JP2019034541A - Composition for forming separate layer, supporting substrate with separation layer, laminate and manufacturing method therefor, and manufacturing method of electronic component - Google Patents

Abstract

To provide a composition for forming a separation layer or the like, capable of forming the separation layer making separability of a supporting substrate from a laminate good by enhancing light reactivity in the laminate having the separation layer between the supporting substrate and a base plate.SOLUTION: There is adopted a composition for forming a separation layer for forming the separation layer 2 capable of separating a supporting substrate 1 from a laminate 10 by modifying the laminate 10 having the separation layer 2 and an adhesive layer 3 between the supporting substrate 1 transmitting a light and a base plate 4 with irradiation of the light from a side of the supporting substrate 1, containing a resin component (P) having a phenol skeleton.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for forming a separation layer, a support base with a separation layer, a laminate and a method of manufacturing the same, and a method of manufacturing an electronic component.

There are various forms of a semiconductor package (electronic component) including a semiconductor element according to the corresponding size, and there are, for example, WLP (Wafer Level Package), PLP (Panel Level Package) and the like.
Semiconductor package technologies include fan-in technology and fan-out technology. As a semiconductor package based on the fan-in type technology, a fan-in type wafer level package (WLP) or the like in which terminals at the end of a bare chip are rearranged in a chip area is known. As a semiconductor package based on the fan-out type technology, a fan-out type wafer level package (WLP) or the like in which the terminal is rearranged outside the chip area is known.

  In recent years, fan-out technology, in particular, has been applied to fan-out panel level packages (PLP) in which semiconductor elements are arranged and packaged on a panel, etc. Attention has been drawn as a method that can realize thinning and downsizing.

In order to miniaturize the semiconductor package, it is important to reduce the thickness of the substrate in the incorporated device. However, if the thickness of the substrate is reduced, the strength thereof is reduced, and the substrate is likely to be damaged when manufacturing a semiconductor package. On the other hand, a laminate in which a support base is bonded to a substrate is employed.
In Patent Document 1, a light-transmitting support base and a substrate are bonded via a light-to-heat conversion layer (separation layer) and an adhesive layer provided on the support base side, and the support is processed after processing the substrate. Disclosed is a method of manufacturing a laminate by separating a substrate after processing and a supporting substrate by irradiating the separation layer from the side with radiant energy (light) to alter the separation layer and decomposing it. .

JP 2004-64040 A

As described in Patent Document 1, when a semiconductor package is miniaturized by adopting a laminate in which a support base is bonded to a substrate, the separation of the support base from the laminate becomes a problem.
The present invention has been made in view of the above-mentioned circumstances, and in a laminate having a separation layer between a support substrate and a substrate, the photoreactivity is enhanced to separate the support substrate from the laminate. It is an object of the present invention to provide a separation layer-forming composition capable of forming a separation layer to be improved, a support base with a separation layer using the same, a laminate and a method of manufacturing the same, and a method of manufacturing an electronic component.

In order to solve the above-mentioned subject, the present invention adopted the following composition.
That is, according to the first aspect of the present invention, in a laminate having a separation layer between a support substrate transmitting light and a substrate, the laminate is denatured by the irradiation of light from the support substrate side, and the lamination is performed. A composition for forming a separation layer for forming the separation layer capable of separating the support base from a body, comprising a resin component (P) having a phenol skeleton, for forming a separation layer It is a composition.

  According to a second aspect of the present invention, there is provided a support base, and a separation layer formed on the support base using the composition for forming a separation layer according to the first aspect, It is a support base with a separation layer.

  A third aspect of the present invention is a laminate comprising a separation layer between a support substrate transmitting light and a substrate, wherein the separation layer is for forming a separation layer according to the first aspect. It is a laminate characterized in that it is a fired body of a composition.

  A fourth aspect of the present invention is a method for producing a laminate comprising a separation layer between a support substrate transmitting light and a substrate, wherein at least one of the substrate and the support substrate is provided. A separation layer forming step of forming the separation layer by applying the composition for forming the separation layer according to the first aspect and then baking the composition, and the substrate and the support base through the separation layer. And a laminating step of laminating.

  According to a fifth aspect of the present invention, after obtaining a laminate by the method for producing a laminate according to the fourth aspect, the separation layer is irradiated with light through the supporting substrate to alter the separation layer. And separating the support substrate from the laminate provided in the laminate, and removing the separation layer attached to the substrate after the separation step. Is a method of manufacturing an electronic component.

  According to the present invention, in a laminate provided with a separation layer between a support substrate and a substrate, a separation layer capable of forming a separation layer capable of enhancing the photoreactivity and improving the separation of the support substrate from the laminate. It is possible to provide a composition for formation, a support base with a separation layer using the same, a laminate and a method for producing the same, and a method for producing an electronic component.

It is a schematic diagram which shows one Embodiment of the laminated body to which this invention is applied. It is a schematic process drawing explaining one embodiment of the manufacturing method of a layered product. FIG. 2A is a view for explaining the separation layer formation step, and FIG. 2B is a view for explaining the lamination step. It is a schematic process drawing explaining the other embodiment of the manufacturing method of a layered product. Fig.3 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 1st Embodiment, FIG.3 (b) is a figure explaining a sealing process. It is a schematic process drawing explaining the other embodiment of the manufacturing method of a layered product. Fig.4 (a) is a figure which shows the sealing body manufactured by the manufacturing method of 2nd Embodiment, FIG.4 (b) is a figure explaining a grinding process, FIG.4 (c) is a re It is a figure explaining a wiring formation process. It is a schematic process drawing explaining one embodiment of the manufacturing method of a semiconductor package (electronic component). Fig.5 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 3rd Embodiment, FIG.5 (b) is a figure explaining a isolation | separation process, FIG.5 (c) is a removal. It is a figure explaining a process. It is a schematic process drawing explaining the other embodiment of the manufacturing method of a semiconductor package (electronic component). FIG. 6 (a) is a schematic view showing another embodiment of a laminate to which the present invention is applied, FIG. 6 (b) is a view for explaining a separation step, and FIG. 6 (c) is a removal It is a figure explaining a process.

In the present specification and claims, “aliphatic” is a concept relative to an aromatic and is defined to mean a group, a compound or the like having no aromaticity.
The term "alkyl group" is intended to include linear, branched and cyclic monovalent saturated hydrocarbon groups, unless otherwise specified. The same applies to the alkyl group in the alkoxy group.
The "alkylene group" is intended to include a linear, branched and cyclic divalent saturated hydrocarbon group unless otherwise specified.
The “halogenated alkyl group” is a group in which part or all of hydrogen atoms of an alkyl group is substituted with a halogen atom, and examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The "fluorinated alkyl group" or "fluorinated alkylene group" refers to a group in which part or all of the hydrogen atoms of the alkyl group or the alkylene group are substituted with a fluorine atom.
The "constituent unit" means a monomer unit (monomer unit) constituting a polymer compound (resin, polymer, copolymer).
When it is described as “optionally substituted” or “optionally substituted”, a hydrogen atom (—H) is substituted with a monovalent group, and a methylene group (—CH ₂₎ It includes both the case where-) is substituted with a divalent group.
"Exposure" is a concept that includes general radiation irradiation.

The “structural unit derived from hydroxystyrene” means a structural unit formed by cleavage of the ethylenic double bond of hydroxystyrene. The “constituent unit derived from hydroxystyrene derivative” means a constituent unit formed by cleavage of the ethylenic double bond of the hydroxystyrene derivative.
The term "hydroxystyrene derivative" is a concept including those in which a hydrogen atom at the alpha position of hydroxystyrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As their derivatives, those in which the hydrogen atom of hydroxystyrene which may be substituted with a hydrogen atom at the α position is substituted with an organic group; even if the hydrogen atom at the α position is substituted by a substituent A compound in which a substituent other than a hydroxyl group is bonded to the benzene ring of good hydroxystyrene, and the like can be mentioned. The alpha position (carbon atom at the alpha position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.
As a substituent which substitutes the hydrogen atom of alpha position of hydroxystyrene, the thing similar to what was mentioned as a substituent of alpha position in the above-mentioned alpha substitution acrylic acid ester is mentioned.

"Styrene" is a concept including styrene and those in which a hydrogen atom at the alpha position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group.
The term "styrene derivative" is a concept that includes those in which a hydrogen atom at the alpha position of styrene is substituted with another substituent such as an alkyl group or a halogenated alkyl group, and derivatives thereof. As the derivatives thereof, those in which a substituent is bonded to a benzene ring of styrene which may be substituted with a hydrogen atom at the α-position may be mentioned. The alpha position (carbon atom at the alpha position) refers to the carbon atom to which the benzene ring is bonded unless otherwise specified.
The “structural unit derived from styrene” and the “structural unit derived from a styrene derivative” mean a structural unit formed by cleavage of an ethylenic double bond of styrene or a styrene derivative.

The alkyl group as a substituent at the α-position is preferably a linear or branched alkyl group, and specifically, an alkyl group having 1 to 5 carbon atoms (a methyl group, an ethyl group, a propyl group, an isopropyl group) , N-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group) and the like.
In addition, specific examples of the halogenated alkyl group as a substituent at the α-position include groups in which part or all of the hydrogen atoms of the above “alkyl group as a substituent at the α-position” are substituted with a halogen atom Be Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom is particularly preferable.
Further, specific examples of the hydroxyalkyl group as a substituent at the α-position include groups in which part or all of the hydrogen atoms of the above-mentioned “alkyl group as a substituent at the α-position” are substituted with a hydroxyl group. The number of hydroxyl groups in the hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

(Composition for forming separation layer)
The composition for forming a separation layer according to the first aspect of the present invention is a laminate comprising a separation layer between a support substrate transmitting light and a substrate, wherein irradiation of light from the support substrate side is performed. It is for forming the said isolation | separation layer which can be denatured and the said support body can be isolate | separated from the said laminated body. The composition for forming a separation layer of the present embodiment contains at least a resin component (P) having a phenol skeleton.

FIG. 1 shows an embodiment of a laminate to which the present invention is applied.
The laminate 10 shown in FIG. 1 is provided with the separation layer 2 and the adhesive layer 3 between the support substrate 1 and the substrate 4, and the separation layer 2, the adhesive layer 3 and the substrate 4 are provided on the support substrate 1. It is laminated in this order.
The support substrate 1 is made of a material that transmits light. In the laminate 10, the separation layer 2 is irradiated with light from the side of the support base 1 to degrade the separation layer 2 so that the support base 1 is separated from the laminate 10.
The separation layer 2 in the laminate 10 can be formed using the composition for forming a separation layer of the present embodiment.

<Resin component (P)>
The resin component (P) (hereinafter also referred to as “component (P)”) is a resin component having a phenol skeleton.
As used herein, "having a phenol skeleton" means containing a hydroxybenzene structure.

