JP2017170870A - Composition for forming separation layer, laminate, and method for producing laminate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new composition for forming a separation layer capable of successfully forming a separation layer having high chemical resistance by applying the composition, and to provide a laminate using the composition.SOLUTION: There are provided a composition for forming a separation layer for forming a separation layer 4 changed in quality by irradiation with light in a laminate 10 formed by laminating a substrate 1, a support body 2 passing light, an adhesive layer 3 and the separation layer 4 which contains a polymerizable resin component and a polymerization initiator; and a laminate and a method for manufacturing the laminate.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for forming a separation layer, a laminate, and a method for producing the laminate.

  In recent years, electronic devices such as IC cards and mobile phones have been required to be thinner, smaller and lighter. In order to satisfy these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. For this reason, the thickness (film thickness) of the wafer substrate that is the basis of the semiconductor chip is currently 125 μm to 150 μm, but it is said that it must be 25 μm to 50 μm for next-generation chips. Therefore, in order to obtain a wafer substrate having the above film thickness, a wafer substrate thinning step is indispensable.

  Since the strength of the wafer substrate decreases due to the thinning of the wafer substrate, a circuit is formed on the wafer substrate while automatically supporting the substrate while the support is bonded to the wafer substrate to prevent damage to the thinned wafer substrate. Etc. are mounted. Then, after the manufacturing process, the wafer substrate is separated from the support. Therefore, various methods for peeling the support from the wafer substrate are used.

  As a method for manufacturing a semiconductor chip in which a support is bonded to a semiconductor wafer, the semiconductor wafer is processed, and then the support is separated, a method described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support, and after the semiconductor wafer is processed, the support side The photothermal conversion layer is decomposed by irradiating radiant energy from the substrate to separate the semiconductor wafer from the support.

JP 2004-64040 A (published February 26, 2004)

  However, in a laminate in which a substrate and a support are bonded via an adhesive layer and a separation layer, it is useful to form a new separation layer with high chemical resistance in order to perform various treatments on the substrate. is there.

  As a result of intensive studies, the present inventors have successfully formed a separation layer with high chemical resistance by a novel composition for forming a separation layer comprising a polymerizable resin component and a polymerization initiator. And the present invention was completed. That is, the present invention has been made in view of the above-mentioned problems, and its purpose is to form a new separation layer that can successfully form a separation layer having high chemical resistance by coating. It is to provide a composition and related technology.

  In order to solve the above-mentioned problems, the composition for forming a separation layer of the present invention comprises a substrate, a support that transmits light, an adhesive layer, and a separation layer that is altered by irradiation with light. A composition for forming a separation layer for forming the separation layer in a laminate obtained by laminating, characterized by comprising a polymerizable resin component and a polymerization initiator.

  The laminate of the present invention is a laminate obtained by laminating a substrate and a support that transmits light through an adhesive layer and a separation layer that is altered by irradiation with light. The separation layer is a fired product of a cured product obtained by polymerizing a polymerizable resin component with a polymerization initiator.

  In addition, the method for producing a laminate of the present invention comprises producing a laminate comprising a substrate and a support that transmits light through an adhesive layer and a separation layer that is altered by being irradiated with light. A method comprising applying a composition for forming a separation layer comprising a polymerizable resin component and a polymerization initiator to any of the substrate and the support, and heating or exposing the polymerizable resin. Forming a separation layer by polymerizing components and baking the polymerized resin component, and forming the separation layer, the substrate or the support on which the separation layer is formed, and the separation layer. And a lamination step of laminating the other of the substrate and the other one of the supports through the separation layer and the adhesive layer.

  According to the present invention, it is possible to provide a novel composition for forming a separating layer and a related technique capable of successfully forming a separating layer having high chemical resistance by coating.

It is a figure explaining the outline of the manufacturing method of the layered product concerning one embodiment of the present invention.

<Composition for forming separation layer>
Hereinafter, the composition for forming a separation layer according to an embodiment of the present invention will be described in detail.

  A composition for forming a separation layer according to an embodiment is a laminate in which a substrate and a support that transmits light are stacked through an adhesive layer and a separation layer that is altered by irradiation with light. A composition for forming a separation layer for forming the separation layer, which comprises a polymerizable resin component and a polymerization initiator. Note that the composition for forming a separation layer may contain a diluting solvent and a surfactant in order to adjust the coating workability.

  The composition for forming a separation layer has high chemical resistance by firing a cured product obtained by polymerizing a polymerizable resin component with a polymerization initiator, and can be altered by irradiating light of a predetermined wavelength. A separation layer can be formed.

