) component is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and even more preferably 80 to 100% by mass.

[0061] If the proportion of the aforementioned epoxy resin (PO) in component (P) is above the lower limit of the aforementioned preferred range, it is less likely to produce marks on the surface of the coating film formed by the separation layer forming composition, and it can prevent the deterioration of surface uniformity during operation.

[0062] As component (P), epoxy resins with 2 or more epoxy functional groups are preferred, and examples include bisphenol type epoxy resins, Novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins or their hydrides, or aliphatic epoxy resins.

[0063] The aforementioned (P) component can be used alone or in combination with two or more components.

[0064] Bisphenol-type epoxy resin As a bisphenol type epoxy resin, any resin having structural units containing a bisphenol backbone is acceptable, and solid bisphenol type epoxy resin is preferred.

[0065] Solid bisphenol type epoxy resin refers to a resin that is solid at 25°C and has structural units containing a bisphenol backbone.

[0066] The epoxy equivalent in the bisphenol type epoxy resin is preferably 100 g / eq. or more, and more preferably 100 to 1000 g / eq.

[0067] As a bisphenol type epoxy resin, epoxy resins represented by the following general formula (anv0) are preferred examples.

[0068] [Chemical Formula 1] [In the formula, R] p1 and R p2 Each is independently an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. Multiple Rs p1 They can be the same or different. Multiple Rs p2 They can be the same or different. n1 is an integer from 1 to 5. R EP It is a group containing an epoxy group. Multiple R EP They can be the same, or they can be different. In the aforementioned equation (anv0), R p1 R p2 The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Examples of cyclic alkyl groups include cyclobutyl, cyclopentyl, etc. Among them, as R... p1 R p2 Each is preferably a hydrogen atom or a methyl group.

[0069] R p1 R p2 Fluoroalkyl groups with 1 to 5 carbon atoms can be exemplified by the aforementioned R. p1 R p2 A group obtained by replacing some or all of the hydrogen atoms of an alkyl group with 1 to 5 carbon atoms with fluorine atoms.

[0070] In equation (anv0), multiple R p1 They can be the same or different. Multiple Rs p2 They can be the same or different.

[0071] In the aforementioned formula (anv0), n1 is an integer from 1 to 5, preferably 2 or 3, and more preferably 2.

[0072] In the aforementioned equation (anv0), R EP It is a group containing an epoxy group.

[0073] As R EP The group containing an epoxy group is not particularly limited, but can be exemplified by: groups formed solely of epoxy groups; groups formed solely of alicyclic epoxy groups; and groups having an epoxy group or alicyclic epoxy group and a divalent linking group.

[0074] The so-called alicyclic epoxy group is an alicyclic group that has an oxetine structure as a 3-membered cyclic ether. Specifically, it is a group that has both an alicyclic group and an oxetine structure.

[0075] The alicyclic group that forms the basic skeleton of the alicyclic epoxy group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. Furthermore, the hydrogen atoms in these alicyclic groups can be replaced by alkyl, alkoxy, or hydroxyl groups.

[0076] In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferred that the epoxy group or the alicyclic epoxy group is bonded by a divalent linking group that is bonded to the oxygen atom (-O-) in (meth)acryloyloxy.

[0077] Here, there is no particular limitation on the divalent linking group, and divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms are preferred divalent linking groups.

[0078] Regarding divalent hydrocarbon groups that can have substituents: The divalent hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0079] The aliphatic hydrocarbon group in the divalent hydrocarbon group can be saturated or unsaturated, but is usually preferred to be saturated.

[0080] More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0081] The aforementioned linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkylene group is preferred; specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0082] The number of carbon atoms in the aforementioned branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, further preferably 2 to 4, and most preferably 2 or 3. As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0083] Examples of aliphatic hydrocarbon groups containing rings in their structure include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups are the same groups described above.

[0084] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0085] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0086] The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Examples include adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0087] The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring only needs to be a cyclic conjugated system with (4n+2) π electrons; there is no particular limitation, and it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include: aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by replacing some carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0088] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (e.g., groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkylene group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0089] Divalent hydrocarbon groups can have substituents.

[0090] The divalent hydrocarbon group, whether straight-chain or branched, may or may not have substituents. Examples of substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms formed by substitution with fluorine atoms, and carbonyl groups.

[0091] Alicyclic hydrocarbon groups, which are divalent hydrocarbon groups and contain rings in their structure, may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0092] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0093] Regarding the alkoxy group used as the aforementioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, and more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, with methoxy and ethoxy being the most preferred.

[0094] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0095] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0096] In the case of alicyclic hydrocarbon groups, a portion of the carbon atoms constituting its ring structure can be replaced with substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0097] In the case of an aromatic hydrocarbon group that is a divalent hydrocarbon group, the hydrogen atom in the aromatic hydrocarbon group can be replaced by a substituent. For example, the hydrogen atom in the aromatic hydrocarbon group that is bonded to the aromatic ring can be replaced by a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, etc.

[0098] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0099] Regarding the alkoxy, halogen atom, and haloalkyl groups that are the aforementioned substituents, examples can be given of groups that replace the hydrogen atoms present in the aforementioned alicyclic hydrocarbon groups.

[0100] Regarding divalent linking groups containing heteroatoms: The heteroatoms in a divalent linker containing heteroatoms are atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0101] Among the divalent linking groups containing heteroatoms, preferred linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-; -C(=O)-NH-, -NH-, -NH-C(=O)-O-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents); -S-, -S(=O)2-, -S(=O)2-O-, and 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 - represents a group [where Y is a group that represents ... 21 and Y 22 Each can be an independent divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m” is an integer from 1 to 3, etc.

[0102] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -NH-, -NH-C(=O)-O-, or -NH-C(=NH)-, the H can be replaced by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0103] 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 Each is an independent divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include the same groups listed in the above description of divalent linking groups as "divalent hydrocarbon groups that may have substituents".

[0104] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0105] As Y 22 Preferably, it is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0106] Formula-[Y 21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 1 to 3, preferably 1 or 2, more preferably 1. That is, as in formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably of the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is of the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0107] Among them, as R EP The epoxy group in it is preferably a glycidyl group.

[0108] Alternatively, epoxy resins represented by the following general formula (abp1) are preferred as bisphenol type epoxy resins.

[0109] [Chemical Formula 2] [In the formula, R] EP It is a group containing an epoxy group. Multiple R EP They can be the same or different. a31 and R a32 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. 31 Integers from 1 to 50. In the aforementioned equation (abp1), R EP It is a group containing an epoxy group.

[0110] As R EPThe group containing an epoxy group is not particularly limited, but can be exemplified by: groups formed solely of epoxy groups; groups formed solely of alicyclic epoxy groups; and groups having an epoxy group or alicyclic epoxy group and a divalent linking group.

[0111] Regarding R EP The description of the epoxy group is consistent with R in the aforementioned formula (anv0). EP It is the same. Among them, as R EP The epoxy group in it is preferably a glycidyl group.

[0112] In the aforementioned equation (abp1), R a31 and R a32 The alkyl group having 1 to 5 carbon atoms is, for example, a straight-chain, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Examples of cyclic alkyl groups include cyclobutyl and cyclopentyl.

[0113] Among them, as R a31 R a32 Each is preferably a hydrogen atom or a straight-chain or branched alkyl group, more preferably a hydrogen atom or a straight-chain alkyl group, and particularly preferably a hydrogen atom or a methyl group.

[0114] In equation (abp1), multiple R a31 They can be the same or different. Multiple Rs a32 They can be the same or different.

[0115] R a31 R a32 Fluoroalkyl groups with 1 to 5 carbon atoms can be exemplified by the aforementioned R. a31 R a32 A group obtained by replacing some or all of the hydrogen atoms of an alkyl group with 1 to 5 carbon atoms with fluorine atoms.

[0116] In the aforementioned formula (abp1), na 31 It is an integer from 1 to 50, preferably an integer from 4 to 15, and more preferably an integer from 4 to 8.

[0117] Commercially available products that can be used as bisphenol-type epoxy resins include, for example, jER-152, jER-154, jER-157S70, jER-157S65 (all manufactured by Mitsubishi Chemical Corporation); jER-4005, jER-4007, jER-4010 (all manufactured by Mitsubishi Chemical Corporation); jER-827, jER-828, jER-834, jER-1001, jER-1002, jER-1003, jER-1055, jER-1007, jER-1009, jER-1010 (all manufactured by Mitsubishi Chemical Corporation); EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (all manufactured by DIC Corporation), etc.

[0118] As a bisphenol type epoxy resin, it can be used alone or in combination with two or more types.

[0119] In the composition for forming the separation layer of this embodiment, the content of bisphenol type epoxy resin is preferably 50% or more by mass relative to the total amount of (P) component 100% by mass, more preferably 60% or more by mass, and may also be 70% or more by mass, 80% or more by mass, 90% or more by mass, or 100% by mass.

[0120] Novolac type epoxy resin As a Novolac type epoxy resin, a resin having structural units represented by the following general formula (anv1) is preferably cited.

[0121] [Chemical Formula 3] [In the formula, R] EP It is a group containing an epoxy group. R a22 and R a23 Each atom is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. In the aforementioned equation (anv1), R a22 R a23 Alkyl groups with 1 to 5 carbon atoms and R in the aforementioned formula (anv0) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms.

[0122] R a22 R a23 The halogen atom is preferably a chlorine atom or a bromine atom.

[0123] In the aforementioned equation (anv1), R EP R in the aforementioned equation (anv0) EP Similarly, glycidyl groups are preferred.