The component (P) has a film-forming ability, and preferably has a molecular weight of 1000 or more. When the molecular weight of the component (P) is 1,000 or more, the film forming ability is improved. As for the molecular weight of (P) component, 1000-30000 are more preferable, 1500-20000 are more preferable, 2000-15000 are especially preferable.
When the molecular weight of the component (P) is not more than the upper limit value of the preferable range described above, the solubility of the composition for forming a separation layer in a solvent is enhanced.
In addition, as a molecular weight of a resin component, the weight average molecular weight (Mw) of polystyrene conversion by GPC (gel permeation chromatography) shall be used.

  Moreover, (P) component is easily denatured (oxidized etc.) by heating etc. by having a phenol skeleton, and photoreactivity increases. Then, the component (P) is decomposed by heat generated by light absorption. Therefore, in the laminate 10, the separation layer 2 is denatured and peeled off from the substrate 4 by the irradiation of light from the supporting substrate 1 side, and the supporting substrate 1 is separated.

The component (P) is not particularly limited as long as it has a phenol skeleton, and, for example, novolac type phenol resin, resol type phenol resin, hydroxystyrene resin, hydroxyphenylsilsesquioxane resin, hydroxybenzylsilsesquioxane resin A phenol skeleton-containing acrylic resin, a resin having a repeating unit represented by General Formula (P2) described later, and the like can be mentioned. Among these, novolac type phenol resins, resol type phenol resins, and resins having a repeating unit represented by formula (P2) are more preferable.
Among them, as the component (P), particularly, one containing a novolac-type phenol resin is preferable since generation of a void by heating can be easily suppressed. Alternatively, as the component (P), one containing a resin having a repeating unit represented by general formula (P2) is particularly preferable since chemical resistance is also easily enhanced.

«Novolak-type phenolic resin»
The novolak type phenol resin (hereinafter also referred to as “resin (P1)”) which can be used as the component (P), for example, contains m-cresol repeating unit (u11) and p-cresol repeating unit (u12) as main components Phenolic resins are preferably used.

  The “phenol resin having“ m-cresol repeating unit (u11) and p-cresol repeating unit (u12) as main components ”” is a repeating unit that occupies the entire repeating units derived from phenols that constitute the phenol resin. It means that the ratio of the sum total of a unit (u11) and a repeating unit (u12) is 50 mol% or more. The proportion of the total is preferably 80 mol% or more, more preferably 80 to 100 mol%, particularly preferably 100 mol%.

In the resin (P1), the mixing ratio (molar ratio) of the repeating unit (u11) to the repeating unit (u12) is preferably the repeating unit (u11) and the repeating unit (u12) = 2/8 to 9/1, and more preferably It is preferably 3/7 to 7/3, more preferably 4/6 to 6/4.
If the mixing ratio in the resin (P1) is within the above-mentioned preferred range, the photoreactivity of the separation layer can be further enhanced. In addition, chemical resistance is also enhanced.
Here, the mixing ratio (molar ratio) of the resin (P1) is the mixing ratio (molar ratio) of the m-cresol repeating unit (u11) and the p-cresol repeating unit (u12) in the novolak-type phenolic resin after production Means

The resin (P1) may have other repeating units in addition to the repeating unit (u11) and the repeating unit (u12).
When the resin (P1) has another repeating unit, the other repeating unit in the resin (P1) may be one type or two or more types.
Other repeating units include repeating units derived from phenols other than m-cresol and p-cresol, and examples thereof include phenol, o-cresol; 2,3-xylenol, 2,5-xylenol and 2,6- Xylenols such as xylenol, 3,5-xylenol and 3,4-xylenol; m-ethylphenol, p-ethylphenol, o-ethylphenol, 2,3,5-trimethylphenol, 2,4,6-trimethylphenol 2,3,5-Triethylphenol, 4-tert-butylphenol, 3-tert-butylphenol, 2-tert-butylphenol, 2-tert-butyl-4-methylphenol, 2-tert-butyl-5-methylphenol etc. Alkyl phenols; p-methoxy And alkoxyphenols such as m-methoxyphenol, p-ethoxyphenol, m-ethoxyphenol, p-propoxyphenol and m-propoxyphenol; o-isopropenyl phenol, p-isopropenyl phenol, 2-methyl-4- 4- Isopropenylphenols such as isopropenylphenol and 2-ethyl-4-isopropenylphenol; arylphenols such as phenylphenol; polyhydroxyphenols such as 4,4'-dihydroxybiphenyl, bisphenol A, resorcinol, hydroquinone and pyrogallol 1-naphthol, 2-naphthol and the like can be mentioned.

  The content ratio of the resin (P1) to the component (P) is appropriately set according to the required characteristics, and for example, is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass or more More preferably, it may be 100% by mass.

Resin (P1) can be obtained, for example, by reacting m-cresol, p-cresol and aldehydes under an acidic catalyst.
In such a reaction, by controlling the ratio of m-cresol to p-cresol, it is possible to produce a novolac phenolic resin having repeating units (u11) and repeating units (u12) at a predetermined mixing ratio.
Such reaction can be carried out in a known manner under an acidic catalyst. As the acidic catalyst, for example, hydrochloric acid, sulfuric acid, formic acid, oxalic acid, p-toluenesulfonic acid and the like can be used.
Examples of the aldehyde include formaldehyde, paraformaldehyde, trioxane, acetaldehyde, propionaldehyde, butyraldehyde, trimethylacetaldehyde, acrolein, crotonaldehyde, cyclohexanealdehyde, furfural, furylacrolein, benzaldehyde, terephthalaldehyde, phenylacetaldehyde, α-phenylpropyl Aldehyde, β-phenylpropyl aldehyde, o-hydroxy benzaldehyde, m-hydroxy benzaldehyde, p-hydroxy benzaldehyde, o-methyl benzaldehyde, m-methyl benzaldehyde, p-methyl benzaldehyde, o-chloro benzaldehyde, m-chloro benzaldehyde, p- Chlorobenzaldehyde, cinnamate Rudedeide, salicylaldehyde and the like can be mentioned. Among these, formaldehyde and salicylaldehyde are preferable. From the viewpoint of imparting heat resistance, salicylaldehyde is preferred.
The aldehydes may be used alone or in combination of two or more.

  In addition, for the resin (P1), for example, a phenol resin containing a naphthol repeating unit and a phenol repeating unit as main components is preferably used from the viewpoint of reduction of firing temperature or suppression of void formation. This phenolic resin can be obtained by reacting naphthol, phenol and aldehyde with an acidic catalyst.

1000-30000 are preferable, as for the weight average molecular weight (Mw) of resin (P1), 1500-20000 are more preferable, and 2000-15000 are especially preferable.
If Mw of resin (P1) is more than the lower limit value of the said preferable range, film formation ability will improve, and if it is below the upper limit value of the said preferable range on the other hand, with respect to the solvent of the composition for isolation layer formation Solubility is enhanced.

«Resol type phenolic resin»
As a resol type phenol resin which can be used as a (P) component, the thing of a weight average molecular weight (Mw) 500-10000 is preferable, the thing of 500-5000 is more preferable, and the thing of 1000-2000 is especially preferable.
If Mw of resol type phenol resin is more than the lower limit value of the above-mentioned preferable range, film formation ability will improve, and if it is below the upper limit value of the above-mentioned preferable range on the other hand, the solvent for composition of separation layer formation Solubility is enhanced.

«Resin (P2)»
The resin (P2) is a resin having a repeating unit represented by the following general formula (P2).

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

[ ^Wherein , L ^p1 is a divalent linking group. R ^P is an (n _{P 0} +1) -valent aromatic hydrocarbon group. n _P0 is an integer of 1 to 3. ]

In the formula (P2), L ^p1 is a divalent linking group, and a divalent linking group containing a hetero atom is preferable. ^Examples of L ^p1 include linking groups into which various skeletons have been introduced in order to impart desired properties.

In the formula (P2), R ^P is a (n _{P 0} +1) -valent aromatic hydrocarbon group.
Examples of the aromatic hydrocarbon group in R ^P include groups in which (n _{P 0} +1) hydrogen atoms have been removed from the aromatic ring. The aromatic ring here is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The aromatic ring preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, still more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, phenanthrene, and the like; aromatic heterocycles in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, etc. Can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
The aromatic hydrocarbon group for R ^P, aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.) may be mentioned groups except from the (n _{P0 +1)} number of hydrogen atoms.

In said Formula (P2), _nP0 is an integer of 1-3, 1 or 2 is preferable, and 1 is especially preferable.

1 mass% or more is preferable with respect to the total amount (100 mass%) of resin (P2), as for the hydroxyl group content rate of resin (P2), 5-50 mass% is more preferable, and 5-20 mass% is more preferable.
When the hydroxyl group content of the resin (P2) is equal to or more than the lower limit value of the above-mentioned preferable range, oxidation is further promoted by baking when forming the separation layer. On the other hand, if it is below the upper limit of the said preferable range, the solubility with respect to the solvent of the composition for separate layer formation will be improved.

  As a repeating unit represented by said general formula (P2), the repeating unit represented by the following general formula (P2-1) is mentioned suitably, for example.

［式中、Ｌ^ｐ１１は、２価の連結基である。Ｒ^Ｐは、（ｎ_Ｐ０＋１）価の芳香族炭化水素基である。ｎ_Ｐ０は、１〜３の整数である。］

[ ^Wherein , L ^p11 is a divalent linking group. R ^P is an (n _{P 0} +1) -valent aromatic hydrocarbon group. n _P0 is an integer of 1 to 3. ]

In the formula (P2-1), L ^p11 is a divalent linking group, and various skeletons are introduced into the linking group according to the desired characteristics.
As L ^p11 , for example, an ether bond group of bisphenols, an ether bond group of diols, an ester bond group of dicarboxylic acids, a Si—O bond group or a repeating structure of these bond groups can be mentioned.
As the said bisphenols, bisphenol F, bisphenol A, bisphenol Z, biphenol, or these polymers etc. are mentioned.
Examples of the diols include ethylene glycol, propylene glycol, 1,6-hexanediol, neopentyl glycol, and polymers of these.
Examples of the dicarboxylic acids include maleic acid, phthalic acid, hydrogenated phthalic acid and terephthalic acid.

When an ether bond group of bisphenols is selected as L ^p11 , the flexibility of a film made of a resin (P2) can be easily enhanced.
When the ether bond group of diols is selected as L ^p11 , the alkali solubility of the resin (P2) can be easily adjusted. As a glycol skeleton, a propylene glycol skeleton is mentioned, for example.
When a Si—O bond is selected as L ^p11 , it becomes easy to lower the dielectric constant of the resin (P 2) molded body.

  The content ratio of the resin (P2) to the component (P) is appropriately set according to the required characteristics, and for example, is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more More preferably, it may be 100% by mass.

1000-30000 are preferable, as for the weight average molecular weight (Mw) of resin (P2), 1500-25000 are more preferable, and 2000-20000 are especially preferable.
If Mw of resin (P2) is more than the lower limit value of the said preferable range, film formation ability will improve, and if it is below the upper limit value of the said preferable range on the other hand, with respect to the solvent of the composition for isolation layer formation Solubility is enhanced.

  As resin (P2), GSP series (made by Gunei Chemical Industry Co., Ltd.) etc. whose brand name is GSP-01, GSP-02, GSP-03 etc. can be used, for example.