(Polymerizable resin component)
Examples of the polymerizable resin component include an addition polymerizable resin component having at least one functional group selected from the group consisting of an ethylenically unsaturated double bond and an epoxy group. . Such a compound group is widely known in the industrial field, and in the composition for forming a separation layer according to one embodiment, these can be used without any particular limitation.

  The polymerizable resin component having an epoxy group is not limited as long as it is a compound that can cleave the epoxy group by using a polymerization initiator and polymerize each other. In addition, the polymerizable resin component having an epoxy group only needs to have an epoxy group introduced into at least one of a side chain and a terminal regardless of its molecular weight. Therefore, the polymerizable resin component having an epoxy group includes, for example, a compound having an epoxy group and an ethylenically unsaturated double bond and a compound having an ethylenically unsaturated double bond not having an epoxy group. It may be a resin obtained by polymerization and introducing an epoxy group into the side chain.

  Further, the polymerizable resin component having an ethylenically unsaturated double bond may be a low molecular compound as long as it has an ethylenically unsaturated double bond, and may be a polymer such as a homopolymer or a copolymer resin. There may be.

  The low molecular weight compound having an ethylenically unsaturated double bond preferably has a molecular weight of 2000 or less, more preferably 1500 or less, and most preferably 900 or less. The low molecular weight compound in the present invention is not a so-called polymer or oligomer obtained by cleaving the unsaturated bond while using a polymerization initiator and growing the bond in a chain, and has a molecular weight of 2000 or less (more preferably Is a compound having a certain molecular weight of 1500 or less, more preferably 900 or less (a compound having substantially no molecular weight distribution). The molecular weight of the low molecular weight compound is usually 100 or more.

  Examples of low molecular weight compounds having an ethylenically unsaturated double bond include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and esters thereof, Examples include amides, and preferred examples include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyvalent amine compounds.

  The low molecular weight compound having an ethylenically unsaturated double bond is, for example, an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group, which is monofunctional or polyfunctional. It may be an addition reaction product added to isocyanates or epoxies. In addition, low molecular compounds having an ethylenically unsaturated double bond include unsaturated carboxylic acid esters or amides having a leaving substituent such as a halogen group or a tosyloxy group, monofunctional or polyfunctional alcohols, Substitution reaction products with amines and thiols can also be suitably used.

  In addition, the copolymer resin having an ethylenically unsaturated double bond is, for example, an unsaturated carboxylic acid ester or amide copolymer having a functional group such as a hydroxyl group, an amino group, or a mercapto group. It may be a resin formed by introducing an ethylenically unsaturated double bond by reacting a compound having an ethylenically unsaturated double bond having an isocyanate group or an epoxy group. The copolymer resin having an ethylenically unsaturated double bond is, for example, a copolymer of an unsaturated carboxylic acid ester or amide having a functional group such as a hydroxyl group, an amino group, or a mercapto group. A resin obtained by condensing a compound having a polymerizable unsaturated double bond may be used.

  In addition, the polymerizable resin component includes, for example, a siloxane skeleton, and at least one of a terminal group and a side chain of the siloxane skeleton, an epoxy group, and at least one of ethylenically unsaturated double bonds It may be a functional group-containing siloxane.

  Two or more kinds of such polymerizable resin components can be used in combination.

[1. Polymerizable resin component having epoxy group]
The polymerizable resin component having an epoxy group may be a resin component having a sufficient epoxy group to be cured by heating or exposure in one molecule. Among them, it contains at least one resin selected from the group consisting of novolak-type epoxy resins (Anv), bisphenol-type epoxy resins (Abp), alicyclic epoxy resins, and acrylic resins having epoxy groups (Aac). preferable. These epoxy-containing polymerizable resin components can be used singly or in combination of two or more. Among these, specific examples of more preferable epoxy resins are shown below.

(1) Novolac type epoxy resin (Anv)
As the novolac type epoxy resin (Anv), a resin represented by the following general formula (anv0) can be used.

(In the formula, R ^a11 and R ^a12 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, na ¹¹ is an integer of 1 to 5. R ^EP is an epoxy group-containing group.)
In the formula (anv0), the C 1-5 alkyl group of R ^a11 and R ^a12 is, for example, a linear, branched, or cyclic alkyl group having 1 to 5 carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, and a neopentyl group. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among these, as R ^a11 and R ^a12 , a hydrogen atom or a methyl group is preferable.