[0124] The following shows a specific example of the structural unit represented by the aforementioned formula (anv1).

[0125] [Chemical Formula 4] Novolac type epoxy resin can be a resin formed solely of the aforementioned structural unit (anv1), or a resin having structural unit (anv1) and other structural units.

[0126] As other structural units, for example, the structural units represented by the following general formulas (anv2) to (anv3) can be cited.

[0127] [Chemical Formula 5] [In the formula, R] a24 It is a hydrocarbon group that can have substituents. R a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R a27 This refers to a group containing an epoxy group or a hydrocarbon group that may have substituents. In the aforementioned equation (anv2), R a24 It is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups that may have substituents include straight-chain or branched alkyl groups, or cyclic hydrocarbon groups.

[0128] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0129] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0130] In R a24 When the hydrocarbon group is cyclic, it can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0131] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically, cyclopentane, cyclohexane, etc. are examples.

[0132] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms. Specifically, examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0133] In R a24 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0134] The aromatic ring need only be a cyclic conjugated system with 4n+2 π electrons; there are no particular limitations. It can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by replacing some carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0135] As R a24 The aromatic hydrocarbon group in the compound can specifically include groups (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups formed by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0136] In the aforementioned equations (anv2) and (anv3), R a25 ~R a26 R a28 ~R a30 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0137] Alkyl groups with 1 to 5 carbon atoms and halogen atoms are respectively associated with the aforementioned R. a22 R a23 same.

[0138] In the aforementioned equation (anv3), R a27 It is a group containing an epoxy group, or a hydrocarbon group that may have substituents. R a27 The epoxy group and R in the aforementioned formula (anv0) EP It's the same. R a27 The hydrocarbon group that may have substituents and R in the aforementioned formula (anv2) a24 It's the same.

[0139] The following are specific examples of the structural units represented by the aforementioned equations (anv2) to (anv3).

[0140] [Chemical Formula 6] In the case where the Novolac type epoxy resin has other structural units besides the structural unit (anv1), the proportion of each structural unit in the Novolac type epoxy resin is not particularly limited. The total number of structural units with epoxy groups is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and even more preferably 30 to 70 mol% relative to the total number of all structural units constituting the Novolac type epoxy resin.

[0141] Commercially available Novolac-type epoxy resins include, for example, EPICLON N-740, EPICLON N-740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON HP5000 (all manufactured by DIC Corporation), and EOCN-1020 (all manufactured by Nippon Kayaku Co., Ltd.).

[0142] As a Novolac type epoxy resin, one type can be used alone, or two or more types can be used in combination.

[0143] In the composition for forming the separation layer of this embodiment, the content of Novolac-type epoxy resin is preferably 25% by mass or more, more preferably 40% by mass or more, or may be 50% by mass or more, or may be 75% by mass or more, or may be 90% by mass or more, or may be 100% by mass, relative to the total amount of (P) component 100% by mass.

[0144] Naphthalene-type epoxy resin As a naphthalene-type epoxy resin, a resin having a structural unit represented by the following general formula (nap1) is preferably cited.

[0145] [Chemical Formula 7] [In the formula, R] EP It is a group containing an epoxy group. R a32 and R a33 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. R a37 It is a group containing an epoxy group, or a hydrocarbon group that may have substituents. R a38 ~R a40 Each atom is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. In the aforementioned equation (nap1), R a32 R a33 Alkyl groups with 1 to 5 carbon atoms and R in the aforementioned formula (anv0) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms.

[0146] R a32 R a33 The halogen atom is preferably a chlorine atom or a bromine atom.

[0147] In the aforementioned equation (nap1), R EP R in the aforementioned equation (anv0) EP Similarly, glycidyl groups are preferred.

[0148] In the aforementioned equation (nap1), R a38 ~R a40 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.

[0149] Alkyl groups with 1 to 5 carbon atoms and halogen atoms are respectively associated with the aforementioned R. a32 R a33 same.

[0150] In the aforementioned equation (nap1), R a37 It is a group containing an epoxy group, or a hydrocarbon group that may have substituents. R a37 The epoxy group and R in the aforementioned formula (anv0) EP It's the same. R a27 The hydrocarbon group that may have substituents and R in the aforementioned formula (anv2) a24 It's the same.

[0151] The following shows a specific example of the structural unit represented by the aforementioned formula (nap1).

[0152] [Chemical Formula 8] Phenylated epoxy resin As a biphenyl-type epoxy resin, a resin having a structural unit represented by the following general formula (bph1) is preferably mentioned.

[0153] [Chemical Formula 9] [In the formula, R] EP It is a group containing an epoxy group. R a42 and R a43 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a group containing an epoxy group. a47 ~R a50 Each atom is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. In the aforementioned formula (bph1), R a42 R a43 Alkyl groups with 1 to 5 carbon atoms and R in the aforementioned formula (anv0) p1 R p2 The same applies to alkyl groups with 1 to 5 carbon atoms.

[0154] R a42 R a43 The halogen atom is preferably a chlorine atom or a bromine atom.

[0155] In the aforementioned formula (bph1), R EP R in the aforementioned equation (anv0) EP Similarly, glycidyl groups are preferred.

[0156] In the aforementioned formula (bph1), R a47 ~R a50 Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom. The alkyl group having 1 to 5 carbon atoms and the halogen atom each have the aforementioned R... a42 R a43 same.

[0157] The following shows a specific example of the structural unit represented by the aforementioned formula (bph1).

[0158] [Chemical Formula 10] Hydride Other examples of (P) components include the various epoxy resin hydrides mentioned above.

[0159] For example, epoxy resins represented by the following general formula (Aep-1) are preferred as the hydride.

[0160] [Chemical Formula 11] [In the formula, Rep] 1 ~Rep 4 Each can independently represent an alkyl group or a trifluoromethyl group having 1 to 4 carbon atoms. Rep 5 Representing a hydrogen atom or glycidyl group, in Rep 5 In cases where there are multiple instances, each Rep 5 They can be the same or different. n is an integer greater than or equal to 1. In the aforementioned equation (Aep-1), Rep 1 ~Rep 4 Each can independently represent an alkyl group or a trifluoromethyl group having 1 to 4 carbon atoms. Rep 1 ~Rep 4 Each is preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group.

[0161] In Rep 1 ~Rep 4 When all components are methyl groups, the epoxy resin represented by the general formula (Aep-1) is a hydrogenated bisphenol A type epoxy resin.

[0162] In the aforementioned equation (Aep-1), Rep 5 This represents a hydrogen atom or a glycidyl group, preferably a hydrogen atom. In Rep 5 In cases where there are multiple instances, each Rep 5 They can be the same or different.

[0163] In the aforementioned formula (Aep-1), n ​​is an integer of 1 or more, preferably an integer of 1 to 20, and more preferably an integer of 3 to 10.

[0164] Aliphatic epoxy resins As an aliphatic epoxy resin, for example, a compound represented by the following general formula (ta1) is preferably cited (hereinafter also referred to as "(ta1) component").

[0165] [Chemical Formula 12] [In the formula, R] EP It is a group containing an epoxy group. Multiple R EP They can be the same, or they can be different. In the aforementioned equation (ta1), R EP It is a group containing an epoxy group, and R in the aforementioned formula (anv0) EP It's the same.

[0166] Commercially available products that can be used as (ta1) ingredients include, for example, the TEPIC series (manufactured by Nissan Chemical Co., Ltd.), such as TEPIC, TEPIC-VL, TEPIC-PAS, TEPIC-G, TEPIC-S, TEPIC-SP, TEPIC-SS, TEPIC-HP, TEPIC-L, TEPIC-FL, and TEPIC-UC; MA-DGIC, DA-MGIC, and TOIC (manufactured by Shikoku Chemical Co., Ltd.).

[0167] As a (ta1) component, one type can be used alone, or two or more types can be used together.

[0168] In addition, as an aliphatic epoxy resin, there are also compounds that contain a partial structure represented by the following general formula (m1) (hereinafter also referred to as "(m1) component").

[0169] [Chemical Formula 13] [In the formula, n2 is an integer from 1 to 4.] Indicates a connection key. In the aforementioned formula (m1), n2 is an integer from 1 to 4, preferably an integer from 1 to 3, and more preferably 2.

[0170] As component (m1), there are several compounds whose partial structures represented by the above general formula (m1) are formed by the bonding of divalent linking groups or single bonds. Among them, compounds whose partial structures represented by the above general formula (m1) are preferably formed by the bonding of divalent linking groups.

[0171] There are no particular limitations on the divalent linking group used here. Examples of preferred divalent linking groups include divalent hydrocarbon groups that may have substituents and divalent linking groups that contain heteroatoms.

[0172] Regarding the divalent hydrocarbon group that may have substituents and the divalent linking group containing heteroatoms mentioned here, they are the same as the divalent hydrocarbon group that may have substituents and the divalent linking group containing heteroatoms described in the "groups containing epoxy groups" section above, wherein the divalent linking group containing heteroatoms is preferred, and -Y is more preferred. 21 -C(=O)-O- represents the group, -C(=O)-OY 21 - indicates a group. As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0173] Commercially available products that can be used as aliphatic epoxy resins include, for example, ADEKA RESIN EP-4080S, ADEKA RESIN EP-4085S, and ADEKA RESIN EP-4088S (all manufactured by ADEKA Corporation); Celloxide 2021P, Celloxide 2081, Celloxide 2083, Celloxide 2085, Celloxide 8000, Celloxide 8010, EHPE-3150, EPOLEAD PB 3600, and EPOLEAD PB 4700 (all manufactured by Daicel Corporation); and Denacol EX-211L, EX-212L, EX-214L, EX-216L, EX-321L, and EX-850L (all manufactured by Nagase Chemtex Corporation).