Alternatively, as the resin (P2), a resin produced by reacting aminophenols, aminonaphthols or anilines with a compound having two epoxy groups in one molecule can also be used.
As aminophenols, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-amino-3-methylphenol, 2-amino-4-methylphenol, 3-amino-2-methylphenol, 5-aminophenol Amino-2-methylphenol and the like. Examples of aminonaphthols include 1-amino-2-naphthol, 3-amino-2-naphthol, 5-amino-1-naphthol and the like.
As a compound having two epoxy groups in one molecule, for example, bisphenol-type epoxy resins such as EPICLON 850, EPICLON 830 (manufactured by DIC Corporation), jERYX-4000 (manufactured by Mitsubishi Chemical Corporation) under the trade name; DENACOL EX-211, A diol type epoxy resin such as DENACOL EX-212, DENACOL EX-810, DENACOL EX-830, DENACOL EX-911, DENACOL EX-920, DENACOL EX-930 (manufactured by Nagase ChemteX Co., Ltd.); DENACOL EX-711, DENACOL Dicarboxylic acid ester type epoxy resins such as EX-721 (manufactured by Nagase ChemteX Co., Ltd.) and jER191P (manufactured by Mitsubishi Chemical Corporation); X-22-163, KF-105 And silicone type epoxy resins such as those manufactured by Otsu Chemical Co., Ltd.).
It is preferable to set it as 60 degreeC or more and 250 degrees C or less, and, as for the heat processing temperature in the case of this reaction, it is more preferable to set it as 80 degreeC or more and 180 degrees C or less.

The component (P) contained in the composition for forming a separation layer of the present embodiment may be one kind or two or more kinds.
As the component (P), one or more selected from the group consisting of the resin (P1) and the resin (P2) described above is preferable, and the resin (P1) and the resin (P2) are appropriately combined according to the required characteristics. Can be used.

  When the separation layer is formed, the higher the content ratio of the resin (P1) in the (P) component is, for example, the effect of suppressing the generation of voids is improved. 5 mass% or more is preferable, as for the content rate of resin (P1) to 100 mass% of this (P) component, 10 mass% or more is more preferable, 20 mass% or more is further more preferable, 30 mass% or more is still more Preferably, 50% by mass or more is particularly preferable.

  When the separation layer is formed, for example, the chemical resistance is improved as the content ratio of the resin (P2) to the (P) component increases. 50 mass% or more is preferable, as for the content rate of resin (P2) to 100 mass% of this (P) component, 70 mass% or more is more preferable, 80 mass% or more is more preferable, 90 mass% or more is especially preferable .

The content of the component (P) in the composition for forming a separation layer of the present embodiment may be adjusted according to the thickness of the separation layer to be formed, and the like.
The content of the component (P) in the composition for forming a separation layer is, for example, preferably 1 to 100% by mass, more preferably 5 to 50% by mass, with respect to the composition (100% by mass). -40 mass% is further more preferable.
When the content of the component (P) is equal to or more than the lower limit value of the preferable range described above, the photoreactivity of the separation layer tends to be further enhanced. In addition, chemical resistance is also likely to be enhanced. On the other hand, when it is below the upper limit value of the above-mentioned preferable range, photoreactivity and releasability become easier to be enhanced.

<Other ingredients>
The composition for forming a separation layer of the present embodiment may further contain components (optional components) other than the component (P) described above.
Examples of such optional components include photosensitizer components, thermal acid generator components, photoacid generator components, organic solvent components, surfactants, and sensitizers described below.

«Photosensitizer composition»
As the photosensitive agent component (hereinafter, also referred to as “component (C)”), for example, an esterification of a phenolic hydroxyl group-containing compound represented by the following chemical formula (c1) with a 1,2-naphthoquinone diazide sulfonic acid compound A reaction product (hereinafter also referred to as “component (C1)”) is mentioned as a suitable one.

  As a 1,2-naphthoquinone diazide sulfonic acid compound, a 1,2-naphthoquinone diazide-5-sulfonyl compound, a 1,2-naphthoquinone diazide-4-sulfonyl compound and the like can be mentioned, and a 1,2-naphthoquinone diazide-5-sulfonyl compound can be mentioned. Compounds are preferred.

  Below, the suitable specific example of (C1) component is shown.

［式（ｃ１−１）中、Ｄ^１〜Ｄ^４は、それぞれ独立に水素原子、又は１，２−ナフトキノンジアジド−５−スルホニル基を表す。Ｄ^１〜Ｄ^４のうち少なくとも１つは、１，２−ナフトキノンジアジド−５−スルホニル基を表す。］

[In Formula (c1-1), D ^{1 to} D ⁴ each independently represent a hydrogen atom, or a 1,2-naphthoquinonediazide-5-sulfonyl group. At least one of D ^{1 to} D ⁴ represents a 1,2-naphthoquinone diazide-5-sulfonyl group. ]

It is preferable that it is 50 to 70%, and, as for the esterification rate of the said (C1) component, it is more preferable that it is 55 to 65%. When the esterification rate is 50% or more, film reduction after alkali development is further suppressed, and the residual film rate is increased. If the esterification rate is 70% or less, the storage stability is further improved.
The term “esterification rate” as used herein means that, for the compound represented by the formula (c1-1), D ^{1 to} D ⁴ in the formula (c1-1) are 1,2-naphthoquinone diazide-5-sulfonyl Indicates the percentage of substitution by a group.
The component (C1) is preferable from the viewpoint of achieving high sensitivity while being very inexpensive.

In addition, as the component (C), other photosensitizer components other than the component (C1) (hereinafter, also referred to as "component (C2)") can be used.
As the component (C2), for example, the following phenolic hydroxyl group-containing compound ((c2-phe) component) and a 1,2-naphthoquinonediazide sulfonic acid compound (preferably, a 1,2-naphthoquinonediazide-5-sulfonyl compound Or an esterification reaction product of 1,2-naphthoquinonediazide-4-sulfonyl compound) is mentioned as a suitable thing.

  Examples of the (c2-phe) component include tris (4-hydroxyphenyl) methane, bis (4-hydroxy-3-methylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,3,5). -Trimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3-hydroxyphenylmethane Bis (4-hydroxy-3,5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -4-hydroxyphenylmethane, bis (4-hydroxy-2,5 -Dimethylphenyl) -3-hydroxyphenylmethane, bis (4-hydroxy-2) 5-dimethylphenyl) -2-hydroxyphenylmethane, bis (4-hydroxy-3,5-dimethylphenyl) -3,4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -3, 4-dihydroxyphenylmethane, bis (4-hydroxy-2,5-dimethylphenyl) -2,4-dihydroxyphenylmethane, bis (4-hydroxyphenyl) -3-methoxy-4-hydroxyphenylmethane, bis (5- Cyclohexyl-4-hydroxy-2-methylphenyl) -4-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3-hydroxyphenylmethane, bis (5-cyclohexyl-4-hydroxy-) 2-Methylphenyl) -2-hydroxyphenyl ester , Bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane, bis (2,3,5-trimethyl-4-hydroxyphenyl) -2-hydroxyphenylmethane, 1- [1- (4-hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- 4 [1,1-Bis (3-methyl-4-hydroxyphenyl) ethyl] benzene, 2- (2,3,4-trihydroxyphenyl) -2- (2 ′, 3 ′, 4′-trihydroxyphenyl) Propane, 2- (2,4-dihydroxyphenyl) -2- (2 ′, 4′-dihydroxyphenyl) propane, 2- (4-hydroxyphenyl) -2 -(4'-hydroxyphenyl) propane, 2- (3-fluoro-4-hydroxyphenyl) -2- (3'-fluoro-4'-hydroxyphenyl) propane, 2- (2,4-dihydroxyphenyl)- 2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl)- 2- (4'-hydroxy-3 ', 5'-dimethylphenyl) propane, bis (2,3,4-trihydroxyphenyl) methane, bis (2,4-dihydroxyphenyl) methane, 2,3,4- Trihydroxyphenyl-4'-hydroxyphenylmethane, 1,1-di (4-hydroxyphenyl) cyclohexane, 2,4-bis [1- (4-hydroxy) Eniru) isopropyl] -5-hydroxy phenols, and the like.

As the component (C) contained in the composition for forming a separation layer of the present embodiment, one type may be used alone, or two or more types may be used in combination.
Among the above, it is preferable to use the component (C1) as the component (C) in the composition for forming a separation layer of the present embodiment.
When the composition for forming a separation layer of the present embodiment contains the component (C), the content of the component (C) is preferably 95 parts by mass or less with respect to 100 parts by mass of the component (P), 50-95 mass parts is more preferable, and 60-90 mass parts is further more preferable.
If the content of the component (C) is within the above-mentioned preferred range, the photoreactivity of the separation layer is further enhanced.

«Thermal acid generator»
In the composition for forming a separation layer of the present embodiment, it is preferable to further contain a thermal acid generator (hereinafter also referred to as "(T) component"). Since the composition for forming the separation layer contains the (T) component, the separation layer is promoted to be oxidized by the action of the acid generated from the (T) component during heating at the time of firing, etc. It is easy to deteriorate (the photoreactivity of the separation layer is enhanced).

The component (T) can be appropriately selected from known ones and used, and the temperature for generating the acid is the temperature or more at the time of prebaking the supporting substrate coated with the composition for forming the separation layer Is preferable, one having 110 ° C. or more is more preferable, and one having 130 ° C. or more is more preferable.
Examples of the component (T) include trifluoromethanesulfonate, hexafluorophosphate, perfluorobutanesulfonate, boron trifluoride salt, boron trifluoride etherate and the like. As a preferable (T) component, the compound which consists of a cation part shown below and an anion part is mentioned.

［式（Ｔ−ｃａ−１）中、Ｒ^ｈ０１〜Ｒ^ｈ０４は、それぞれ独立して、水素原子、炭素数１〜２０のアルキル基及びアリール基からなる群より選択される基であり、Ｒ^ｈ０１〜Ｒ^ｈ０４のうちの少なくとも１つは、アリール基である。前記のアルキル基又はアリール基は、置換基を有していてもよい。式（Ｔ−ｃａ−２）中、Ｒ^ｈ０５〜Ｒ^ｈ０７は、それぞれ独立して、炭素数１〜２０のアルキル基及びアリール基からなる群より選択される基であり、Ｒ^ｈ０５〜Ｒ^ｈ０７のうちの少なくとも１つは、アリール基である。前記のアルキル基又はアリール基は、置換基を有していてもよい。］

[In the formula (T-ca-1), R ^{h01 to} R ^h04 each independently represent a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, and an aryl group, and R ^{h01 -At} least one of R ^h04 is an aryl group. The aforementioned alkyl group or aryl group may have a substituent. In the formula (T-ca-2), R ^{h05 to} R ^h07 are each independently a group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an aryl group, and R ^{h05 to} R ^h07 is a group At least one of them is an aryl group. The aforementioned alkyl group or aryl group may have a substituent. ]

^-About the cation part of (T) component In said Formula (T-ca-1), the alkyl group in R ^h01- R ^h04 is C1-C20, C1-C10 is preferable, C1 is one -5 is more preferable, and a C1-C5 linear or branched alkyl group is further more preferable. Specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Ethyl is preferred.