Wherein ^{(anv0), R EP} is an epoxy group-containing group. The epoxy group-containing group R ^EP is not particularly limited, groups composed of only an epoxy group; group consists of only alicyclic epoxy group; and an epoxy group or an alicyclic epoxy group, and a divalent linking group A group having The alicyclic epoxy group is an alicyclic group having an oxacyclopropane structure which is a three-membered ring ether, and specifically, a group having an alicyclic group and an oxacyclopropane structure. The alicyclic group serving as the basic skeleton of the alicyclic epoxy group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Moreover, the hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, the epoxy group or alicyclic epoxy is bonded via a divalent linking group bonded to an oxygen atom (—O—) in the formula. It is preferred that the groups are bonded. Here, although it does not specifically limit as a bivalent coupling group, The bivalent hydrocarbon group which may have a substituent, the bivalent coupling group containing a hetero atom, etc. are mentioned as a suitable thing.

Regarding the divalent hydrocarbon group which may have a substituent:
Such a divalent hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group as the divalent hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated. More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group having a ring in the structure, and the like.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, more preferably 1 to 4, and more preferably 1 to 3. Is most preferred. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned.

The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6, more preferably 2 to 4, more preferably 2 or 3. Is most preferred. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 An alkylethylene group such as CH ₃ ) ₂ CH ₂ —; an alkyl trimethylene group such as —CH (CH ₃ ) CH ₂ CH ₂ —, —CH ₂ CH (CH ₃ ) CH ₂ —; —CH (CH ₃ ) CH _{2 CH 2 CH 2 -, -} CH 2 CH (CH 3) CH 2 CH 2 - , etc. And alkyl alkylene group such as an alkyl tetramethylene group. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

  Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group that is linear or branched. Examples include a group bonded to the end of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. Examples of the linear or branched aliphatic hydrocarbon group include those described above. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane.

  The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms. Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

  The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, further preferably 6-15, and particularly preferably 6-12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Etc. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

  Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic group containing two or more aromatic rings. Group in which two hydrogen atoms are removed from an aromatic compound (for example, biphenyl, fluorene, etc.); a hydrogen atom in a group (aryl group or heteroaryl group) in which one hydrogen atom is removed from the aromatic hydrocarbon ring or aromatic heterocyclic ring Are substituted with an alkylene group (for example, an aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.) And a group obtained by further removing one hydrogen atom from the above. The alkylene group bonded to the aryl group or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

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

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

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

For divalent linking groups containing heteroatoms:
The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. In the divalent linking group containing a hetero atom, preferred examples of the linking group include —O—, —C (═O) —O—, —C (═O) —, and —O—C (═O). -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H is an alkyl group, an acyl group, etc. may be substituted with a _{group); -. S -, -} S (= O) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 ^{-O -, - Y 21 -C (} = O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C (= O) -O] m "-Y 22 - or A group represented by —Y ²¹ —O—C (═O) —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent; O is an oxygen atom, and m ″ is 0 to 0. Of an integer. ] Etc. are mentioned. When the divalent linking group containing a hetero atom is —C (═O) —NH—, —NH—, —NH—C (═O) —O—, —NH—C (═NH) —, The H may be substituted with a substituent such as an alkyl group or acyl. The substituent (alkyl group, acyl group, etc.) preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and particularly preferably 1 to 5 carbon atoms. Formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -O-Y 21 -, - [Y 21 -C (═O) —O] _{m ″} —Y ²² — or —Y ²¹ —O—C (═O) —Y ²² —, Y ²¹ and Y ²² each independently have a substituent. The divalent hydrocarbon group may be “a divalent hydrocarbon group optionally having substituent (s)” mentioned in the description of the divalent linking group. And the like. Y ²¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, particularly a methylene group or an ethylene group. preferable. Y ²² is preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. In the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² —, m ″ is an integer of 0 to 3, preferably an integer of 0 to 2, Or 1 is more preferable, and 1 is particularly preferable. That is, the group represented by the formula — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² — is represented by the formula —Y ²¹ —C (═O) —O—Y ²² —. Especially preferred are groups represented by the formula — (CH ₂ ) _{a ′} —C (═O) —O— (CH ₂ ) _{b ′} —, wherein a ′ is 1 to It is an integer of 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b ′ is an integer of 1 to 10, and 1 to 8 preferably an integer of, more preferably an integer of 1 to 5, more preferably 1 or 2, 1 is the most preferred. Among these, the epoxy group-containing group for R ^EP, a glycidyl group are preferable.

  Moreover, as a novolak-type epoxy resin (Anv), resin containing the structural unit represented by the following general formula (anv1) can be used conveniently.

(Wherein R ^EP is an epoxy group-containing group, and R ^a22 and R ^a23 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom.)
In the formula (anv1), the alkyl group having 1 to 5 carbon atoms of R ^a22 and R ^a23 is the same as the alkyl group having 1 to 5 carbon atoms of R ^a11 and R ^{a12 in} the formula (anv0). The halogen atom for R ^a22 and R ^a23 is preferably a chlorine atom or a bromine atom. Wherein ^(ANV1), the ^{R EP} be the same as ^{R EP} in the formula (anv0), a glycidyl group is preferable.