[0174] In the separation layer forming composition of this embodiment, the (P) component is preferably a component containing an epoxy resin (P1), wherein the epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

[0175] Alternatively, as component (P), it is preferred to include a hydride (P2) of epoxy resin (P1), wherein the epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

[0176] Alternatively, as component (P), it is preferably a component comprising both epoxy resin (P1) and a hydride (P2) of the aforementioned epoxy resin (P1), wherein the epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

[0177] When both epoxy resin (P1) and hydride (P2) are included, the mixing ratio of the two, expressed as the mass ratio of epoxy resin (P1) / hydride (P2), is preferably 5 / 95 to 95 / 5, more preferably 10 / 90 to 90 / 10, and even more preferably 20 / 80 to 80 / 20.

[0178] Alternatively, component (P) may be a component that combines the aforementioned aliphatic epoxy resin. For example, a component that combines the aforementioned epoxy resin (P1) and the aforementioned aliphatic epoxy resin can be cited as an example, and a component that combines the aforementioned epoxy resin (P1) and the aforementioned component (m1) can be cited as an example. In this case, the mixing ratio of the two, expressed as a mass ratio of epoxy resin (P1) / (m1) component, is preferably 50 / 50 to 95 / 5, more preferably 60 / 40 to 90 / 10, and even more preferably 70 / 30 to 85 / 15.

[0179] If the mixing ratio of the two is within the aforementioned preferred range, it is less likely to leave marks on the coating surface.

[0180] The weight-average molecular weight of component (P), converted to polystyrene, is preferably 500 to 10,000, more preferably 750 to 5,000, and even more preferably 1,000 to 2,500. By setting such a weight-average molecular weight, the strength of the formed cured film can be sufficiently improved.

[0181] The content of component (P) in the composition for forming the separation layer in this embodiment can be adjusted according to the film thickness of the coating of the separation layer to be formed.

[0182] In the separation layer forming composition of this embodiment, the content of component (P) is preferably 40 to 99% by mass, more preferably 50 to 95% by mass, and even more preferably 60 to 90% by mass, relative to the total amount of solid components (100% by mass) of the separation layer forming composition.

[0183] <Light absorber> The composition for forming the separation layer in this embodiment contains a light absorber that absorbs at wavelengths of 300 nm to 1300 nm.

[0184] Here, "absorption at wavelengths above 300 nm and below 1300 nm" means that in spectrophotometry, there are absorption spectral peaks at wavelengths above 300 nm and below 1300 nm.

[0185] Therefore, in terms of light irradiated from the support matrix side in the laminate, lasers with wavelengths from 300 nm to 1300 nm are suitable.

[0186] In this embodiment, the temperature at which the light-absorbing agent contained in the composition for forming the separation layer decreases by 1% by weight is preferably 200°C or higher, more preferably 210°C or higher, and even more preferably 220°C or higher; the higher the temperature, the more preferred.

[0187] If the temperature at which the light absorber decreases by 1% by weight is above the lower limit of the aforementioned preferred range, the heat resistance of the separation layer formed by the separation layer forming composition containing the light absorber is easily improved.

[0188] Method for determining the 1% weight reduction temperature of absorbent: The temperature was reduced by 1% by weight of the absorber as described below.

[0189] (1) Mix the light absorber with a dispersion medium to prepare a dispersion of the light absorber. The dispersion medium can be a solvent that makes the mixture of epoxy resin, light absorber and acid-producing agent homogeneous.

[0190] (2) The dispersion of the light absorber is coated on a glass substrate and a heat treatment is performed to remove the dispersion medium to form a light absorber film with a thickness of 1.0 μm.

[0191] (3) In thermogravimetric analysis (TGA), for a light absorber film with a thickness of 1.0 μm, the film was heated from 25 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, and the weight change of the light absorber film was measured. The temperature at which the weight of the light absorber film decreased by 1% relative to the weight at the time point of 25 °C was taken as the 1% weight reduction temperature.

[0192] The transmittance of the light-absorbing agent contained in the composition for forming the separation layer in this embodiment at a wavelength of 532 nm is preferably 20% or less, more preferably 10% or less, even more preferably 5% or less, particularly preferably 1% or less, and the lower the transmittance, the more preferred.

[0193] If the transmittance of the absorber at a wavelength of 532 nm is below the upper limit of the aforementioned preferred range, it is easy to improve the responsiveness to lasers including wavelengths from 300 nm to 1300 nm.

[0194] Method for determining the transmittance of a light-absorbing agent at a wavelength of 532 nm: Regarding the transmittance of the absorber, the transmittance of light when a 1.0 μm thick absorber film formed on a glass substrate is irradiated with light of 532 nm was measured using a UV-Vis spectrophotometer.

[0195] Examples of light-absorbing agents contained in the composition for forming the separation layer in this embodiment include, for example, carbon black, graphite powder, particulate metal powders such as iron, aluminum, copper, nickel, cobalt, manganese, chromium, zinc, and tellurium; metal oxide powders such as black titanium dioxide; aromatic diamine metal complexes; aromatic amide compounds; aliphatic diamine metal complexes; aromatic dithiol metal complexes; and mercaptophenol metal complexes.

[0196] Among them, from the viewpoint of the laser reactivity and heat resistance of the separation layer, particulate metal powder is preferred, and from the viewpoint of improving the heat resistance of the separation layer, carbon black is more preferred.

[0197] The aforementioned light absorbers can be used alone or in combination with two or more.

[0198] In the composition for forming the release layer of this embodiment, the content of the light absorber is preferably 10 parts by mass or more and 100 parts by mass or less, more preferably more than 10 parts by mass and less than 100 parts by mass, even more preferably 15 parts by mass or more and 75 parts by mass or less, and particularly preferably 20 parts by mass or more and 50 parts by mass or less.

[0199] If the content of the light absorber is above the lower limit of the aforementioned preferred range, the laser reactivity of the separation layer is more easily improved. On the other hand, if it is below the upper limit of the aforementioned preferred range, a more uniform composition is easier to prepare.

[0200] <Acid-producing agent> The composition for forming the separation layer in this embodiment contains at least one acid-producing agent selected from the group consisting of thermal acid-producing agents and photo-acid-producing agents.

[0201] Acid-generating agents produce acid using heat or light. Through the action of this acid, the epoxy groups in the epoxy resin undergo ring-opening polymerization to form a resin film, which is then cured to form a release layer.

[0202] Heat-generating acid agents As a heat-generating acid agent, it is appropriate to select and use from known heat-generating acid agents. In terms of heat-generating acid agents, the temperature at which acid is generated is preferably above the temperature at which the support substrate coated with the composition for forming the release layer is pre-baked, more preferably above 110°C, and even more preferably above 130°C.

[0203] Examples of heat-generating acid agents include trifluoromethanesulfonate, tetra(pentafluorophenyl)gallate, hexafluorophosphate, perfluorobutanesulfonate, boron trifluoride salt, and boron trifluoride ether complex.

[0204] As preferred thermal acid-producing agents, compounds formed from the cation and anion portions shown below can be cited.

[0205] [Chemical Formula 14] In formula (T-ca-1), R h01 ~R h04 Each is independently a group selected from the group consisting of hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, and aryl groups, R h01 ~R h04 At least one of them is an aryl group. The aforementioned alkyl or aryl group may have substituents. In formula (T-ca-2), R h05 ~R h07Each is independently a group selected from the group consisting of alkyl and aryl groups having 1 to 20 carbon atoms, R h05 ~R h07 At least one of them is an aryl group. In formula (T-ca-3), R h08 and R h09 Each is independently a group selected from the group consisting of alkyl and aryl groups having 1 to 20 carbon atoms, R h08 and R h09 At least one of them is an aryl group. The aforementioned alkyl or aryl groups may have substituents. ...Regarding the cationic portion of thermally produced acid agents In the aforementioned formula (T-ca-1), R h01 ~R h04 The alkyl group has 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 5, and even more preferably a straight-chain or branched alkyl group with 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., among which methyl and ethyl are preferred.

[0206] R h01 ~R h04 The alkyl group may have substituents. Examples of such substituents include alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups.

[0207] The alkoxy group that is a substituent for an alkyl group is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0208] Examples of halogen atoms that can be used as substituents for alkyl groups include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0209] Haloalkyl groups that are substituents of alkyl groups include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms.

[0210] The carbonyl group that is a substituent for an alkyl group is a group that substitutes the methylene group (-CH2-) that constitutes the alkyl group (>C=O).

[0211] Examples of cyclic groups that can be substituents for alkyl groups include aromatic hydrocarbon groups and alicyclic hydrocarbon groups (which can be polycyclic or monocyclic). Aromatic hydrocarbon groups mentioned here include those related to R described later. h01 ~R h04The same group as the aryl group. Among the alicyclic hydrocarbon groups here, as monocyclic alicyclic hydrocarbon groups, groups obtained by removing one or more hydrogen atoms from a monocyclic alkane are preferred. As such a monocyclic alkane, a monocyclic alkane with 3 to 6 carbon atoms is preferred; specifically, cyclopentane, cyclohexane, etc., are examples. Furthermore, as polycyclic alicyclic hydrocarbon groups, groups obtained by removing one or more hydrogen atoms from a polycyclic alkane are preferred; as such a polycyclic alkane, a polycyclic alkane with 7 to 30 carbon atoms is preferred. Among these, as such a polycyclic alkane, more preferably, is adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc., which have a polycyclic skeleton with a bridging ring system; or polycyclic alkanes with a cyclic group having a steroidal skeleton, etc., which have a polycyclic skeleton with a condensed ring system.