The alkyl group in R ^{h01 to} R ^h04 may have a substituent. Examples of this substituent include an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group and a cyclic group.

The alkoxy group as a substituent of the alkyl group is preferably an alkoxy group having a carbon number of 1 to 5, and more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group or a tert-butoxy group , Methoxy and ethoxy are more preferred.
A fluorine atom, a chlorine atom, a bromine atom, an iodine atom etc. are mentioned as a halogen atom as a substituent of an alkyl group, A fluorine atom is preferable.
The halogenated alkyl group as a substituent of the alkyl group is a part or all of hydrogen atoms such as an alkyl group having 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group and tert-butyl group And the group substituted by the said halogen atom are mentioned.
Carbonyl group as the substituent for the alkyl group are methylene group constituting the alkyl group - is to replace the group (> C = O) (-CH 2).
The cyclic group as a substituent of the alkyl group includes an aromatic hydrocarbon group and an alicyclic hydrocarbon group (which may be polycyclic or may be monocyclic). As the aromatic hydrocarbon group here, those similar to the aryl group in R ^{h01 to} R ^h04 described later can be mentioned. In the alicyclic hydrocarbon group here, as the monocyclic alicyclic hydrocarbon group, a group in which one or more hydrogen atoms have been removed from a monocycloalkane is preferable. The monocycloalkane is preferably one having 3 to 6 carbon atoms, and specific examples include cyclopentane, cyclohexane and the like. Moreover, as a polycyclic alicyclic hydrocarbon group, the group which remove | eliminated one or more hydrogen atoms from polycyclo alkane is preferable, and as this polycyclo alkane, a C7-C30 thing is preferable. Among them, as the polycycloalkane, a polycycloalkane having a bridged ring type polycyclic skeleton such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like; a condensed ring system such as a cyclic group having a steroid skeleton More preferred are polycycloalkanes having a polycyclic skeleton of

In the formula (T-ca-1), the aryl group in R ^{h01 to} R ^h04 is a hydrocarbon group having at least one aromatic ring.
The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n + 2 π electrons, and may be monocyclic or polycyclic. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12.
Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene and phenanthrene; and aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom, etc. It can be mentioned. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.
Specifically, as the aryl group for R ^{h01 to} R ^h04, a group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; an aromatic compound containing two or more aromatic rings (eg, biphenyl) And a group in which one hydrogen atom is removed from fluorene and the like); a group in which one hydrogen atom of the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkylene group (for example, benzyl group, phenethyl group, 1- And arylalkyl groups such as naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group and the like. It is preferable that carbon number of the alkylene group couple | bonded with the said aromatic hydrocarbon ring or aromatic heterocycle is 1-4, It is more preferable that it is 1-2, It is especially preferable that it is 1. Among these, a group obtained by removing one hydrogen atom from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle, one of the hydrogen atoms of the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle is substituted by an alkylene group A group is more preferable, and a group in which one hydrogen atom is removed from the aromatic hydrocarbon ring, and a group in which one hydrogen atom of the aromatic hydrocarbon ring is substituted with an alkylene group are more preferable.

The aryl group in R ^{h01 to} R ^h04 may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, a cyclic group, an alkylcarbonyloxy group and the like.

The alkyl group as a substituent of the aryl group is preferably an alkyl group having 1 to 5 carbon atoms, and is preferably a methyl group, an ethyl group, a propyl group, an n-butyl group or a tert-butyl group.
The description about the alkoxy group as a substituent of an aryl group, a halogen atom, a halogenated alkyl group, a carbonyl group, and a cyclic group is the alkoxy group as a substituent of the alkyl group mentioned above, a halogen atom, a halogenated alkyl group, a carbonyl The same applies to the groups and cyclic groups.
In the alkylcarbonyloxy group as a substituent of the aryl group, the number of carbon atoms of the alkyl moiety is preferably 1 to 5, and examples of the alkyl moiety include a methyl group, an ethyl group, a propyl group and an isopropyl group. And an ethyl group is preferable, and a methyl group is more preferable.

However, in said Formula (T-ca-1), at least one of R ^{h01 to} R ^h04 is an aryl group which may have a substituent.
Below, the specific example of the cation represented by said Formula (T-ca-1) is shown.

In the formula (T-ca-2), the ^description of the alkyl group and the aryl group in R ^{h05 to} R ^h07 is the same as the description of the alkyl group and the aryl group in R ^{h01 to} R ^h04 described above.

However, in said Formula (T-ca-2), at least one of R ^{h05 to} R ^h07 is an aryl group which may have a substituent.
Below, the specific example of the cation represented by said Formula (T-ca-2) is shown.

-About the anion part of (T) component As the anion part of (T) component, for example, hexafluorophosphate anion, trifluoromethanesulfonic acid anion, perfluorobutanesulfonic acid anion, tetrakis (pentafluorophenyl) borate anion Etc.
Among these, hexafluorophosphate anion, trifluoromethanesulfonate anion and perfluorobutanesulfonate anion are preferable, and hexafluorophosphate anion and trifluoromethanesulfonate anion are more preferable.

  In the composition for forming a separation layer of the present embodiment, as the (T) component, for example, trade names San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI- 100, SI-100L, SI-110, SI-110L, SI-145, I-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 ( Above, Sanshin Chemical Industry Co., Ltd.); CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (manufactured by Nippon Soda Co., Ltd.); CP-66, CP-77 (made by ADEKA Co., Ltd.); FC-520 (made by 3M company); K-PURE TAG-2396, TAG-2713S, TAG-2713, TAG-217 , TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG-2678, TAG-2681, TAG-2679, TAG-2690, TAG-2700, TAG-2710, 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 Commercial products such as CXC-1736, CXC-1756, CXC-1821, and CXC-1802-60 (all manufactured by KING INDUSTRY Co., Ltd.) can be used.

The component (T) contained in the composition for forming a separation layer of the present embodiment may be one kind or two or more kinds.
In the composition for forming a separated layer according to this embodiment, among the above, hexafluorophosphate, trifluoromethanesulfonate, and perfluorobutanesulfonate are preferable as the component (T), and trifluoromethanesulfonate is More preferred is the quaternary ammonium salt of trifluoromethanesulfonic acid.
When the composition for forming a separation layer of the present embodiment contains the (T) component, the content of the (T) component is 0.01 to 20 parts by mass with respect to 100 parts by mass of the (P) component. Is preferable, 1 to 15 parts by mass is more preferable, and 2 to 10 parts by mass is more preferable.
If the content of the component (T) is within the above-mentioned preferable range, it is likely to be denatured by light irradiation (the photoreactivity of the separation layer is enhanced). For example, by firing, it is possible to easily form a fired body capable of preferably absorbing light in a wavelength range of 600 nm or less. In addition, chemical resistance is further improved.

<< photo-acid generator >>
The composition for forming a separation layer of the present embodiment may further contain a photoacid generator. Such a composition for forming a separation layer also contains a photoacid generator, as in the case of containing the (T) component as described above, the action of the acid generated from the photoacid generator during heating at the time of firing, etc. Since the separation layer is promoted to be oxidized by this, it is likely to be denatured by light irradiation (the photoreactivity of the separation layer is enhanced).
As a photo-acid generator, onium salt-type acid generators, such as a sulfonium salt, are mentioned suitably, for example.

  As a preferable cation part in an onium salt type acid generator, a sulfonium cation and an iodonium cation are mentioned.

Preferred examples of the anion moiety in the onium salt-based acid generator include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ); tetrakis [(trifluoromethyl) phenyl] borate ([B (C) ₆ H ₄ CF ₃ ) ₄ ] ⁻ ); difluorobis (pentafluorophenyl) borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ); trifluoro (pentafluorophenyl) borate ([[(C ₆ F ₅ )) BF _3] ^-); tetrakis (difluorophenyl) borate _{([B (C 6 H 3} F 2) 4] -) , and the like. Moreover, the anion represented by the following general formula (b0-2a) is also preferable.

［式中、Ｒ^ｂｆ０５は、置換基を有していてもよいフッ素化アルキル基である。ｎｂ^１は、１〜５の整数である。］

[ ^Wherein , R ^bf05 is a fluorinated alkyl group which may have a substituent. nb ¹ is an integer of 1 to 5; ]

In the formula (b0-2a), the fluorinated alkyl group for R ^{bf 05} preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and 1 to 5 carbon atoms Is more preferred. Among ^them, as R ^{bf 05} , a fluorinated alkyl group of 1 to 5 carbon atoms is preferable, a perfluoroalkyl group of 1 to 5 carbon atoms is more preferable, and a trifluoromethyl group or a pentafluoroethyl group is more preferable.
In the formula (b0-2a), nb1 is preferably an integer of ¹ to 4, more preferably an integer of 2 to 4, and most preferably 3.
When nb ¹ is 2 or more, a plurality of R ^{bf 05} may be the same or different.

The photoacid generator contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.
When the composition for forming a separation layer of the present embodiment contains a photoacid generator, the content of the photoacid generator is 0.01 to 20 parts by mass with respect to 100 parts by mass of the component (P). Is preferable, 1 to 15 parts by mass is more preferable, and 2 to 10 parts by mass is more preferable.
If the content of the photoacid generator is within the above-mentioned preferred range, it is likely to be altered by light irradiation (the photoreactivity of the separation layer is enhanced). For example, by firing, it is possible to easily form a fired body capable of preferably absorbing light in a wavelength range of 600 nm or less. In addition, chemical resistance is further improved.

«Organic solvent component»
The composition for forming a separation layer of the present embodiment may contain an organic solvent component (hereinafter also referred to as “(S) component”) in order to adjust coating workability and the like.
Examples of the component (S) include linear hydrocarbons such as hexane, heptane, octane, nonane, methyl octane, decane, undecane, dodecane and tridecane; branched hydrocarbons having 4 to 15 carbon atoms; cyclohexane And cyclic hydrocarbons such as cycloheptane, cyclooctane, naphthalene, decahydronaphthalene and tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpin, 1,8-terpin, bornane, Norbornan, Pinan, Tujan, Callan, Longiphorene, Geraniol, Nerol, Linalol, Linalol, Citralol, Citronellol, Menthol, Isomenthol, Neomenthol, α-Terpineol, β-Terpineol, γ-Terpineol, Terpinen-1-ol, Terpinene Terpene solvents such as 4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonone, touyon, camphor, d-limonene, l-limonene, dipentene, etc .; γ-butyrolactone Lactones such as acetone; ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone and 2-heptanone; polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol and dipropylene glycol Compounds having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate, etc .; Derivatives of polyhydric alcohols such as monomethyl ether, monoethyl ether, monopropyl ether, monoalkyl ether such as monobutyl ether, monobutyl ether, etc. or compounds having an ether bond such as monophenyl ether (these compounds 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 Esters such as methoxypropyl acetate, methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate and ethyl ethoxypropionate; anisole, ethyl benzyl ester Le, cresyl methyl ether, diphenyl ether, dibenzyl ether, phenetole, aromatic organic solvents such as butyl phenyl ether.
The component (S) contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.