  Specific examples of the structural unit represented by the formula (anv1) are shown below.

  The novolak-type epoxy resin (Anv) may be a resin composed only of the structural unit (anv1), and is preferably a resin having the structural unit (anv1) and another structural unit. Examples of other structural units include structural units represented by the following general formulas (anv2) to (anv3), respectively.

(In the formula, R ^a24 is a hydrocarbon group which may have a substituent, and R ^{a25 to} R ^a26 and R ^{a28 to} R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, Or a halogen atom, and R ^a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent.)
In the formula (anv2), R ^a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group and a cyclic hydrocarbon group. The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and still more preferably 1 or 2. Specific examples include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and an n-pentyl group. Among these, a methyl group, an ethyl group or an n-butyl group is preferable, and a methyl group or an ethyl group is more preferable.

  The branched alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples include isopropyl group, isobutyl group, tert-butyl group, isopentyl group, neopentyl group, 1,1-diethylpropyl group, 2,2-dimethylbutyl group, and the like is preferably isopropyl group.

When R ^a24 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the aliphatic hydrocarbon group which is a monocyclic group, a group in which one hydrogen atom has been removed from a monocycloalkane is preferable. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group which is a polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycycloalkane, and the polycycloalkane is preferably a group having 7 to 12 carbon atoms, specifically Includes adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

When the cyclic hydrocarbon group of R ^a24 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having (4n + 2) π electrons, and may be monocyclic or polycyclic. The 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, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms. Etc. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group for R ^a24 include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring (aryl group or heteroaryl group); two or more aromatic rings A group in which one hydrogen atom has been removed from an aromatic compound containing, for example, biphenyl, fluorene, etc .; a group in which one of the hydrogen atoms of the aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (for example, benzyl Group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl groups such as 2-naphthylethyl group, etc.). The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

In formulas (anv2) and (anv3), R ^{a25 to} R ^a26 and R ^{a28 to} R ^a30 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogen atom, and having 1 to 5 carbon atoms The alkyl group and the halogen atom are the same as R ^a22 and R ^a23 , respectively.

In the formula (anv3), R ^a27 is an epoxy group-containing group or a hydrocarbon group which may have a substituent. Epoxy group-containing group of R ^a27 is the same as ^{R EP} of the formula (anv0) ^in, hydrocarbon group which may have a substituent ^{R a27} are the same as ^{R a24.}

  Specific examples of the structural units represented by the formulas (anv2) to (anv3) are shown below.

  In addition to the structural units represented by the formulas (anv2) to (anv3), other structural units that can replace the structural unit represented by the general formula (anv1) include polycycloalkane structural units. Can be mentioned. Such polycycloalkane structural units are preferably those having 7 to 12 carbon atoms, specifically, adamantane structural units, norbornane structural units, isobornane structural units, tricyclodecane structural units, tetracyclododecane structural units. Etc.

  In the case where the novolac type epoxy resin (Anv) has other structural units in addition to the structural unit (anv1), the ratio of each structural unit in the resin (Anv) is not particularly limited, but the resin (Anv ) Is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol%. More preferably.

  As a novolak type epoxy resin (Anv) which is a commercial product, for example, JER-152, JER-154, JER-157S70, JER-157S65 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, EPICLON N -740, EPICLON N-770, EPICLON N-775, EPICLON N-660, EPICLON N-665, EPICLON N-670, EPICLON N-673, EPICLON N-680, EPICLON N-690, EPICLON N-695, EPICLON EPICLON HP7200 (manufactured by DIC Corporation), EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), and the like.

(2) Bisphenol type epoxy resin (Abp)
As the bisphenol type epoxy resin (Abp), an epoxy resin having a structure represented by the following general formula (abp1) can be used.

(In the formula, R ^EP is an epoxy group-containing group, R ^a31 and R ^a32 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and na ³¹ is an integer of 1 to 50. )
Wherein ^(abp1), an alkyl group having 1 to 5 carbon atoms for R ^{a31, R a32} are the same alkyl group of 1 to 5 carbon atoms for ^{R a11, R a12} in the above formula (anv0). Among these, as R ^a31 and R ^a32 , a hydrogen atom or a methyl group is preferable. R ^EP is a similar to ^{R EP} in the formula (anv0), a glycidyl group is preferable.

  Examples of the bisphenol type epoxy resin (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, JER-1009, JER- 1010 (manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (manufactured by DIC Corporation), and the like; bisphenol F type epoxy resins include JER-806 and JER-807. , JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON 830, EPICLON 835 (above, made by DIC Corporation), LCE-21, RE-602S (above Manufactured by Nippon Kayaku Co., Ltd.), and the like.