[0212] In the aforementioned formula (T-ca-1), R h01 ~R h04 The aryl group in the figure is a hydrocarbon group having at least one aromatic ring.

[0213] The aromatic ring only needs to be a cyclic conjugated system with 4n+2 π electrons; there is no particular limitation, and it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12.

[0214] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing some carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0215] As R h01 ~R h04 Specifically, the aryl group can be exemplified by a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); or a group formed by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1. Among them, more preferred are groups obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle, and groups obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group; even more preferred are groups obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring, and groups obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring with an alkylene group.

[0216] R h01 ~R h04 The aryl group may have substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, cyclic group, alkylcarbonyloxy, etc.

[0217] The alkyl group used as a substituent for the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0218] The descriptions of alkoxy groups, halogen atoms, haloalkyl groups, carbonyl groups, and cyclic groups that are substituents of aryl groups are the same as those of alkoxy groups, halogen atoms, haloalkyl groups, carbonyl groups, and cyclic groups that are substituents of alkyl groups described above.

[0219] In the alkyl carbonyloxy group that is a substituent for aryl, the number of carbon atoms in the alkyl moiety is preferably 1 to 5. Examples of alkyl moiety include methyl, ethyl, propyl, and isopropyl, among which methyl and ethyl are preferred, and methyl is more preferred.

[0220] In the aforementioned formula (T-ca-1), R h01 ~R h04 At least one of them is an aryl group that may have substituents.

[0221] The following shows specific examples of cations represented by the aforementioned formula (T-ca-1).

[0222] [Chemical Formula 15] In the aforementioned equation (T-ca-2), regarding R h05 ~R h07 The descriptions of alkyl and aryl groups in the above are respectively related to the descriptions of R. h01 ~R h04 The explanations for alkyl and aryl groups are the same.

[0223] In the aforementioned formula (T-ca-2), R h05 ~R h07 At least one of them is an aryl group that may have substituents.

[0224] The following shows specific examples of cations represented by the aforementioned formula (T-ca-2).

[0225] [Chemical Formula 16] In the aforementioned equation (T-ca-3), regarding R h08 and R h09 The descriptions of alkyl and aryl groups in the above are respectively related to the descriptions of R. h01 ~Rh04 The explanations for alkyl and aryl groups are the same.

[0226] In the aforementioned formula (T-ca-3), R h08 and R h09 At least one of them is an aryl group that may have substituents.

[0227] The following shows specific examples of cations represented by the aforementioned formula (T-ca-3).

[0228] [Chemical Formula 17] ...Regarding the anionic portion of thermally generated acid agents Examples of anionic derivatives used as thermally generated acid agents include hexafluorophosphate anion, trifluoromethanesulfonate anion, perfluorobutyrate anion, and tetra(pentafluorophenyl)gallate ([Ga(C6F5)4)). - Tetra[(trifluoromethyl)phenyl]gallate ([Ga(C6H4CF3)4]) - ), difluorobis(pentafluorophenyl)gallium ion ([(C6F5)2GaF2]) - Tetrafluorophenyl)gallium ion ([Ga(C6H3F2)4]) - Tetra(pentafluorophenyl)borate ([B(C6F5)4)) - ), tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), tetra(difluorophenyl)borate ([B(C6H3F2)4] - )wait.

[0229] Among them, trifluoromethanesulfonate anion, perfluorobutyrate anion, and tetra(pentafluorophenyl)gallate anion are preferred, and trifluoromethanesulfonate anion and tetra(pentafluorophenyl)gallate anion are more preferred.

[0230] In the separation layer forming composition of this embodiment, the thermally generated acid agent can be, for example, the following products manufactured by San-Aid: SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-110, SI-110L, SI-145, SI-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 (all manufactured by San-Shin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Corporation); CP-66, CP-77 (manufactured by ADEKA Corporation); FC-520 (manufactured by 3M Corporation); K-PURE. TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2 678, TAG-2681, TAG-2679, TAG-2689, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC- 1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, CXC-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60, CXC-2689 (all manufactured by KING INDUSTRY); TA-100, TA-100FG, IK-1, IK-1FG (all manufactured by San-Apro Co., Ltd.) and other commercially available products.

[0231] The following are specific examples of preferred heat-generating acid agents.

[0232] [Chemical Formula 18] Photo-acid generator As photoacid generators, onium salt-based acid generators such as sulfonium salts are preferred examples.

[0233] Preferred cations among onium salt-based acid-producing agents include sulfonium cations and iodonium cations, with organic cations represented by the following general formulas (ca-1) to (ca-5) being particularly preferred.

[0234] [Chemical Formula 19] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can independently represent an aryl, heteroaryl, alkyl, or alkenyl group that may have substituents. R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 They can also bond with each other to form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each can independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms. R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent. L 201 This represents -C (=O)- or -C (=O)-O-. Y 201 Each can independently represent an arylene, alkylene, or alkenyl group. x is 1 or 2. W 201 This represents a linking group with a valence of (x+1). As R 201 ~R 207 and R 211 ~R 212 The aryl group in the aryl group can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0235] As R 201 ~R 207 and R 211 ~R 212 The heteroaryl group in the above-mentioned aryl group can be exemplified by a group obtained by replacing a portion of the carbon atoms of the aforementioned aryl group with heteroatoms. Examples of heteroatoms include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroaryl groups include those obtained by removing one hydrogen atom from 9H-thioxanthone; examples of substituted heteroaryl groups include those obtained by removing one hydrogen atom from 9H-thioxanthone-9-one.

[0236] As R 201 ~R 207 and R 211 ~R 212 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0237] As R 201 ~R 207 and R 211 ~R 212 The alkenyl group in the form of the group preferably has 2 to 10 carbon atoms.

[0238] As R201 ~R 207 and R 210 ~R 212 The substituents that may be present include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, oxo (=O), aryl, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

[0239] [Chemical Formula 20] [In the formula, R'] 201 Each group can be an independent hydrogen atom, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. In the aforementioned equations (ca-r-1) to (ca-r-10), R' 201 Each can be an independent hydrogen atom, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents.

[0240] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or a cyclic aliphatic hydrocarbon group. Aliphatic hydrocarbon groups refer to hydrocarbon groups that are not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0241] R' 201 The aromatic hydrocarbon group in the form is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0242] As R' 201 The aromatic rings contained in aromatic hydrocarbon groups can be specifically exemplified by benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles obtained by replacing some carbon atoms in these aromatic rings with heteroatoms, or rings obtained by replacing some hydrogen atoms in these aromatic rings or aromatic heterocycles with oxo groups, etc. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc.

[0243] As R' 201The aromatic hydrocarbon group in the alkyl group can specifically include groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, anthracene, etc.), groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups), groups obtained by removing one hydrogen atom from a ring obtained by substituting a portion of the hydrogen atoms constituting the aforementioned aromatic ring with an oxo group or the like (for example, anthraquinone), and groups obtained by removing one hydrogen atom from an aromatic heterocycle (for example, 9H-thioxanth, 9H-thioxanth-9-one, etc.). The number of carbon atoms in the aforementioned alkylene group (alkyl chain in arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0244] R' 201 Examples of cyclic aliphatic hydrocarbon groups include aliphatic hydrocarbon groups that contain rings in their structure.

[0245] Examples of aliphatic hydrocarbon groups containing a ring in their structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups with an alicyclic hydrocarbon group located in the middle of a straight-chain or branched aliphatic hydrocarbon group.

[0246] The number of carbon atoms in the aforementioned alicyclic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0247] The aforementioned alicyclic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms; specifically, cyclopentane, cyclohexane, etc., are examples. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, it is preferably a polycyclic alkane with 7 to 30 carbon atoms. More preferably, it is a polycyclic alkane with a bridging ring system, such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a condensed ring system, such as a cyclic group with a steroidal skeleton.

[0248] Among them, as R' 201 The cyclic aliphatic hydrocarbon group in the form is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane, more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl or norbornyl, and most preferably adamantyl.

[0249] The number of carbon atoms in the aliphatic hydrocarbon group that can bond with the alicyclic hydrocarbon group, whether straight-chain or branched, is preferably 1 to 10, more preferably 1 to 6, further preferably 1 to 4, and most preferably 1 to 3.

[0250] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], 1,3-propylene [-(CH2)3-], 1,4-butylene [-(CH2)4-], and 1,5-pentylene [-(CH2)5-].

[0251] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyl-1,3-propylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl-1,4-butylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0252] Alkyl groups that may have substituents: As R' 201 The alkyl group is a chain, which can be either straight-chain or branched.

[0253] As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, etc.

[0254] As a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0255] Alkenyl groups that may have substituents in a chain-like structure: As R' 201 The chain-like alkenyl group can be of any shape, either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0256] Of the above, the alkenyl group is preferably a linear alkenyl group, more preferably a vinyl or propenyl group, and particularly preferably a vinyl group.

[0257] As R' 201 Substituents in cyclic groups, chain-like alkyl or alkenyl groups, for example, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, oxo groups, and the aforementioned R' groups. 201 The cyclic groups, alkyl carbonyl groups, thiophene carbonyl groups, etc.

[0258] Among them, R' 201 Preferably, it is a cyclic group that may have substituents or a chain alkyl group that may have substituents.