  In the composition for forming a separation layer of the present embodiment, the amount of the component (S) used is not particularly limited, and can be appropriately set according to the applied film thickness and the coatability at a concentration that can be applied to a support substrate or the like. Preferably, the total amount of the components (P) in the composition for forming a separation layer is 70% by mass or less, more preferably 10 to 50% by mass, based on the total mass (100% by mass) of the composition. The (S) component is used as it is inside.

«Surfactant»
The composition for forming a separation layer of the present embodiment may contain a surfactant in order to adjust coating workability and the like.
As surfactant, silicone type surfactant and fluorine type surfactant are mentioned, for example. Silicone surfactants include, for example, BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK-320, BYK-322, BYK -323, BYK-325, BYK-330, BYK-331, BYK-333, BYK-335, BYK-341, BYK-344, BYK-345, BYK-346, BYK-348, BYK-354, BYK-355 , BYK-356, BYK-358, BYK-361, BYK-370, BYK-371, BYK-375, BYK-380, BYK-390 (all by BYK Chemie) and the like can be used. As a fluorine-based surfactant, for example, F-114, F-177, F-410, F-410, F-450, F-493, F-494, F-443, F-444, F-445, F -446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483, F-484 , F-486, F-487, F-172D, MCF-350SF, TF-1025SF, TF-1117SF, TF-1026SF, TF-1128, TF-1127, TF-1129, TF-1126, TF-1130, TF -1116SF, TF-1131, TF-1132, TF-1027SF, TF-1441, TF-1442 (all manufactured by DIC Corporation); Polyfox series PF-636, PF-6320, PF-656, PF-6520 (above, manufactured by OMNOVA Solutions Inc.) can be used.

The surfactant contained in the composition for forming a separation layer of the present embodiment may be one type or two or more types.
When the composition for forming the separation layer of the present embodiment contains a surfactant, the content of the surfactant is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the component (P). And 0.02 to 2 parts by mass, and more preferably 0.03 to 1 part by mass.
When the content of the surfactant is within the above-mentioned preferable range, a separation layer having high flatness can be easily formed when the composition for forming a separation layer is applied on a supporting substrate.

(Support base with separation layer)
A support base with a separation layer according to a second aspect of the present invention comprises a support base, and a separation layer formed on the support base using the composition for forming a separation layer according to the first aspect. It is
The separation base with the separation layer of this embodiment is provided with a separation layer formed using the separation layer forming composition of the above-described embodiment on a support base. Therefore, the photoreactivity and chemical resistance are enhanced in the support substrate with such a separation layer.

<Supporting base>
The support substrate has the property of transmitting light. The support base is a member for supporting the substrate, and is attached to the substrate through the separation layer. Therefore, it is preferable that the supporting substrate has a strength necessary to prevent breakage or deformation of the substrate during thinning of the sealing body, transportation of the substrate, mounting on the substrate, and the like. In addition, the supporting substrate is preferably one that transmits light of a wavelength that can alter the separation layer.
As a material of a support base, glass, silicon, acrylic resin etc. are used, for example. Examples of the shape of the support base include, but not limited to, a rectangle, a circle, and the like.
Further, as the supporting substrate, it is also possible to use a large sized supporting substrate having a large size in a circular shape or a large panel having a rectangular shape in top view in order to further increase the high density integration and improve the production efficiency.

<Separation layer>
The separation layer can be formed using the composition for forming a separation layer of the embodiment described above, and is formed of a fired body formed by firing the resin component (P) contained in the composition for forming a separation layer. It is a layer. This separation layer is suitably degraded by absorbing the light transmitted through the supporting substrate.
The separation layer may be a layer containing a material that does not have a light-absorbing structure, as long as the essential characteristics of the present invention are not impaired. Therefore, it is preferable to be formed only of a material that absorbs light.

  The sintered body as referred to herein means one obtained by sintering a composition containing the (P) component. The fired body is formed by firing a composition containing the (P) component in an air environment, that is, in an environment where oxygen is present, and at least a part of the composition is carbonized. The sintered body constituting the separation layer in the present embodiment can preferably absorb light in the wavelength range of 600 nm or less, and preferably has high chemical resistance.

  The “deterioration” of the separation layer means a phenomenon in which the separation layer can be destroyed by an external force or the adhesion to the layer in contact with the separation layer is reduced. The separation layer becomes brittle by absorbing light and loses its strength or adhesiveness before being irradiated with light. Such alteration of the separation layer occurs as a result of decomposition of absorbed light by energy, change of configuration, or dissociation of functional groups.

The thickness of the separation layer is, for example, preferably in the range of 0.05 μm or more and 50 μm or less, and more preferably in the range of 0.3 μm or more and 1 μm or less.
If the thickness of the separation layer is in the range of 0.05 μm or more and 50 μm or less, desired deterioration can be caused in the separation layer by the irradiation of light for a short time and the irradiation of light of low energy. The thickness of the separation layer is particularly preferably in the range of 1 μm or less from the viewpoint of productivity.

  For example, in the laminate 10 shown in FIG. 1, it is preferable that the separation layer has a flat surface on the side in contact with the adhesive layer (no unevenness is formed), which facilitates the formation of the adhesive layer, and Thus, it becomes easy to uniformly bond the supporting substrate and the substrate.

  The support base with the separation layer of the present embodiment can be manufactured by performing the operation of the later-described [separation layer formation step] in the same manner.

  Since the support base with the separation layer of the embodiment described above is provided with the separation layer to which the composition for forming the separation layer of the embodiment described above is applied, the photoreactivity is enhanced, and preferably the chemical resistance is also preferable. It is being enhanced.

(Laminate)
The laminate according to the third aspect of the present invention is provided with a separation layer between a support substrate transmitting light and a substrate.
As shown in FIG. 1, in the laminate 10 of the present embodiment, the separation layer 2, the adhesive layer 3, and the substrate 4 are laminated in this order on the support base 1.

The description of the support base 1 is the same as the description of the <support base>.
The description of the separation layer 2 is the same as the description of the above <separation layer>.

<Adhesive layer>
The adhesive layer 3 is a layer for bonding the support base 1 and the substrate 4 and can be formed using a composition for forming an adhesive layer.
Examples of such a composition for forming an adhesive layer include those containing other components such as a thermoplastic resin, a diluent, and an additive. The thermoplastic resin may be any one that exhibits adhesive strength, and one kind of hydrocarbon resin (preferably cycloolefin polymer etc.), acrylic-styrene resin, maleimide resin, elastomer resin, polysulfone resin etc. Or two or more types can be produced. As a diluent, the thing similar to the said (S) component is mentioned. Other components include additional resins for improving the performance of the adhesive layer, curable monomers, photopolymerization initiators, plasticizers, adhesion promoters, stabilizers, coloring agents, thermal polymerization inhibitors, surfactants, etc. It can be mentioned.

The thickness of the adhesive layer 3 is, for example, preferably in the range of 0.1 μm to 50 μm, and more preferably in the range of 1 μm to 10 μm.
If the thickness of the adhesive layer is in the range of 0.1 μm or more and 50 μm or less, the support base 1 and the substrate 4 can be bonded to each other more favorably. In addition, when the thickness of the adhesive layer is 1 μm or more, the substrate can be sufficiently fixed on the supporting substrate, and when the thickness of the adhesive layer is 10 μm or less, the adhesive layer is removed in the subsequent removal step. It can be easily removed.

<Board>
The substrate 4 is subjected to processes such as thinning and mounting while being supported by the support base 1. On the substrate 4, for example, a structure such as an integrated circuit or a metal bump is mounted.
Although a silicon wafer substrate is typically used as the substrate 4, the present invention is not limited to this, and a ceramic substrate, a thin film substrate, a flexible substrate or the like may be used.

  In the present embodiment, the device is a semiconductor device or other device, and may have a single layer or multiple layer structure. When the element is a semiconductor element, an electronic component obtained by dicing the sealing substrate is a semiconductor device.

The laminate of the above-described embodiment is provided with the separation layer to which the composition for forming the separation layer of the above-described embodiment is applied, so that the photoreactivity is enhanced (deteriorated by irradiation of light suitably) The separability of the support base from the laminate is good.
In addition, since the laminate of the embodiment is provided with the separation layer to which the composition for forming the separation layer of the embodiment described above is applied, the chemical resistance is enhanced. Thereby, the layered product of an embodiment does not break easily under the influence of chemicals etc. which are used by etching processing, lithography processing, etc.

  In the laminate of the embodiment described above, the support base 1 and the separation layer 2 are adjacent to each other, but the present invention is not limited to this. Another layer is further formed between the support base 1 and the separation layer 2 May be In this case, the other layers may be made of a material that transmits light. According to this, it is possible to appropriately add a layer that imparts desirable properties and the like to the laminate 10 without blocking the incidence of light on the separation layer 2. The wavelength of light that can be used differs depending on the type of material that constitutes the separation layer 2. Therefore, the material forming the other layer does not have to transmit light of all the wavelengths, and can be appropriately selected from materials transmitting light of the wavelength that can change the material forming the separation layer 2.

  Moreover, although the laminated body of embodiment mentioned above is equipped with the contact bonding layer 3 for bonding together the support base 1 and the board | substrate 4, it is not limited to this, The separation layer between the support base 1 and the board | substrate 4 It may have only two. In this case, for example, a separation layer that also functions as an adhesive layer is used.

(Method of manufacturing laminate)
A fourth aspect of the present invention is a method of manufacturing a laminate having a separation layer between a support substrate transmitting light and a substrate, which comprises a separation layer forming step and a lamination step.

First Embodiment
FIG. 2 is a schematic process diagram illustrating an embodiment of a method of manufacturing a laminate. FIG. 2A is a view for explaining the separation layer formation step, and FIG. 2B is a view for explaining the lamination step.
In the method for manufacturing a laminate of the present embodiment, a composition for forming a separation layer in which a resin component having a phenol skeleton ((P) component) is dissolved in an organic solvent component ((S) component) is used. Further, a composition for forming an adhesive layer in which a hydrocarbon resin is dissolved in the (S) component is used.

[Separation layer formation process]
The separation layer forming step in the embodiment is a step of forming the separation layer by applying the composition for forming the separation layer of the above-mentioned embodiment on one side of the supporting substrate and then baking it.
In FIG. 2 (a), the separation layer 2 is formed by applying the composition for forming a separation layer of the above-described embodiment onto the support base 1 and thereafter baking it (ie, the support base with the separation layer) Is made).

  The method for applying the composition for forming the separation layer onto the support substrate 1 is not particularly limited, and examples thereof include methods such as spin coating, dipping, roller blade, spray application, and slit application.

In the separation layer forming step, the film is formed by removing the (S) component from the coating layer of the composition for forming a separation layer coated on the support substrate 1 in a heating environment or a reduced pressure environment. The removal of the component (S) can be performed, for example, by performing baking treatment at a temperature condition of 80 to 150 ° C. for 120 to 360 seconds.
Thereafter, the film obtained by removing the component (S) from the coating layer is fired in the air environment to form the separation layer 2 composed of a fired body.