(3) Alicyclic epoxy resin (A1)
As the polymerizable resin component having an epoxy group, an alicyclic epoxy resin (A1) (hereinafter also referred to as “(A1) component”) can be used. Here, the alicyclic epoxy resin (A1) is represented by the following formula (A1).

(In the formula, R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. Y ¹ and Y ² are each independently a single bond or a divalent linking group.)
In formula (A1), R ¹ and R ² are each independently an organic group optionally having an alicyclic epoxy group, and at least ^one of R ¹ and R ² is an alicyclic epoxy group. Have In the present embodiment, the “organic group optionally having an alicyclic epoxy group” means not only a combination of an alicyclic epoxy group and an organic group, but also a group consisting of only an alicyclic epoxy group (organic Group).

  Examples of the organic group include a linear, branched or cyclic alkyl group which may have a substituent, an aryl group which may have a substituent, and a hetero which may have a substituent. Examples thereof include an aryl group, an aralkyl group which may have a substituent, and a heteroaralkyl group which may have a substituent.

The organic group of R ¹ and R ² may have an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. The organic groups that may have an alicyclic epoxy group of R ¹ and R ² may be different or the same. R ¹ and R ² are preferably both organic groups having an alicyclic epoxy group, more preferably both are groups composed of an alicyclic epoxy group, and both are 1,2-epoxycyclohexyl. Particularly preferred is a group.

In formula (A1), Y ¹ and Y ² are each independently a single bond or a divalent linking group. Although it does not specifically limit as a bivalent coupling group, The aliphatic hydrocarbon group which contains a ring in a linear or branched chain structure, or an aromatic hydrocarbon group is mentioned. The aliphatic hydrocarbon group or aromatic hydrocarbon group 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, and a carbonyl group. In the aliphatic hydrocarbon group or the aromatic hydrocarbon group, a part of carbon atoms and hydrogen atoms constituting the structure may be substituted with a substituent containing a hetero atom. Examples of the substituent containing a hetero atom include —O—, —C (═O) —O—, —C (═O) —, —O—C (═O) —O—; —C (═O) —. NH—, —NH—, —NH—C (═O) —O—, —NH—C (═NH) — (H may be substituted with a substituent such as an alkyl group or an acyl group); _{-S -, - S (= O} ) 2 -, - S (= O) 2 -O-, the formula ^{-Y 21 -O-Y 22 -,} - Y 21 -O -, - Y 21 -C (= O) —O—, —C (═O) —O—Y ²¹ —, — [Y ²¹ —C (═O) —O] _{m ″} —Y ²² — or —Y ²¹ —O—C (═O) A group represented by —Y ²² —, wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, and may be linear or branched An alkylene group is preferred, wherein O is an oxygen atom, "It is an integer of 0 to 3. ] Etc. are mentioned.

Y ¹ and Y ² may be different or the same. When Y ¹ and Y ² are a divalent linking group, the divalent linking group may be a linear or branched chain which may have a substituent, or an aliphatic carbon containing a ring in the structure. A hydrogen group is preferable, a linear or branched aliphatic hydrocarbon group which may have a substituent is more preferable, and a linear or branched alkylene group which may have a substituent Is more preferable. The number of carbon atoms of the aliphatic hydrocarbon group and the alkylene group is preferably 1-30, more preferably 1-10, and even more preferably 1-3. Y ¹ and Y ² are preferably a single bond, a methylene group, an ethylene group or a propylene group, more preferably a single bond or a methylene group, particularly preferably Y ¹ is a single bond and Y ² is a methylene group.

  Preferred examples of the component (A1) include compounds represented by the following formulas (A1-1) to (A1-2).

Wherein R ¹ and R ² are the same as above, Y ⁰² is a single bond or a divalent linking group, n ¹ and n ⁴ are each independently an integer of 0 to 3, and n ² is 0 is an integer from to 10, ^{n 3} is 0 or 1.)
In formulas (A1-1) to (A1-2), R ¹ and R ² are the same as described above, and both are preferably organic groups having an alicyclic epoxy group, and both are alicyclic epoxy groups. It is more preferable that Wherein ^{(A1-1) ~ (A1-2),} Y 02 is a single bond or a divalent linking group, the divalent linking group include the same groups as the ^Y 1, ^{Y 2.} Among these, a single bond or a linear or branched chain which may have a substituent or an aliphatic hydrocarbon group containing a ring in the structure is preferable. In formulas (A1-1) to (A1-2), n ¹ and n ⁴ are each independently an integer of 0 to 3, and 0 or 1 is preferable. In formulas (A1-1) to (A1-2), n ² is an integer of 0 to 10, preferably an integer of 0 to 5, and more preferably 0. In formulas (A1-1) to (A1-2), n ³ is 0 or 1, and 0 is preferable.