[0259] In R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 When they bond together and form a ring with the sulfur atom in the formula, they can be intermediates such as sulfur atoms, oxygen atoms, nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. The ring skeleton containing the sulfur atom in the formula is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathracene rings, phenoxathia rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0260] In the aforementioned equation (ca-3), R 208 ~R 209 Each alkyl group independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms. In the case of alkyl groups, they can bond together to form a ring.

[0261] In the aforementioned equation (ca-3), R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent.

[0262] As R 210 The aryl group in the aryl group can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0263] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms.

[0264] As R 210 The alkenyl group in the form of the group preferably has 2 to 10 carbon atoms.

[0265] In the aforementioned equations (ca-4) and (ca-5), Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0266] Y 201 The aryl group in R' can be cited as an example. 201 The aromatic hydrocarbon group is a group obtained by removing one hydrogen atom from the aryl group, as exemplified by the aromatic hydrocarbon group.

[0267] Y 201 Examples of alkylene and alkenylene groups in R' are derived from... 201 A group obtained by removing one hydrogen atom from a chain-like alkyl group or a chain-like alkenyl group.

[0268] In the aforementioned equations (ca-4) and (ca-5), x is 1 or 2.

[0269] W 201 It is a (x+1) valence, that is, a divalent or trivalent linker.

[0270] As W 201 The divalent linking group in the W is preferably a divalent hydrocarbon group that can have substituents. 201 The divalent linking group can be any of the following: linear, branched, or cyclic, with a cyclic form being preferred. Preferably, it is a group formed by combining two carbonyl groups at both ends of the arylene group, or a group formed solely of arylene groups. Examples of arylene groups include phenylene and naphthylene, with phenylene being particularly preferred.

[0271] As W 201 The trivalent linker in the W can be cited as an example. 201 Groups obtained by removing one hydrogen atom from a divalent linker, and groups obtained by further bonding the aforementioned divalent linker to the aforementioned divalent linker, etc. As W201 The trivalent linking group is preferably a group obtained by bonding two carbonyl groups to an arylene group.

[0272] As preferred cations represented by the aforementioned formula (ca-1), examples include the cations represented by the following formulas (ca-1-1) to (ca-1-24).

[0273] [Chemical Formula 21] [Chemical Formula 22] [In the formula, R”] 201 It is a hydrogen atom or a substituent. As this substituent, it is related to the aforementioned R... 201 ~R 207 and R 210 ~R 212 The same applies to substituents that can be present. Furthermore, the cation represented by the aforementioned formula (ca-1) is preferably the cation represented by each of the following general formulas (ca-1-25) to (ca-1-35).

[0274] [Chemical Formula 23] [Chemical Formula 24] [In the formula, R'] 211 It is an alkyl group. R hal It consists of hydrogen atoms or halogen atoms. Furthermore, the cation represented by the aforementioned formula (ca-1) is preferably the cation represented by each of the following chemical formulas (ca-1-36) to (ca-1-48).

[0275] [Chemical Formula 25] Furthermore, the cation represented by the aforementioned formula (ca-1) is preferably a cation represented by each of the following chemical formulas (ca-1-49) to (ca-1-56) having benzoylphenyl.

[0276] [Chemical Formula 26] Preferred cations represented by the aforementioned formula (ca-2) include, specifically, diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, etc.

[0277] As preferred cations represented by the aforementioned formula (ca-3), examples include the cations represented by each of the following formulas (ca-3-1) to (ca-3-6).

[0278] [Chemical Formula 27] As preferred cations represented by the aforementioned formula (ca-4), examples include the cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0279] [Chemical Formula 28] Furthermore, the cation represented by the aforementioned formula (ca-5) is preferably the cation represented by each of the following general formulas (ca-5-1) to (ca-5-3).

[0280] [Chemical Formula 29] [In the formula, R'] 212 It consists of an alkyl group or a hydrogen atom. R' 211 It is an alkyl group. Of the above, the preferred cation portion of the onium salt-based acid-producing agent is preferably a cation represented by the aforementioned general formula (ca-1), more preferably a cation represented by each of formulas (ca-1-1) to (ca-1-56), and even more preferably a cation represented by each of formulas (ca-1-25) to (ca-1-56).

[0281] As a preferred anionic component in onium salt-based acid-producing agents, tetra(pentafluorophenyl)borate ([B(C6F5)4)) is an example. - Tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4]) - ); difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ); Trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - Tetrafluorophenyl)borate ([B(C6H3F2)4) - )wait.

[0282] In addition, the anions represented by the following general formula (b0-2a) are also preferred.

[0283] [Chemical Formula 30] [In the formula, R] bf05 It is a fluoroalkyl group that can have substituents. 1 Integers between 1 and 5. In the aforementioned equation (b0-2a), R bf05 The fluoroalkyl group in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and even more preferably 1 to 5 carbon atoms. Wherein, as R... bf05 Preferably, it is a fluoroalkyl group with 1 to 5 carbon atoms, more preferably a perfluoroalkyl group with 1 to 5 carbon atoms, and even more preferably trifluoromethyl or pentafluoroethyl.

[0284] In the aforementioned equation (b0-2a), nb 1 Preferably, it is an integer from 1 to 4, more preferably an integer from 2 to 4, and particularly preferably 3.

[0285] In nb 1 When the value is 2 or higher, multiple R bf05 They can be the same, or they can be completely different.

[0286] The following are specific examples of preferred photoacid-generating agents.

[0287] [Chemical Formula 31] The aforementioned acid-producing agents can be used alone or in combination with two or more.

[0288] In the composition for forming the separation layer of this embodiment, the total content of at least one acid-generating agent selected from the group consisting of thermal acid-generating agents and photo-acid-generating agents is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the aforementioned epoxy resin (P).

[0289] If the total content of the acid-generating agent is within the aforementioned preferred range, sufficient acid can be generated by light irradiation or heat, which can promote the ring-opening polymerization of epoxy groups in epoxy resin and easily improve the heat resistance of the release layer.

[0290] <Other Ingredients> The composition for forming the separation layer in this embodiment may contain other components as needed, in addition to the above-mentioned (P) components, light absorbers, and acid-producing agents.

[0291] Other components mentioned include photosensitizers, surfactants, organic solvents, sensitizers, etc.

[0292] Photosensitive ingredients The composition for forming the separation layer in this embodiment may contain a photosensitizer component. For example, the esterification product of a compound containing a phenolic hydroxyl group represented by the following chemical formula (c1) and a 1,2-diazidonaphthoquinone sulfonic acid compound is a preferred photosensitizer component.

[0293] [Chemical Formula 32] Examples of 1,2-diazidonaphthoquinone sulfonic acid compounds include 1,2-diazidonaphthoquinone-5-sulfonyl compounds and 1,2-diazidonaphthoquinone-4-sulfonyl compounds, with 1,2-diazidonaphthoquinone-5-sulfonyl compounds being preferred.

[0294] Surfactants To adjust coating workability, the composition for forming the release layer in this embodiment may contain a surfactant. Examples of surfactants include silicone-based surfactants and fluorinated surfactants.

[0295] Organic solvent components In order to adjust the coating workability, the composition for forming the release layer in this embodiment may contain an organic solvent component (hereinafter also referred to as "(S) component").

[0296] Examples of (S) components include, for example: straight-chain hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane, and tridecane; branched hydrocarbons with 4 to 15 carbon atoms; cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, and tetrahydronaphthalene; and p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpene diol, 1,8-terpene diol, camphene, norbornene, pinane, thujone, carene, and longifene. Geraniol, nerol, linalool, citral, citronellol, menthol, isomenthol, neomenthol, α-terpineol, β-terpineol, γ-terpineol, terpinene-1-ol, terpinene-4-ol, dihydroterpineol acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, ionone, thujone, camphor, d-limonene, l-limonene, dipentene, and other terpene solvents; γ-butyrolactone and other lactones; acetone, methyl ethyl ketone, cyclohexanone (CH4) Ketones such as methyl n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and polyol derivatives such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., or monoalkyl ethers or monophenyl ethers, etc., of the aforementioned polyols or compounds containing ester bonds. (Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferred); cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; aromatic organic solvents such as anisole, ethyl benzyl ether, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butylphenyl ether, etc.

[0297] The (S) component contained in the composition for forming the separation layer in this embodiment may be one type or two or more types.

[0298] In the separation layer forming composition of this embodiment, the amount of component (S) is not particularly limited, and can be appropriately set according to the coating film thickness and coatability within a concentration that allows it to be coated onto a support substrate, etc. Preferably, the total amount of the above-mentioned component (P) in the separation layer forming composition is preferably 50% by mass or less, more preferably 5 to 40% by mass, and even more preferably 10 to 30% by mass relative to the total mass (100% by mass) of the composition.

[0299] The separation layer forming composition of this embodiment includes the following separation layer forming composition, which contains an epoxy resin (P1), a light absorber having absorption at a wavelength of 300 nm to 1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator, and the 1% weight reduction temperature of the cured product is 200°C or higher. The epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl type epoxy resin and naphthalene type epoxy resin, and has 2 or more epoxy functional groups.

[0300] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains a hydride (P2) of the aforementioned epoxy resin (P1), a light absorber having absorption at a wavelength of 300 nm to 1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator, and the 1% weight reduction temperature of the cured product is 200°C or higher.

[0301] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains the aforementioned epoxy resin (P1), the aforementioned epoxy resin (P1) hydride (P2), a light absorber having absorption at a wavelength of 300 nm to 1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator, and the 1% weight reduction temperature of the cured product is 200°C or higher.

[0302] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains the aforementioned epoxy resin (P1), carbon black having absorption at wavelengths of 300 nm to 1300 nm, and a thermal acid-generating agent, and the curing temperature for a 1% weight reduction of the cured product is 200°C or higher.