The temperature at which the film formed by removing the (S) component from the coating layer is fired is appropriately set according to the type of the (P) component, and is preferably 200 ° C. or higher, for example, 250 ° C. or higher It is more preferable to If the temperature at the time of firing is equal to or higher than the lower limit value of the above-mentioned preferable range, it is possible to more stably form a separation layer capable of absorbing light in the wavelength range of 600 nm or less.
Although the upper limit of the temperature at the time of baking is not particularly limited, it is preferably, for example, 800 ° C. or less, and more preferably 600 ° C. or less.

  The baking time is preferably 3 minutes or more and 3 hours or less, more preferably 3 minutes or more and 30 minutes or less. As a result, it is possible to reliably form a separation layer capable of absorbing light in the wavelength range of 600 nm or less.

[Lamination process]
The laminating step in the embodiment is a step of laminating the support base on which the separation layer is formed, and the substrate on which the separation layer is not formed, via the separation layer and the adhesive layer.
In FIG. 2B, the support base 1 on which the separation layer 2 is formed and the substrate 4 on which the separation layer 2 is not formed are laminated via the separation layer 2 and the adhesive layer 3, The laminated body 10 in which the separation layer 2, the adhesive layer 3, and the substrate 4 are stacked in this order is obtained.

  As a specific method of the lamination step, a composition for forming an adhesive layer is applied on the separation layer 2 and heated to form the adhesive layer 3, and thereafter, the support substrate 1 and the substrate 4 are bonded to each other. Can be mentioned.

The method for applying the composition for forming an adhesive layer on the separation layer 2 is not particularly limited, but may be performed in the same manner as the method for applying the composition for forming a separation layer on the supporting substrate 1 described above.
The baking treatment for forming the adhesive layer 3 is performed, for example, by stepwise heating while raising the temperature to form the adhesive layer 3 by removing the (S) component from the composition for forming an adhesive layer. .

  In the method of bonding the support substrate 1 and the substrate 4, the substrate 4 is disposed at a predetermined position on the adhesive layer 3 and heated (for example, about 100 ° C.) under vacuum, the support substrate 1 and the substrate 4 by a die bonder or the like. By crimping.

  According to the method of manufacturing the laminate of the first embodiment, since the separation layer is provided by applying the composition for forming the separation layer of the embodiment described above, the photoreactivity is enhanced, and the support base from the laminate is obtained. It is possible to produce a laminate having good separability and preferably high chemical resistance.

Although the separation layer 2 is formed on the support base 1 in the method of manufacturing the laminate of the present embodiment described above, the present invention is not limited to this. The separation layer 2 may be formed on the substrate 4.
Although the adhesive layer 3 is formed on the separation layer 2 in the method of manufacturing the laminate of the present embodiment described above, the present invention is not limited to this, and the adhesive layer 3 may be formed on the substrate 4.
In addition, the separation layer 2 may be formed on both the support substrate 1 and the substrate 4, and in this case, the support substrate 1 and the substrate 4 may be formed via the separation layer 2, the adhesive layer 3 and the separation layer 2. It is pasted together.

Second Embodiment
FIG. 3 is a schematic process diagram for explaining another embodiment of the method for manufacturing a laminate. Fig.3 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 1st Embodiment, FIG.3 (b) is a figure explaining a sealing process.
The method for manufacturing a laminate of such another embodiment further includes a sealing step in addition to the separation layer forming step and the laminating step described above.

[Sealing process]
The sealing step in the embodiment is a step of sealing the substrate bonded to the support base via the adhesive layer after the laminating step with a sealing material to produce a sealed body.
In FIG. 3B, a sealed body 20 (laminated body) is obtained in which the whole of the substrate 4 disposed on the adhesive layer 3 is sealed with a sealing material.

  In the sealing step, a sealing material heated to, for example, 130 to 170 ° C. is supplied onto the adhesive layer 3 so as to cover the substrate 4 while maintaining a high viscosity state, and compression molded. The sealing body 20 (laminated body) in which the sealing material layer 5 is provided on the adhesive layer 3 is manufactured.

  As the sealing material, for example, a composition containing an epoxy resin or a silicone resin can be used. The sealing material layer 5 is not provided for each substrate 4 but is preferably provided so as to cover the entire substrate 4 on the adhesive layer 3.

  According to the method for manufacturing a laminate of the second embodiment, a sealing substrate provided with a substrate (wiring layer) on the separation layer and the adhesive layer by applying the composition for forming the separation layer of the embodiment described above is preferable. It is possible to form

Third Embodiment
FIG. 4 is a schematic process diagram for explaining another embodiment of the method for manufacturing a laminate. Fig.4 (a) is a figure which shows the sealing body manufactured by the manufacturing method of 2nd Embodiment, FIG.4 (b) is a figure explaining a grinding process, FIG.4 (c) is It is a figure explaining a rewiring formation process.
The method of manufacturing the laminate according to the other embodiment further includes a grinding step and a rewiring forming step in addition to the separation layer forming step, the stacking step, and the sealing step.

[Grinding process]
The grinding process in the embodiment is a process of grinding the sealing material portion (sealing material layer 5) in the sealing body 20 so that a part of the substrate 4 is exposed after the sealing process.
Grinding of the sealing material portion is performed, for example, by shaving the sealing material layer 5 to a thickness substantially equal to that of the substrate 4 as shown in FIG.

[Rewiring formation process]
The rewiring formation step in the embodiment is a step of forming the rewiring layer 6 on the exposed substrate 4 after the grinding step.
The rewiring layer is also called RDL (Redistribution Layer), is a thin film wiring body that constitutes a wiring connected to the element, and may have a single layer or multiple layer structure. For example, the rewiring layer may be formed of a dielectric (eg, silicon oxide (SiO _x ), photosensitive resin such as photosensitive epoxy), a conductor (eg, metal such as aluminum, copper, titanium, nickel, gold, silver, etc.) and silver-tin. The wiring may be formed of an alloy such as an alloy, but is not limited thereto.

As a method of forming the rewiring layer 6, first, on the sealing material layer 5, a dielectric layer such as silicon oxide (SiO _x ) or photosensitive resin is formed. The dielectric layer made of silicon oxide can be formed, for example, by sputtering or vacuum evaporation. The dielectric layer made of a photosensitive resin can be formed by applying a photosensitive resin on the sealing material layer 5 by, for example, a method such as spin coating, dipping, roller blade, spray coating, slit coating, etc. .

Subsequently, in the dielectric layer, a wire is formed of a conductor such as metal.
As a method of forming the wiring, for example, a known semiconductor process method such as a lithography process such as photolithography (resist lithography) or an etching process can be used. Examples of such lithography processing include lithography processing using a positive resist material and lithography processing using a negative resist material.

As described above, when the photolithography process and the etching process are performed, the separation layer 2 is formed of an acid such as hydrofluoric acid, an alkali such as tetramethyl ammonium hydroxide (TMAH), or a resist solvent for dissolving the resist material. Exposed to In particular, in the fan-out type technique, PGMEA, cyclopentanone, cycloheptanone, N-methyl-2-pyrrolidone (NMP), cyclohexanone or the like is used as a resist solvent.
However, the separation layer is provided with high chemical resistance by forming the separation layer using the composition for forming the separation layer of the embodiment described above. Therefore, the separation layer is not easily dissolved or peeled off even when exposed to a resist solvent as well as an acid and an alkali.
Thus, the redistribution layer 6 can be suitably formed on the sealing material layer 5.

According to the method of manufacturing the laminate of the third embodiment, the support base 1, the separation layer 2, the adhesive layer 3, the sealing material layer 5 covering the substrate 4, and the rewiring layer 6 are stacked in this order. Can be stably manufactured.
The laminate 30 is a laminate manufactured in a process based on fan-out technology in which the terminals provided on the substrate 4 are mounted on the rewiring layer 6 extending outside the chip area.

  In the method of manufacturing a laminate according to this embodiment, bumps can be formed on the rewiring layer 6 or elements can be mounted. The mounting of the element on the redistribution layer 6 can be performed using, for example, a chip mounter or the like.

(Method of manufacturing electronic parts)
A method of manufacturing an electronic component according to a fifth aspect of the present invention includes a separation step and a removal step after obtaining a laminate by the method of manufacturing a laminate according to the fourth aspect.

  FIG. 5 is a schematic process diagram for explaining an embodiment of a method of manufacturing a semiconductor package (electronic component). Fig.5 (a) is a figure which shows the laminated body manufactured by the manufacturing method of 3rd Embodiment, FIG.5 (b) is a figure explaining a isolation | separation process, FIG.5 (c) is a removal. It is a figure explaining a process.

[Separation process]
The separation step in the embodiment is a step of separating the support base 1 from the laminate 30 by irradiating the separation layer 2 with light (arrows) through the support base 1 to deteriorate the separation layer 2.

As shown in FIG. 5A, in the separation step, the separation layer 2 is degraded by irradiating the separation layer 2 with light (arrows) through the supporting substrate 1.
The wavelength at which the separation layer 2 can be altered includes, for example, the range of 600 nm or less.
The type and the wavelength of the light to be irradiated may be appropriately selected according to the transparency of the support substrate 1 and the material of the separation layer 2. For example, YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber Use solid laser such as laser, liquid laser such as dye laser, gas laser such as CO ₂ laser, excimer laser, Ar laser, He-Ne laser, semiconductor laser, laser light such as free electron laser, non-laser light it can. As a result, the separation layer 2 can be denatured, and the support substrate 1 and the substrate 4 can be easily separated.

When irradiating a laser beam, the following conditions can be mentioned as an example of laser beam irradiation conditions.
The average output value of the laser beam is preferably 1.0 W or more and 5.0 W or less, and more preferably 3.0 W or more and 4.0 W or less. The repetition frequency of the laser light is preferably 20 kHz or more and 60 kHz or less, and more preferably 30 kHz or more and 50 kHz or less. The scanning speed of the laser beam is preferably 100 mm / s or more and 10000 mm / s or less.

After the separation layer 2 is irradiated with light (arrows) to alter the separation layer 2, the support base 1 is separated from the laminate 30 as shown in FIG. 5 (b).
For example, the supporting base 1 and the substrate 4 are separated by applying a force in a direction away from each other. Specifically, in a state where one of the support base 1 or the substrate 4 side (rewiring layer 6) is fixed to the stage, the other is adsorbed and held by a separation plate provided with a suction pad such as a bellows pad or the like. The support substrate 1 and the substrate 4 can be separated.
The force applied to the laminate 30 may be appropriately adjusted according to the size of the laminate 30, etc., and is not limited. For example, in the case of a laminate having a diameter of about 300 mm, 0.1 to 5 kgf (0 By applying a force of about .98 to 49 N), the support base 1 and the substrate 4 can be suitably separated.

[Removal process]
The removal step in the embodiment is a step of removing the adhesive layer 3 attached to the substrate 4 after the separation step.
In FIG. 5B, the adhesive layer 3 and the separation layer 2 adhere to the substrate 4 after the separation process. In the present embodiment, the electronic component 40 shown in FIG. 5C is obtained by removing the adhesive layer 3 and the separation layer 2 attached to the substrate 4 in the removing step.