Specific examples of the component (A1) are listed below. In the following formula, n ²¹ is an integer of 1 to 10.

  Preferred examples of commercially available alicyclic epoxy compounds include Celoxide 2021, 2021P, 2081, 2083, 2085 (manufactured by Daicel Chemical Industries).

(4) Polyfunctional alicyclic epoxy resin (A2)
As the polymerizable resin component having an epoxy group, a polyfunctional alicyclic epoxy resin (A2) (hereinafter, also referred to as “(A2) component”) can be used. A polyfunctional alicyclic epoxy resin (A2) is a compound which does not correspond to the said (A1) component. The component (A2) may be a low molecular compound or a polymer compound, but is preferably a polymer compound. The component (A2) is a bifunctional or higher polyfunctional epoxy compound, and is preferably a trifunctional or higher functional epoxy compound. As the component (A2), a compound represented by the following formula (A2-1) is preferable because of excellent chemical resistance and light resistance.

(In the formula, R ¹¹ is a residue obtained by removing active hydrogen groups in an organic compound having q active hydrogen groups. N ¹¹ , n ¹² ,..., N ^q are each independently 0 to 100. an integer, .A their sum indicating the it .q an integer of 1 to 100 1 to 100 is used, the number oxycyclohexane skeleton containing substituents ^{R 12,} or an oxy norbornene skeleton containing substituents ^{R 12} And represented by the following formula (a1) or (a2).)

(In the formula, R ¹² is each independently a group represented by the following formulas (a11) to (a13), and the compound represented by the formula (A2-1) is a group represented by (a11)). The group represented by the formulas (a1) and (a2) is bonded to R ¹¹ in the compound represented by the formula (A2-1) at the wavy bond, and at the bond indicated by *. Bonded to a hydrogen atom (H) in the compound represented by the formula (A2-1).)

(R ¹³ represents an alkyl group, an alkylcarbonyl group, or an arylcarbonyl group. The groups represented by the formulas (a11) to (a13) are represented by the formulas (a1) and (a2) at the wavy bond. Bond to the group
In the formula (A2-1), R ¹¹ is a residue obtained by removing an active hydrogen group in an organic compound having an active hydrogen group, but as an “organic compound having an active hydrogen group” as a precursor thereof, , Alcohols, phenols, carboxylic acids, amines, thiols and the like.

  The alcohols may be monohydric alcohols or polyhydric alcohols. Specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol; aromatic alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene Glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, hydroxypivalic acid neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, Examples thereof include polyhydric alcohols such as trimethylolpropane, trimethylolethane, pentaerythritol and dipentaerythritol. Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, 4,4'-dihydroxybenzophenone, bisphenol S, a phenol resin, and a cresol novolac resin. Examples of the carboxylic acids include formic acid, acetic acid, propionic acid, butyric acid, fatty acids of animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanedioic acid, trimellitic acid, pyromellitic acid, polyacrylic acid, phthalic acid, isophthalic acid And terephthalic acid. Moreover, the compound which has both a hydroxyl group and a carboxyl group, such as lactic acid, a citric acid, and oxycaproic acid, is also mentioned. Examples of the amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4′-diaminodiphenylmethane, isophorone. Examples include diamine, toluene diamine, hexamethylene diamine, xylene diamine, diethylenetriamine, triethylenetetramine, and ethanolamine. Examples of the thiols include mercapto such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan; mercapto such as ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptopropionate, etc. And propionic acid or mercaptopropionic acid polyhydric alcohol ester.

  In addition, organic compounds having active hydrogen groups include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene. -Maleic acid copolymer resin, alkyd resin, polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin, polypropylene polyol, polytetramethylene glycol and the like can also be mentioned.

  The organic compound having an active hydrogen group may have an unsaturated double bond in its skeleton. Specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, tetrahydrophthalic acid and the like. The above organic compounds having an active hydrogen group may be used alone or in combination of two or more.

In the formula ^{(A2-1), n 11, n} 12, ···, n q are independently an integer of 0 to 100, the sum is 1-100. Moreover, q shows the integer of 1-100. Of these ^{n 11, n 12, ···,} n q is preferably independently 2-10 integer, an integer of 3-6 is more preferable. ^Further, n ^11, n 12, · · ·, the sum of ^{n q} is preferably 4 to 30, more preferably 4 to 20. By setting the sum to 4 or more, the crosslinking density after curing can be increased and the hardness can be increased. Moreover, by making the said sum 30 or less, the solubility to a solvent can be improved and handling property can be improved.