[0303] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains the aforementioned epoxy resin (P1), the aforementioned epoxy resin (P1) hydride (P2), carbon black having absorption at wavelengths of 300 nm to 1300 nm, and a thermal acid-generating agent, and the curing temperature for a 1% weight reduction of the cured product is 200°C or higher.

[0304] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains the aforementioned epoxy resin (P1), carbon black having absorption at wavelengths of 300 nm to 1300 nm, and a photoacid generator, and the curing temperature for a 1% weight reduction of the cured product is 200°C or higher.

[0305] Alternatively, the separation layer forming composition of this embodiment may include the following separation layer forming composition, which contains the aforementioned epoxy resin (P1), the aforementioned aliphatic epoxy resin, carbon black having absorption at wavelengths of 300 nm to 1300 nm, and a thermal acid-generating agent, and the curing temperature for a 1% weight reduction of the cured product is 200°C or higher.

[0306] As described above, the separation layer forming composition of this embodiment contains epoxy resin (P), a light absorber having absorption at wavelengths of 300 nm to 1300 nm, and at least one acid generator selected from the group consisting of a thermal acid generator and a photoacid generator, and the curing temperature of the separation layer forming composition is 200°C or higher.

[0307] In the composition for forming the release layer, a light absorber with absorption at wavelengths between 300 nm and 1300 nm is used to enhance laser absorption and improve the laser reactivity of the release layer. Furthermore, the combination of epoxy resin (P) and an acid-generating agent, and by reducing the cured temperature by 1% by weight to 200°C or higher, improves the heat resistance of the release layer. For example, even in thermal processes involving prolonged application of temperatures exceeding 200°C, the generation of escaping gases from the release layer can be suppressed.

[0308] More preferably, a composition for forming a release layer with a 1% weight reduction of the aforementioned light absorber at a temperature of 200°C or higher is selected, thereby easily improving the heat resistance of the release layer.

[0309] (Layered structure) One embodiment of the laminate is a laminate having a separation layer between a first layer and a second layer. The first layer is a light-transmitting support substrate, and the separation layer is formed by curing a separation layer forming composition. The second layer is, for example, a seed layer.

[0310] As mentioned above, Figure 1 and Figure 2 Examples of stacked bodies are shown below.

[0311] <Supporting Substrate> The support substrate in this embodiment has the property of allowing light to pass through. The support substrate is a component that supports the substrate and is attached to the substrate through a release layer. Therefore, as a support substrate, it is preferable to have the strength required to prevent damage or deformation of the substrate during thinning of the sealant, handling of the substrate, mounting to the substrate, etc. Furthermore, the support substrate is preferably able to transmit light of wavelengths that can deform the release layer.

[0312] Materials used as the supporting substrate can include, for example, glass, silicone, acrylic resin, etc. The shape of the supporting substrate can include, for example, rectangles, circles, etc., but is not limited to these.

[0313] In addition, as a support substrate, in order to further achieve high-density integration and improve production efficiency, a substrate obtained by enlarging the size of a circular support substrate and a large panel with a quadrilateral shape when viewed from above can also be used.

[0314] <Separation Layer> The separation layer in the embodiment is a layer that can be denatured by irradiation from the support substrate side, thereby separating the support substrate from the laminate. In order to form this separation layer, the above-described (separation layer forming composition) is used.

[0315] The term "deterioration" of the separation layer refers to the phenomenon where the separation layer becomes susceptible to damage under external forces, or where the adhesive strength between the separation layer and the layers in contact with it decreases. The separation layer becomes brittle by absorbing light, losing its strength or adhesiveness before exposure to light. This deterioration occurs through processes such as decomposition caused by the absorbed light energy, changes in its stereostructure, or the dissociation of functional groups.

[0316] The thickness of the separation layer is preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 10 μm or less.

[0317] If the thickness of the separation layer is between 0.05 μm and 50 μm, the desired denaturation can be achieved by short-duration and low-energy light irradiation. Furthermore, from a productivity perspective, a thickness of 1 μm or less is particularly preferred.

[0318] <Metallic layer or redistribution layer> Examples of metal layers in the embodiments include layers mainly formed of Ti and layers mainly formed of Cu, and each layer may also contain other metals. The layer mainly formed of Cu may also be a seed layer for wiring in which a redistribution layer is formed using a plating method.

[0319] The metal layer can be formed, for example, by sputtering. The thickness of the metal layer is, for example, in the range of 10 nm or more and 1000 nm or less.

[0320] Regarding the redistribution layer in the embodiments, for example, a layer obtained by forming wiring on an insulating layer formed by a conductor (metals such as aluminum, copper, titanium, nickel, gold, silver, and alloys such as silver-tin alloys) can be described.

[0321] <Other Layers> In the laminate of the embodiment, in addition to the support substrate, release layer, metal layer or redistribution layer, other layers (other layers) may be further provided.

[0322] The laminates 10 and 20 of the embodiments also include sealing material layers 18 and 28 that seal the substrate.

[0323] The substrate is supplied for thinning, mounting, and other processes while being supported by a support substrate. Structures such as integrated circuits and metal bumps are mounted on the substrate.

[0324] As a substrate, silicon wafer substrates can typically be used, but are not limited to this; ceramic substrates, thin film substrates, flexible substrates, etc., can also be used.

[0325] The laminates involved in this method are not limited to the embodiments described above. For example, other examples include... Figure 1 The laminate 10 shown does not include a metal layer 14; that is, a separation layer 12, a redistribution layer 16, and a sealing material layer 18 that seals the substrate are sequentially laminated on a support substrate 11. Additionally, for example, in... Figure 2 The stack 20 shown can also be a method of forming bumps or mounting components on the redistribution layer 26.

[0326] Alternatively, another embodiment of the laminate may include additional layers between the support substrate and the separator layer. In this case, the additional layers can be made of a light-transmitting material. Thus, layers that impart desirable properties to the laminate can be appropriately added without hindering light incidence into the separator layer. The wavelength of the light that can be used varies depending on the type of material constituting the separator layer. Therefore, the materials constituting the additional layers do not need to transmit all wavelengths of light; they can be appropriately selected from materials that transmit wavelengths of light that can alter the properties of the materials constituting the separator layer (e.g., 532 nm).

[0327] The laminate involved in this method does not necessarily have an adhesive layer. The laminate in the above-described embodiment is a laminate in which the metal layer is bonded to the support substrate without the use of an adhesive layer.

[0328] As a non-essential adhesive layer, examples typically include layers in which one or more of the following main components are hydrocarbon resins such as cycloolefin polymers, acrylic-styrene resins, maleimide resins, elastomer resins, or polysulfone resins. Examples of non-essential adhesive layers include layers in which one or more of the following components are present in a content of 10% by mass or more relative to the total material forming the adhesive layer (100% by mass).

[0329] (Manufacturing methods for electronic components) The third aspect of the present invention relates to a method for manufacturing an electronic component, which is a manufacturing method having the following steps: a separation step in which light is irradiated from the support substrate side toward the separation layer to deform the separation layer, thereby separating the support substrate from the laminate; and a removal step in which the separation layer attached to the metal layer or redistribution layer is removed after the separation step.

[0330] Regarding the manufacturing method of the electronic components involved in this method, the first and second embodiments shown below are preferred. Each embodiment will be described with reference to the accompanying drawings.

[0331] It should be noted that in the accompanying drawings, in order to facilitate the observation of each component, the components are sometimes shown schematically, and sometimes they are shown at different scales depending on the components.

[0332] <First Implementation> One embodiment of the manufacturing method for electronic components is a manufacturing method having the following steps: a step of preparing a laminate (1-1); a separation step of separating a support substrate from the laminate (1-2); and a removal step of removing the separation layer attached to the metal layer or redistribution layer (1-3).

[0333] Figure 3A This diagram illustrates the method for forming the separation layer.

[0334] Figure 3B A diagram illustrating an example of a laminate prepared in the first embodiment.

[0335] Figure 3C A diagram illustrating the process of separating the support matrix from the laminate.

[0336] Figure 3D A diagram showing the state after the separation process.

[0337] Figure 3E This diagram illustrates the state after the removal process and shows an example of a semiconductor package (electronic component) manufactured in the first embodiment.

[0338] In the first embodiment, the laminate 10 is configured such that a metal layer 14 is provided immediately above the separation layer 12, and a redistribution layer 16 and a sealing material layer 18 are sequentially laminated on the metal layer 14.

[0339] [Preparation of the laminated body process (1-1)] Process (1-1) includes, for example, the operation of forming a release layer on a support substrate and the operation of forming a metal layer or a redistribution layer on the release layer.

[0340] • Operation of forming a separation layer on the support substrate Figure 3A In the middle, a separation layer 12 is formed on the support substrate 11.

[0341] The separation layer 12 can be formed by coating one side of the support substrate 11 with the above-described (separation layer forming composition) and curing it.

[0342] • Operations of forming a metal layer or redistribution layer on the release layer Next, on the separation layer 12 formed on the support substrate 11, a metal layer 14 and a redistribution layer 16 are formed by means of, for example, sputtering or plating.

[0343] Regarding the redistribution layer 16, the formation of the insulating layer formed by the dielectric, the seed layer, and the wiring can be repeated as described above, thereby creating a wiring layer having an insulating layer and wiring formed within the insulating layer. As a method for forming the wiring, known semiconductor process methods such as photolithography (resist photolithography) and etching can be used.

[0344] Through the operations so far, a support substrate with a thin metal film can be created.