Examples of the method for removing the adhesive layer 3 and the like attached to the substrate 4 include a method for removing the residue of the adhesive layer 3 and the separation layer 2 using a cleaning liquid, or a method for irradiating plasma.
As the cleaning solution, a cleaning solution containing an organic solvent is suitably used. As the organic solvent, it is preferable to use the organic solvent blended in the composition for forming the separation layer and the organic solvent blended in the composition for forming the adhesive layer.

<Other embodiments>
FIG. 6 is a schematic process diagram for explaining another embodiment of the method for manufacturing a semiconductor package (electronic component). FIG. 6 (a) is a schematic view showing another embodiment of a laminate to which the present invention is applied, FIG. 6 (b) is a view for explaining a separation step, and FIG. 6 (c) is a removal It is a figure explaining a process.

  In the laminate 50 of the embodiment shown in FIG. 6A, the support base 51, the separation layer 52, the wiring layer 57, the substrate 54, and the sealing material layer 55 are laminated in this order from the outermost surface 51s side.

The description of the support base 51 is the same as the description of the <support base>.
The description of the separation layer 52 is the same as the description of the <separation layer>.

The wiring layer 57 is made of, for example, a dielectric (a silicon oxide (SiO _x ), a photosensitive resin such as photosensitive epoxy, etc.), a conductor (a metal such as aluminum, copper, titanium, nickel, gold, silver, etc.) and silver-tin. What formed wiring by alloy, such as an alloy, is mentioned.
The description of the substrate 54 is the same as the description in the above <substrate>.
The sealing material layer 55 is, for example, one formed using a composition containing an epoxy resin or a silicone resin.

The laminate 50 can be manufactured, for example, as follows.
First, the separation layer 52 is formed on the surface of the support base 51 opposite to the outermost surface 51s. The formation of the separation layer 52 may be performed in the same manner as the above [separation layer formation step].
Next, the wiring layer 57 is formed on the surface of the separation layer 52 opposite to the support base 51. The formation of the wiring layer 57 may be performed in the same manner as the above [rewiring formation step].
Next, the substrate 54 is attached to the surface of the wiring layer 57 opposite to the separation layer 52, for example, via bumps.
Next, the substrate 54 sealed with the wiring layer 57 is sealed with a sealing material to form a sealing material layer 55. The formation of the sealing material layer 55 may be performed in the same manner as the above [sealing process]. Thereby, the stacked body 50 is manufactured.

As shown in FIG. 6A, in the separation step in the embodiment, light (arrows) is irradiated to the separation layer 52 through the support base 51 to deteriorate the separation layer 52.
After the separation layer 52 is irradiated with light (arrows) to change the quality of the separation layer 52, as shown in FIG. 6B, the support base 51 is separated from the laminate 50. The operation in this separation step may be performed in the same manner as the operation in the above-mentioned [separation step].

As shown in FIG. 6C, in the removal step in the embodiment, the electronic component 60 is obtained by removing the separation layer 52 attached to the wiring layer 57 after the separation step.
As a method of removing the separation layer 52 attached to the wiring layer 57, for example, a method of irradiating plasma or a method of removing the residue of the separation layer 52 using a cleaning liquid may be mentioned. Oxygen plasma is suitably used as the plasma.

  In the method of manufacturing an electronic component of the present embodiment, after the above removal step, the electronic component may be further subjected to processing such as solder ball formation, dicing, or oxide film formation.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

<Resin component (P)>
In the present example, resins (P-1) to (P-4) shown below were used.
Resin (P-1): aminophenol-containing resin, trade name GSP01, manufactured by Gunei Chemical Industry Co., Ltd. Weight average molecular weight 12000.
Resin (P-2): aminophenol-containing resin, trade name GSP02, manufactured by Gunei Chemical Industry Co., Ltd. Weight average molecular weight 2300.
Resin (P-3): aminophenol-containing resin, trade name GSP03, manufactured by Gunei Chemical Industry Co., Ltd. Weight average molecular weight 6000.
Resin (P-4): Naphthol novolac type phenol resin. Weight average molecular weight 3280.

<Preparation of Composition for Forming Separate Layer (1)>
(Examples 1-5)
Each component shown in Table 1 was mixed and dissolved to prepare a composition for forming a separation layer (resin component concentration: 30% by mass) of each example.

Each abbreviation in Table 1 has the following meaning. The numerical values in [] are compounding amounts (parts by mass).
(P) -1: the above resin (P-1).
(P) -2: The above resin (P-2).
(P) -3: The above resin (P-3).

(T) -1: quaternary ammonium salt block species, trade name TAG 2689, manufactured by KING INDUSTRY.
(S) -1: mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 1/1 (mass ratio).

<Formation of separation layer>
The separation layer-forming composition of each example is spin-coated on a bare glass support (12 inches, 0.7 mm thick) and heated at 100 ° C. for 300 seconds, followed by 150 ° C. The solvent was removed by heating under the conditions of 300 seconds to form a film having a film thickness of 1.8 μm.
Next, the formed film was fired under the conditions of a temperature of 300 ° C. for 20 minutes in an air environment to form a separation layer on a bare glass support substrate, to obtain a support substrate with a separation layer. The thickness of the separation layer formed at that time is shown in Table 2.

[Evaluation of light transmittance in separation layer]
In <Formation of separation layer> described above, a spectrometric measurement device UV is applied to the film in the state before firing and the film in the state after firing (separation layer) formed using the composition for forming the separation layer in each example. The transmittance | permeability of the light of wavelength 532 nm in each film | membrane formed on the bare glass support base was evaluated by irradiating light with a wavelength of 380-780 nm using -3600 (made by Shimadzu Corporation Corp.). The evaluation results are shown in Table 2.

[Evaluation of laser reactivity in separation layer]
The separation layer formed using the composition for forming the separation layer is irradiated with a laser beam having a wavelength of 532 nm under the conditions of a scanning speed of 3000 mm / sec, a frequency of 40 kHz, an output (current value) 24A, and an irradiation pitch of 140 μm. By doing this, the laser reactivity was evaluated.
The evaluation of the laser reactivity was performed by observing the state of the trace of the laser beam irradiated to the separation layer using a microscope VHX-600 (manufactured by Keyence).
The criteria for evaluation of the laser reactivity were set as follows, using the size of the trace of the laser beam on the surface of the separation layer (dentation diameter) as an index. The evaluation results are shown in Table 2.
Criteria for evaluation of laser reactivity ◎: indentation diameter of 100 μm or more.
○: Bent mark diameter is 50 μm or more and less than 100 μm.
Δ: Bent mark diameter less than 50 μm.
X: no trace of laser light.

  From the results shown in Table 2, all of the separation layers formed using the separation layer forming compositions of Examples 1 to 5 show absorption at a wavelength of 532 nm, and additionally have photoreactivity. Can be confirmed.

[Evaluation of chemical resistance in separation layer]
A separation layer was formed on a bare glass supporting substrate using the composition for forming a separation layer of Example 2 in the same manner as <Formation of separation layer> described above.
Further, as Comparative Example 1, a separation layer of fluorocarbon was formed on a glass supporting substrate. This fluorocarbon separation layer was formed on a glass supporting substrate by using the reactive gas C ₄ F ₈ under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W and a deposition temperature of 240 ° C. (Layer thickness 1.0 μm).

Then, the separation layer formed on the bare glass support substrate is treated with propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone (NMP) and cycloheptanone at 25 ° C. for 10 minutes. It was immersed and evaluated for chemical resistance.
In addition, the separation layer formed on the bare glass supporting base was immersed in a resist stripping solution ST120 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at a temperature of 60 ° C. for 30 minutes to evaluate chemical resistance.
The above-mentioned chemical resistance was evaluated by visual observation, and the separation layer formed on the glass support was evaluated as "A" without swelling and peeling, and at least one of swelling and peeling was recognized. The thing was evaluated as "C". The evaluation results are shown in Table 3.

  With respect to the separation layer formed using the composition for forming the separation layer of Example 2 and the separation layer of the fluorocarbon of Comparative Example 1, in the same manner as the above-mentioned [Evaluation of light transmittance in separation layer], each film The transmittance of light at a wavelength of 532 nm was evaluated. The evaluation results are shown in Table 3.

  From the results shown in Table 3, it can be confirmed that the separation layer formed using the composition for forming a separation layer of Example 2 has higher chemical resistance than the separation layer of the fluorocarbon of Comparative Example 1.

<Preparation of Composition for Forming Separate Layer (2)>
(Examples 6 to 15)
Each component shown in Table 4 was mixed and dissolved to prepare a composition for forming a separated layer (resin component concentration: 30% by mass) of each example.

Each abbreviation in Table 4 has the following meaning. The numerical values in [] are compounding amounts (parts by mass).
(P) -1: the above resin (P-1).
(P) -2: The above resin (P-2).
(P) -4: The above resin (P-4).

(T) -1: quaternary ammonium salt block species, trade name TAG 2689, manufactured by KING INDUSTRY.
(S) -1: mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 1/1 (mass ratio).

<Formation of separation layer>
The separation layer-forming composition of each example is spin-coated on a bare glass support (12 inches, 0.7 mm thick) and heated at 100 ° C. for 300 seconds, followed by 150 ° C. The solvent was removed by heating under the conditions of 300 seconds to form a film having a film thickness of 1.8 μm.
Next, the formed film is fired at a temperature of 260 ° C., 280 ° C. or 300 ° C. for 20 minutes in an air environment to form a separation layer on a bare glass support substrate, thereby forming a support substrate with a separation layer. Obtained. The thickness of the separation layer formed at that time is shown in Tables 5 and 6.

[Evaluation of light transmittance in separation layer]
In <Formation of separation layer> described above, with respect to the film (separation layer) in the state after firing formed using the composition for forming separation layer of each example, a spectrometric measurement device UV-3600 (manufactured by Shimadzu Corporation) The transmittance | permeability of the light of wavelength 532 nm in each film | membrane formed on the bare glass support base was evaluated by irradiating with the light of wavelength 380-780 nm using 2.). The evaluation results are shown in Tables 5 and 6.

[Evaluation of laser reactivity in separation layer]
The separation layer formed using the composition for forming the separation layer is irradiated with a laser beam having a wavelength of 532 nm under the conditions of a scanning speed of 3000 mm / sec, a frequency of 40 kHz, an output (current value) 24A, and an irradiation pitch of 140 μm. By doing this, the laser reactivity was evaluated.
The evaluation of the laser reactivity was performed by observing the state of the trace of the laser beam irradiated to the separation layer using a microscope VHX-600 (manufactured by Keyence).
The criteria for evaluation of the laser reactivity were set as follows, using the size of the trace of the laser beam on the surface of the separation layer (dentation diameter) as an index. The evaluation results are shown in Tables 5 and 6.
Criteria for evaluation of laser reactivity ◎: indentation diameter of 100 μm or more.
○: Bent mark diameter is 50 μm or more and less than 100 μm
Δ: Bent mark diameter less than 50 μm.
X: no trace of laser light.