In the formula (A2-1), A is represented by a oxy norbornene skeleton containing oxycyclohexane skeleton or substituents ^{R 12} contains a substituent ^{R 12,} and the formula (a1) or (a2) The A is preferably represented by the formula (a1). Note that q A's may be the same or different.

  In the epoxy compound represented by the formula (A2-1), it is essential that one or more groups represented by the formula (a11) are contained, and the more the more, the more preferable. On the other hand, the smaller the group represented by the formula (a13), the better.

The epoxy compound represented by the formula (A2-1) is prepared by using an organic compound having an active hydrogen group as an initiator, as described in Japanese Patent Publication No. 7-119270, or 4-vinylcyclohexene-1-oxide or Polyether resin obtained by ring-opening polymerization of a mixture of 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide and a compound having one epoxy group, that is, a vinyl group side chain And a polyether resin having a cyclohexane skeleton or a vinyl side chain and a norbornene skeleton is produced by epoxidation with peracetic acid or hydrogen peroxide. Examples of commercially available products, manufactured by Daicel Chemical Industries, Ltd. of EHPE3150 ^(sum of ⁿ 11 ~n ^q is 15 on average), and as is preferred.

  Moreover, (A1) component and (A2) component when preparing the composition for formation of a separated layer by using an alicyclic epoxy resin (A1) and a polyfunctional alicyclic epoxy resin (A2) together. The blending ratio is (A1) / (A2) = 70/30 to 51/49 (mass ratio), and more preferably 70/30 to 60/40 (mass ratio). By setting it as the said mixture ratio, the melt viscosity of the composition for separated layer formation obtained can be made into the preferable range mentioned later. Thereby, the composition for separation layer formation can be apply | coated so that a film thickness may become uniform. In addition, a separation layer having high chemical resistance can be formed. As a commercial item of the epoxy resin that uses the alicyclic epoxy resin (A1) and the polyfunctional alicyclic epoxy resin (A2) in combination, for example, EHPE3150CE manufactured by Daicel Chemical Industries, Ltd. is preferable.

(5) Acrylic resin having epoxy group (Aac)
Examples of the polymerizable resin component having an epoxy group include an acrylic resin having an epoxy group obtained by copolymerizing at least an unsaturated carboxylic acid and a compound having an epoxy group and an ethylenically unsaturated double bond ( Aac) can be used.

  Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  In the present specification, “(meth) acrylic acid” means both acrylic acid and methacrylic acid.

  In the present specification, the “compound having an ethylenically unsaturated double bond” may be referred to as an “unsaturated compound”.

  The proportion of the structural unit derived from the unsaturated carboxylic acid (the structural unit having a carboxyl group) in the acrylic resin having an epoxy group is preferably 5 to 29% by mass, and more preferably 10 to 25% by mass. .

  Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and anhydrides of these dicarboxylic acids; It is done. Among these, (meth) acrylic acid and maleic anhydride are preferable in terms of copolymerization reactivity, alkali solubility of the resulting resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  The compound having an epoxy group and an ethylenically unsaturated double bond may have no alicyclic epoxy group, or may have an alicyclic epoxy group. Those having an epoxy group are more preferred.

  Examples of the compound having an epoxy group that is not an alicyclic epoxy group and an ethylenically unsaturated double bond include glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate, (Meth) acrylic acid epoxy alkyl esters such as 6,7-epoxyheptyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; glycidyl α-ethyl acrylate, glycidyl α-n-propyl acrylate, α Α-alkylacrylic acid epoxy alkyl esters such as glycidyl n-butyl acrylate and α-ethyl acrylate 6,7-epoxyheptyl; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Such as ether Glycidyl ethers; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl from the viewpoints of copolymerization reactivity, strength of cured resin, and the like. Glycidyl ether, m-vinylbenzyl glycidyl ether, and p-vinylbenzyl glycidyl ether are preferred.

  The alicyclic group of the compound having an epoxy group which is an alicyclic epoxy group and an ethylenically unsaturated double bond may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the compound having an epoxy group that is an alicyclic epoxy group and an ethylenically unsaturated double bond include compounds represented by the following formulas (a4-1) to (a4-16). . Among these, the compounds represented by the following formulas (a4-1) to (a4-6) are preferable in order to make the curability of the composition for forming a separation layer moderate, and the following formula (a4-1) ) To (a4-4) are more preferred.

In the above formula, R ^a3 represents a hydrogen atom or a methyl group, R ^a4 represents a divalent saturated aliphatic hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Represents a group, and n represents an integer of 0 to 10. R ^a4 is preferably a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a5 , for example, methylene group, ethylene group, propylene group, tetramethylene group, ethylethylene group, pentamethylene group, hexamethylene group, phenylene group, cyclohexylene group, —CH ₂ —Ph—CH ₂ — (Ph is A phenylene group) is preferred.