[0345] Figure 3B In the stack 10 shown, a sealing material layer 18 for sealing the substrate is further provided on the redistribution layer 16.

[0346] The sealing material layer 18 can be formed by molding, for example, using a composition containing epoxy resin or silicone resin. The sealing material layer 18 here is not a layer that seals individual substrates, but rather preferably a layer that seals the entire substrate beneath the sealing material layer 18.

[0347] [Separation process (1-2) of separating the support matrix from the laminate] In the separation process (1-2), light is irradiated from the support substrate side onto the separation layer, thereby denaturing the separation layer and separating the support substrate from the laminate.

[0348] like Figure 3C As shown, in this process (1-2), light (arrow) is irradiated onto the separation layer 12 through the support substrate 11, thereby causing the separation layer 12 to deform.

[0349] Examples of wavelengths that can alter the separation layer 12 include wavelengths between 300 and 1300 nm, with wavelengths between 600 and 600 nm being preferred (e.g., 532 nm).

[0350] The type and wavelength of the irradiated light can be appropriately selected based on the transmittance of the support substrate 11 and the material constituting the separation layer 12. For example, solid-state lasers such as YAG lasers, ruby ​​lasers, glass lasers, YVO4 lasers, LD lasers, and fiber lasers, liquid lasers such as pigment lasers, gas lasers such as CO2 lasers, excimer lasers, Ar lasers, and He-Ne lasers, semiconductor lasers, and free-electron lasers can be used.

[0351] As an example of laser irradiation conditions, the following conditions can be cited.

[0352] The average output power of the laser is preferably 1.0W or more and 7.0W or less, more preferably 3.0W or more and 6.0W or less. The repetition frequency of the laser is preferably 20kHz or more and 60kHz or less, more preferably 30kHz or more and 50kHz or less. The scanning speed of the laser is preferably 100mm / s or more and 10000mm / s or less.

[0353] Next, light (arrow) is irradiated onto the separation layer 12 to denature it, and then the support substrate 11 is separated from the laminate 10. Figure 3D The state after the support substrate 11 is separated from the laminate 10 is shown.

[0354] Regarding the operation of separating the support substrate 11 from the laminate 10, methods such as applying force along the direction away from the support substrate 11 and the metal layer 14 or the redistribution layer 16 can be employed. For example, with one of the support substrate 11 side, or the metal layer 14 side, or the redistribution layer 16 side fixed to the worktable, the other side can be lifted while maintaining vacuum adsorption using a separation plate equipped with a suction cup (such as a bellows-type suction cup), thereby separating the support substrate 11 from the metal layer 14 or the redistribution layer 16. Alternatively, fluid can be injected into the gap formed between the support substrate 11 and the metal layer 14 or the redistribution layer 16, and the pressure of the injected fluid can be used to separate the support substrate 11 from the metal layer 14 or the redistribution layer 16.

[0355] The fluid used for jetting can be, for example, a gas, a liquid, or a mixture of gas and liquid, with a gas being preferred. As a gas, at least one selected from the group consisting of air, dry air, nitrogen, and argon can be cited.

[0356] [Removal process (1-3) to remove the release layer attached to the metal layer or redistribution layer] In the removal process (1-3), after the aforementioned separation process (1-2), the separation layer attached to the metal layer or redistribution layer is removed.

[0357] Figure 3D In the process, after the separation process (1-2), a separation layer 12 is attached to the metal layer 14. In this removal process (1-3), the separation layer 12 attached to the metal layer 14 is removed.

[0358] As a method for removing the separation layer 12 attached to the metal layer 14, examples include removing the residue of the separation layer 12 using a washing liquid or irradiating it with plasma.

[0359] As the washing liquid, a washing liquid containing an organic solvent is preferred. As the organic solvent, the organic solvent incorporated in the separation layer forming composition is preferred.

[0360] Figure 3E In the end, an electronic component 100 with a stacked structure of a redistribution layer 16 and a sealing material layer 18 is obtained.

[0361] As explained above, according to the manufacturing method of the electronic component using the first embodiment of the laminate 10, a sealing material layer 18 that seals the substrate (wiring layer) can be suitably formed on the separation layer 12.

[0362] In the manufacturing method of the electronic component according to the first embodiment, after the removal process (1-3) described above, there may be a process of forming solder balls, cutting or forming an oxide film.

[0363] <Second Implementation Method> Another embodiment of the manufacturing method for electronic components is a manufacturing method having the following steps: a step of preparing a laminate (2-1); a separation step of separating the support substrate from the laminate (2-2); and a removal step of removing the separation layer attached to the metal layer or redistribution layer (2-3).

[0364] Figure 4A This diagram illustrates the method for forming the separation layer.

[0365] Figure 4B A diagram illustrating an example of a laminate prepared in the second embodiment.

[0366] Figure 4C A diagram illustrating the process of separating the support matrix from the laminate.

[0367] Figure 4D A diagram showing the state after the separation process.

[0368] Figure 4E This diagram illustrates the state after the removal process and shows an example of a semiconductor package (electronic component) manufactured in the second embodiment.

[0369] In the second embodiment, the laminate 20 is configured such that a metal layer 24 is provided immediately above the separation layer 22, and a sealing material layer 28 and a redistribution layer 26 are sequentially laminated on the metal layer 24. The laminate 20 may also be a laminate obtained by forming the redistribution layer 26 on a substrate that has been exposed by grinding the sealing material layer 28 in a manner that exposes a portion of the substrate.

[0370] [Preparation of the laminated body process (2-1)] Process (2-1) includes, for example, the operation of forming a release layer on a support substrate, and the operation of forming a metal layer and a redistribution layer on the release layer.

[0371] • Operation of forming a separation layer on the support substrate Figure 4A In the middle, a separation layer 22 is formed on the support substrate 21.

[0372] The separation layer 22 can be formed by coating one side of the support substrate 21 with the above-mentioned (separation layer forming composition) and curing it.

[0373] • Operations of forming a metal layer and a redistribution layer on the release layer Next, a metal layer 24 is formed on the separation layer 22 formed on the support substrate 21 by means of, for example, sputtering or plating.

[0374] Figure 4B In the laminate 20 shown, a sealing material layer 28 is provided on the metal layer 24 to seal the substrate, and a redistribution layer 26 is provided on the sealing material layer 28.

[0375] The sealing material layer 28 can be formed by molding, for example, using a composition containing epoxy resin or silicone resin. The sealing material layer 28 here is not a layer that seals individual substrates, but rather preferably a layer that seals the entire substrate on the layer below the sealing material layer 28.

[0376] Regarding the redistribution layer 26, the formation of the insulating layer formed by the dielectric, the seed layer, and the wiring can be repeated as described above, thereby creating a wiring layer having an insulating layer and wiring formed within the insulating layer. As a method for forming the wiring, known semiconductor process methods such as photolithography (resist photolithography) and etching can be used.

[0377] [Separation process of the support substrate from the laminate (2-2)] In the separation process (2-2), light is irradiated from the support substrate side onto the separation layer, thereby denaturing the separation layer and separating the support substrate from the laminate.

[0378] like Figure 4C As shown, in this process (2-2), light is irradiated onto the separation layer 22 through the support substrate 21 (arrow), thereby causing the separation layer 22 to deform.

[0379] The method for separating the support substrate 21 from the laminate 20 can be performed in the same way as the separation process (1-2) described above.

[0380] [Removal process (2-3) to remove the release layer attached to the metal layer or redistribution layer] In the removal process (2-3), after the aforementioned separation process (2-2), the separation layer attached to the metal layer is removed.

[0381] Figure 4D In the process, after the separation step (2-2), a separation layer 22 is attached to the metal layer 24. In this removal step (2-3), the separation layer 22 attached to the metal layer 24 is removed.

[0382] The method for removing the separation layer 22 attached to the metal layer 24 can be the same as the operation in the removal process (1-3) described above.

[0383] Figure 4E In the end, an electronic component 200 with a stacked structure having a sealing material layer 28 and a rewiring layer 26 is obtained.

[0384] As explained above, according to the manufacturing method of the electronic component using the second embodiment employing the laminate 20, a sealing material layer 28 that seals the substrate (wiring layer) can be formed on the separation layer 22, and a redistribution layer 26 can be further suitably formed on the sealing material layer 28.

[0385] In the manufacturing method of the electronic component according to the second embodiment, bumps can be formed or components can be mounted on the redistribution layer. The mounting of components onto the redistribution layer can be performed using, for example, a pick-and-place machine.

[0386] Example The present invention will be described in more detail below through examples, but the present invention is not limited to these examples.

[0387] The transmittance of the absorber at a 1% weight reduction temperature and at a wavelength of 532 nm was measured as follows.

[0388] [1% by weight of absorber reduces temperature] The temperature was reduced by 1% by weight of the absorber as described below.

[0389] (1) The light absorber was mixed with a dispersion medium to prepare a dispersion of the light absorber. The dispersion medium selected was PGMEA, a solvent that makes the mixture of epoxy resin, light absorber and acid-producing agent homogeneous.

[0390] (2) The dispersion of the light absorber is coated on a glass substrate and subjected to a heat treatment (90°C, 3 minutes) to remove the dispersion medium, forming a light absorber film with a thickness of 1.0 μm.

[0391] (3) In thermogravimetric analysis (TGA), for a light absorber film with a thickness of 1.0 μm, the film was heated from 25 °C at a heating rate of 10 °C / min under a nitrogen atmosphere, and the weight change of the light absorber film was measured. The temperature at which the weight of the light absorber film decreased by 1% relative to the weight at the time point of 25 °C was taken as the 1% weight reduction temperature.