[Evaluation of chemical resistance in separation layer]
A separation layer was formed on a bare glass supporting substrate using the composition for forming a separation layer of Examples 6 to 15 in the same manner as in <Formation of separation layer> described above.
Next, the separation layer formed on the bare glass support was immersed in N-methyl-2-pyrrolidone (NMP) at a temperature of 60 ° C. for 10 minutes to evaluate its chemical resistance.
The above-mentioned chemical resistance was evaluated by visual observation, and the separation layer formed on the glass support was evaluated as "A" without swelling and peeling, and at least one of swelling and peeling was recognized. The thing was evaluated as "C". The evaluation results are shown in Tables 5 and 6.

[Evaluation of hygroscopicity in separated layers]
About the separated layer formed using the composition for forming a separated layer of each example, the simultaneous measurement of thermogravimetric-differential heat (TG-DTA) is carried out using a differential thermal and thermal weight simultaneous measuring device (TG / DTA 6200, manufactured by SII) The weight change from 25 ° C. to 100 ° C. was confirmed. The results are shown in Tables 5 and 6 as "hygroscopicity (%)".
The smaller the hygroscopic value, the less the generation of voids due to heating.

[Evaluation of residual film rate]
About the separation layer formed using the composition for forming a separation layer of each example, the film thickness before and after firing is confirmed, and the film thickness after firing is divided by the film thickness before firing to obtain “the remaining film The results are shown in Table 6 as “percent (%)”. The term “baking” as used herein refers to an operation of heating a film obtained by removing the solvent from the coating layer of the composition for forming a separation layer at 260 ° C. or 280 ° C.
As the value of the residual film rate is higher, it means that the film thickness after firing remains.

  From the results shown in Table 5, all of the separation layers formed using the compositions for forming separation layers of Examples 1, 2 and 6 show absorption at a wavelength of 532 nm, and additionally, photoreactivity is obtained. It can be confirmed that it has.

  In addition, it can be confirmed that the separation layer formed using the composition for forming a separation layer of Example 6 has particularly high photoreactivity, a small hygroscopic value, and hardly generates voids due to heating.

  From the results shown in Table 6, all of the separation layers formed using the composition for forming a separation layer of Examples 6 to 15 exhibit absorption at a wavelength of 532 nm and additionally have photoreactivity. Can be confirmed.

  In Examples 11 to 15, the composition for forming a separation layer having a higher content ratio of the resin (P-4) to the resin component (P) has a smaller hygroscopic value and is less likely to generate a void due to heating. Can be confirmed. It can also be confirmed that the firing temperature can be reduced.

  It can be confirmed that the separation layer formed using the composition for forming a separation layer of Examples 10 to 15 has high photoreactivity and enhanced chemical resistance.

<Production of laminates>
The composition for forming a separation layer of each example was spin-coated on a bare glass support (12 inches, thickness 0.7 mm) by the same method as <Formation of separation layer> above, and the temperature was 100 ° C. The solvent was removed by heating at conditions of 300 seconds and then heating at conditions of 150 ° C. for 300 seconds to form a film. Then, the formed film was fired at 300 ° C. for 20 minutes in the air environment to form a 0.5 μm-thick separation layer on the bare glass support substrate (separation layer formation step).
On the other hand, adhesive composition TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on a semiconductor wafer substrate (12 inches, silicon), and each of them is heated at 90 ° C, 160 ° C, and 220 ° C. After baking for a minute, an adhesive layer with a thickness of 50 μm was formed.
Next, the bare glass support base on which the separation layer is formed and the semiconductor wafer substrate on which the adhesive layer is formed are stacked such that the semiconductor wafer substrate, the adhesive layer, the separation layer and the bare glass support base are in this order, It was pressed for 2 minutes with a pressure of 4000 kgf (about 39.2 kN) under the conditions of 215 ° C. under (5 Pa) pressure. Thereby, the bare glass support base and the semiconductor wafer substrate were laminated via the separation layer and the adhesive layer to obtain a laminated body (lamination process).

After obtaining the laminate, from the support base side of the laminate, a laser beam with a wavelength of 532 nm is applied to the separation layer under the conditions of a scanning speed of 3000 mm / sec, a frequency of 40 kHz, an output (current value) 24A, and an irradiation pitch of 140 μm. Irradiated (separation step).
After this, the adhesive layer was washed and removed using p-menthane (removal step).
By the above operation, it was confirmed that the support base is separated from the semiconductor wafer substrate provided in the laminate.

<Production example of electronic parts (1)>
The composition for forming a separation layer of each example was spin-coated on a bare glass support (12 inches, thickness 0.7 mm) by the same method as <Formation of separation layer> above, and the temperature was 100 ° C. The solvent was removed by heating at conditions of 300 seconds and then heating at conditions of 150 ° C. for 300 seconds to form a film. Next, the formed film is baked at 300 ° C. for 20 minutes in an air environment to form a 0.5 μm-thick separated layer on a bare glass supporting substrate, thereby forming a separated base with a separation layer. Obtained (separation layer formation step).
Thereafter, an adhesive composition TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on this separation layer, and baked at temperatures of 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each. An adhesive layer having a thickness of 50 μm was formed.
Then, using a die bonder (manufactured by TRESKY Co., Ltd.), the plate of the die bonder was heated to 150 ° C., and a 2 mm square silicon bare chip was crimped onto the adhesive layer at a pressure of 35 N for 1 second. After placing a bare silicon chip, the laminate was heated at 200 ° C. for 1 hour in a nitrogen atmosphere to obtain a laminate (lamination step).

  The obtained laminate is placed on a plate heated to 50 ° C., and 12 g of a sealing agent containing an epoxy resin is placed so as to cover the bare chip, using a sticking apparatus under a reduced pressure condition lower than 10 Pa. A pressure of 1 ton was applied with a pressing plate heated to 130 ° C. and compressed for 5 minutes. Thus, the bare chip disposed on the adhesive layer was sealed with a sealing material to produce a sealed body (sealing step).

After producing the sealing body, from the supporting substrate side of the sealing body, a laser with a wavelength of 532 nm under the conditions of a scanning speed of 3000 mm / sec, a frequency of 40 kHz, an output (current value) 24 A, and an irradiation pitch of 140 μm It was irradiated with light (separation step).
After this, the adhesive layer was washed and removed using p-menthane (removal step).
By the above operation, it was confirmed that the support base is separated from the sealing body.

<Production example of electronic parts (2)>
The composition for forming a separation layer of Example 15 was spin-coated on a bare glass supporting substrate (12 inches, thickness 0.7 mm) by the same method as <Formation of separation layer> described above, and 180 at 90 ° C. The solvent was removed by heating for 2 seconds to form a film. Next, the formed film is baked under the conditions of 300 ° C. for 10 minutes in the air environment to form a 0.35 μm-thick separated layer on the bare glass supporting substrate, thereby forming the separated base with the separation layer. Obtained (separation layer formation step).
Next, a material for forming a wiring layer (trade name: TMMR S2000) is applied onto the separation layer, and baked under the conditions of 90 ° C. for 3 minutes in the air environment to form a wiring layer with a thickness of 10 μm on the separation layer. To obtain a laminate.

After forming the wiring layer, the separation layer is irradiated with a laser beam with a wavelength of 532 nm under the conditions of an irradiation amount of 200 mJ / cm ² , an output (current value) 22 A, and an irradiation pitch of 80 μm from the bare glass support base side of the laminate. did. Then, the substrate was immersed in propylene glycol monomethyl ether acetate (PGMEA) as a washing solution, and baked at 90 ° C. for 5 minutes. Subsequently, the supporting substrate was separated from the laminate by repeating the baking three times at 200 ° C. for 60 minutes in a nitrogen atmosphere (separation step).
After that, the surface of the wiring layer on the separation layer side is irradiated with oxygen plasma (power 2000 W, oxygen flow 2000 sccm, pressure 75 Pa, temperature 50 ° C., irradiation time 5 minutes) to remove the separation layer attached to the wiring layer. (Removal process).
It was confirmed by the above operation that the support base is separated from the laminate.

DESCRIPTION OF SYMBOLS 1 support base | substrate, 2 isolation | separation layer, 3 adhesion layer, 4 board | substrate, 5 sealing material layer, 6 rewiring layer, 10 laminated body, 20 sealed body, 30 laminated body, 40 electronic components, 50 laminated body, 51 support base , 52 separation layers, 54 substrates, 55 sealing material layers, 57 wiring layers, 60 electronic components.

Claims (10)

In a laminate comprising a separation layer between a support substrate that transmits light and a substrate, the above-mentioned support substrate can be separated from the laminate by being denatured by irradiation of light from the support substrate side. A composition for forming a separation layer for forming a separation layer, the composition comprising:
A composition for forming a separation layer, which comprises a resin component (P) having a phenol skeleton. In a laminate comprising a separation layer and an adhesive layer between a support substrate transmitting light and a substrate, the support substrate can be separated from the laminate after being denatured by irradiation of light from the support substrate side A composition for forming a separation layer for forming the separation layer
The composition for forming a separation layer according to claim 1, which contains a resin component (P) having a phenol skeleton.   The composition for forming a separation layer according to claim 1, further comprising a thermal acid generator. The composition for formation of a separation layer according to any one of claims 1 to 3, wherein the resin component (P) contains a resin (P2) having a repeating unit represented by the following general formula (P2).

[ ^Wherein , L ^p1 is a divalent linking group. R ^P is an (n _{P 0} +1) -valent aromatic hydrocarbon group. n _P0 is an integer of 1 to 3. ] A supporting substrate,
A separation layer formed on the support base using the composition for forming a separation layer according to any one of claims 1 to 4.
And a support substrate with a separation layer.   It is a laminated body provided with a separation layer between a support base which transmits light and a substrate, wherein the separation layer is a composition for forming a separation layer according to any one of claims 1 to 4. A laminate that is a fired body. What is claimed is: 1. A method of producing a laminate comprising a separation layer between a light transmitting support substrate and a substrate,
A separation layer which forms the separation layer by applying the composition for forming a separation layer according to any one of claims 1 to 4 on at least one of the substrate and the support substrate, and thereafter firing the composition. Forming process,
A laminating step of laminating the substrate and the support base via the separation layer;
The manufacturing method of the laminated body which has.   8. The method according to claim 7, further comprising a sealing step of sealing the substrate bonded to the support base via the separation layer with the sealing material after the laminating step to produce a sealed body. Method of manufacturing a laminate. A grinding step of grinding the sealing material portion of the sealing body so as to expose a part of the substrate after the sealing step;
Forming a rewiring on the exposed substrate after the grinding step;
The manufacturing method of the laminated body of Claim 8 which has further. After obtaining a laminate by the method for producing a laminate according to any one of claims 7 to 9,
A separation step of separating the support base from the laminate by irradiating the separation layer with light through the support base to deteriorate the separation layer;
A removal step of removing the separation layer attached to the substrate after the separation step;
A method of manufacturing an electronic component, comprising:

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