[0392] [Transmittance of the absorber at a wavelength of 532nm] Regarding the transmittance of the absorber, the transmittance of light when a 1.0 μm thick absorber film formed on a glass substrate is irradiated with light of 532 nm was measured using a UV-Vis spectrophotometer.

[0393] <Preparation of the composition for separating layer formation> (Examples 1-15, Comparative Examples 1-4) The components shown in Tables 1-3 were mixed and dissolved to prepare the separation layer formation compositions for each example.

[0394] [Table 1] [Table 2] [Table 3] In Tables 1-3, each abbreviation has the following meaning. The value in [ ] is the amount of the mixture (parts by mass).

[0395] Epoxy resin (P) P1-1: Bisphenol-type epoxy resin; State at 25°C: Solid P1-2: Novolac type epoxy resin; state at 25°C: solid P1-3: Naphthalene-type epoxy resin; State at 25℃: Solid P1-4: Biphenyl-type epoxy resin; State at 25°C: Solid The chemical structures of P1-1, P1-2, P1-3 and P1-4 are shown below.

[0396] [Chemical Formula 33] P2-1: Hydroxide of bisphenol type epoxy resin; State at 25°C: solid The chemical structures of P2-1 are shown below.

[0397] [Chemical Formula 34] P3-1: Alicyclic epoxy resin; state at 25°C: liquid The chemical structure of P3-1 is shown below.

[0398] [Chemical Formula 35] Other resins Carbamate acrylate, trade name "Ebecryl8804", manufactured by Daicel Corporation; state at 25°C: liquid. light absorber Light absorber (1): Trade name "CF BLACK TEN", manufactured by Mikuni Shiki Co., Ltd.; 1% weight reduction temperature is 271°C, transmittance at wavelength of 532nm is 0.2%. Light absorber (2): Trade name "ARY BLACK", manufactured by Mitsubishi Pencil Co., Ltd.; 1% weight reduction at 275°C, transmittance at 532nm is 0.8%. Light absorber (3): Trade name "LAC25", manufactured by Mitsubishi Pencil Co., Ltd.; 1% weight reduction temperature is 291°C, transmittance at wavelength 532nm is 0.6%. Light absorber (4): Trade name "TK-1992", manufactured by Mikuni Pigment Co., Ltd.; 1% weight reduction temperature is 275°C, transmittance at wavelength of 532nm is 0.7%. Light absorber (5): Trade name "D-6169", manufactured by Daido Chemical Industry Co., Ltd.; 1% weight loss temperature is 222°C, transmittance at 532nm is 0.6%. filler Packing material (1): Trade name "SO-C1", manufactured by Admatechs Co., Ltd.; 1% weight loss at 120°C, transmittance at 532nm is 95%. acid-producing agents Acid-producing agent (1): Thermal acid-producing agent Acid-producing agent (2): Thermal acid-producing agent Acid-producing agent (3): Photo-acid-producing agent The chemical structures of acid-producing agent (1), acid-producing agent (2) and acid-producing agent (3) are shown below.

[0399] [Chemical Formula 36] Free radical initiators Free radical initiator (1): The following chemical structure represents a compound [Chemical Formula 37] Other ingredients Surfactant (1): Polyester-modified silicone surfactant, trade name "BYK-310", manufactured by BYK-Chemie. Organic solvent component: Propylene glycol monomethyl ether acetate (PGMEA) [Transmittance at 532 nm of the cured composition for forming the release layer] Regarding the transmittance of the cured composition for forming the release layer, the light transmittance was measured using a UV-Vis spectrophotometer when a 1.0 μm thick cured film formed on a glass substrate was irradiated with light of 532 nm. The measurement results are shown in Tables 4-6 according to the transmittance criteria described below.

[0400] Benchmark of transmittance A: Transmittance is below 20% B: Transmittance greater than 20% and less than 30% C: Transmittance greater than 30% [Temperature reduction of 1% by weight of the cured composition for separating layer formation] The temperature was reduced by 1% by weight of the cured product of the composition for forming the separation layer as described below.

[0401] In thermogravimetric analysis (TGA), for a sample amount of 5 mg, under a nitrogen atmosphere, the sample was heated from 25 °C at a heating rate of 10 °C / min, and the weight change of the sample was measured. The temperature at which the sample weight decreased by 1% relative to the weight at the 25 °C time point was defined as the 1% weight reduction temperature. The measurement results, based on the 1% weight reduction temperature reference described below, are shown in Tables 4–6.

[0402] 1% weight reduction temperature benchmark A: 1% weight reduction at temperatures above 260℃ B: 1% weight reduction at temperatures above 200℃ and below 260℃ C: 1% weight reduction at temperatures below 200℃ <Example of manufacturing laminates> Each of the respective separation layer forming compositions was used to spin-coat a film on a 12-inch glass substrate. The coating was then heated at 90°C for 3 minutes and further heated at 250°C for 60 minutes to form a separation layer with a thickness of 1.0 μm on the glass substrate.

[0403] Next, a Ti layer (50 nm thick) and a Cu seed layer (300 nm thick) are formed on the separation layer formed on the glass substrate using a sputtering apparatus to obtain a support substrate with a metal thin film as a laminate.

[0404] <Evaluation> The laser reactivity, heat resistance, and coating adhesion were evaluated using the evaluation methods shown below. The evaluation results are presented in Tables 4-6.

[0405] [Laser Reactivity] For the glass substrate in the above-mentioned <manufacturing example of the laminate>, a separation layer with a film thickness of 1.0 μm is formed, and a laser with a wavelength of 532 nm is irradiated onto the separation layer from the glass substrate side.

[0406] The laser irradiation conditions were set as follows: frequency 50kHz, 6.0W, scanning speed 7000mm / s, and irradiation spacing 140μm.

[0407] After laser irradiation, a debonder is used to attempt to separate the separation layer from the glass substrate. The laser reactivity is evaluated based on the following evaluation criteria.

[0408] Evaluation Criteria A: It can be peeled vertically with a force of less than 2 kg.

[0409] B: Capable of vertical peeling with a force greater than 2kg and less than 4kg.

[0410] C: Failed to separate.

[0411] [Heat resistance] The laminate obtained in the above-described <Example of Laminate Manufacturing> was subjected to a heat treatment at 260°C for 1 hour. After the heat treatment, the state of the escaping gas (number of bubbles) generated in the laminate was observed visually, and the heat resistance was evaluated based on the following evaluation criteria.

[0412] Evaluation Criteria A: The number of bubbles is 0 to 2.

[0413] B: The number of bubbles is 3 or more.

[0414] [Coating adhesion] In the above-mentioned <Example of Manufacturing a Laminate>, the surface of the release layer formed on the glass substrate is touched, and it is observed by visual inspection whether there are any traces left on the surface of the release layer caused by touching. The adhesion of the coating is evaluated based on the following evaluation criteria.

[0415] Evaluation Criteria A: It is a separation layer that does not leave any traces.

[0416] B: This is a separation layer that shows slight signs of wear.

[0417] [Table 4] [Table 5] [Table 6] The results shown in Tables 4-6 confirm that the separation layer forming compositions according to Examples 1-15 can form a separation layer that allows the glass substrate to be separated from the laminate by light irradiation and improves heat resistance.

Claims

1. A composition for forming a separation layer, which is used to form the separation layer in a laminate having a separation layer between a first layer and a second layer. The first layer is a support substrate that allows light to pass through. The separation layer is a layer that can be denatured by irradiation from the support substrate side, thereby causing the support substrate to separate from the laminate. The composition for forming the separation layer contains an epoxy resin (P), a light absorber having absorption at wavelengths between 300 nm and 1300 nm, and at least one acid-generating agent selected from the group consisting of thermal acid-generating agents and photo-acid-generating agents. The curing temperature of the composition for forming the separation layer is above 200°C, with a reduction of 1% by weight.

2. The composition for forming a release layer as claimed in claim 1, wherein, The epoxy resin (P) comprises epoxy resin (PO) that is solid at 25°C. The proportion of epoxy resin (P0) in the epoxy resin (P) is 50 to 100% by mass relative to the total mass (100% by mass) of the epoxy resin (P).

3. The composition for forming a release layer as claimed in claim 1, wherein, The epoxy resin (P) comprises epoxy resin (P1), wherein the epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl-type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

4. The composition for forming a release layer as claimed in claim 1, wherein, The epoxy resin (P) comprises a hydride (P2) of epoxy resin (P1), wherein the epoxy resin (P1) is at least one selected from the group consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl-type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

5. The composition for forming a separation layer as claimed in claim 1, wherein, The epoxy resin (P) comprises both epoxy resin (P1) and a hydride of the epoxy resin (P1) (P2). The epoxy resin (P1) is selected from at least one of the groups consisting of bisphenol type epoxy resin, Novolac type epoxy resin, biphenyl-type epoxy resin and naphthalene type epoxy resin, and has two or more epoxy functional groups.

6. The composition for forming a separation layer as claimed in claim 1, wherein, The light absorber has a 1% weight reduction temperature of 200°C or higher.

7. The composition for forming a release layer as claimed in claim 1, wherein, The transmittance of the light absorber at a wavelength of 532 nm is less than 20%.

8. The composition for forming a release layer as claimed in claim 1, wherein, The content of the light absorber is 10 to 100 parts by weight relative to 100 parts by weight of the epoxy resin (P).

9. A laminated body, wherein a separation layer is provided between the first and second layers. The first layer is a support substrate that allows light to pass through. The separation layer is formed by curing the separation layer forming composition according to any one of claims 1 to 8.

10. The laminate as claimed in claim 9, wherein, The second layer is a seed crystal layer.

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