  These compounds having an epoxy group and an ethylenically unsaturated double bond can be used alone or in combination of two or more.

  The proportion of the structural unit derived from an unsaturated compound having an epoxy group (the structural unit having an epoxy group) in the acrylic resin having an epoxy group is preferably 5 to 90% by mass, and preferably 15 to 85% by mass. Is more preferable, and it is especially preferable that it is 50-85 mass%. By setting it as the said range, the acrylic resin which has an epoxy group can be hardened suitably.

  The acrylic resin having an epoxy group is preferably one obtained by further copolymerizing a compound having an alicyclic group and an ethylenically unsaturated double bond.

  The alicyclic group of the compound having an alicyclic group and an ethylenically unsaturated double bond may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic alicyclic group include an adamantyl group, a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specifically, examples of the compound having an alicyclic group and an ethylenically unsaturated double bond include compounds represented by the following formulas (a5-1) to (a5-8). Among these, the compounds represented by the following formulas (a5-3) to (a5-8) are preferable in order to make the curability of the composition for forming a separation layer moderate, and the following formula (a5-3) ) And a compound represented by (a5-4) are more preferable.

In the above formula, R ^a6 represents a hydrogen atom or a methyl group, R ^a7 represents a single bond or a divalent aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a8 represents a hydrogen atom or 1 to 5 carbon atoms. Represents an alkyl group. R ^a7 is preferably a single bond or a linear or branched alkylene group such as a methylene group, an ethylene group, a propylene group, a tetramethylene group, an ethylethylene group, a pentamethylene group, or a hexamethylene group. As R ^a8 , for example, a methyl group and an ethyl group are preferable.

  The proportion of the structural unit derived from the compound having an alicyclic group and an ethylenically unsaturated double bond in the acrylic resin having an epoxy group is preferably 1 to 40% by mass, and 5 to 30% by mass. More preferably.

  Moreover, the acrylic resin which has an epoxy group may further copolymerize other compounds other than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, and the like. These compounds can be used alone or in combination of two or more.

  As (meth) acrylic acid esters, linear or branched chain such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, t-octyl (meth) acrylate, etc. Alkyl (meth) acrylates; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; etc. are mentioned.

  (Meth) acrylamides include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-dialkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N -Methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-methyl (meth) acrylamide and the like.

  Examples of the allyl compound include allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate, etc .; allyloxyethanol; Can be mentioned.

  As vinyl ethers, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethyl hexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether , Alkyl vinyl ethers such as diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichloropheny And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

  Vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinyl vinyl. Examples include enyl acetate, vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthoate and the like.

  Styrenes include: styrene; methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxy Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, Dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethyl Styrene, halostyrenes such as 4-fluoro-3-trifluoromethyl styrene; and the like.

  The mass average molecular weight of the acrylic resin having an epoxy group is preferably 2000 to 50000, and more preferably 3000 to 30000.

[2. Polymerizable resin component having an ethylenically unsaturated double bond]
The polymerizable resin component having an ethylenically unsaturated double bond is a low molecular compound as long as it has sufficient ethylenically unsaturated double bonds to cure by heating or exposure in one molecule. It may be a polymer such as a homopolymer or a copolymer resin. Among these, specific examples of the polymerizable resin component having a more preferable ethylenically unsaturated double bond are shown below.

(1) Low molecular compound having an ethylenically unsaturated double bond Typically, a low molecular compound having an ethylenically unsaturated double bond includes (meth) acrylic acid and a polyhydric alcohol or polycarboxylic acid. Or an unsaturated carboxylic acid ester or amide having a functional group such as a hydroxyl group, amino group, or mercapto group, and a polyhydric alcohol or polycarboxylic acid, an isocyanate group or an epoxy group. And polyfunctional monomers such as addition polymers obtained by addition polymerization via a monofunctional monomer and monofunctional monomers having an ethylenically unsaturated double bond.

  Polyfunctional monomers include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, butylene glycol di ( (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexane glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, glycerin di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate , Dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (meth) acrylate Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydi Ethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) Acrylate, diethylene glycol diglycidyl ether di (meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meta Acrylate, urethane (meth) acrylate (ie, tolylene diisocyanate), a reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylene bis (meth) acrylamide, (meth) acrylamide methylene ether, Examples thereof include polyfunctional monomers such as a condensate of polyhydric alcohol and N-methylol (meth) acrylamide, and triacryl formal. These polyfunctional monomers can be used alone or in combination of two or more.

  Monofunctional monomers include (meth) acrylamide, methylol (meth) acrylamide, methoxymethyl (meth) acrylamide, ethoxymethyl (meth) acrylamide, propoxymethyl (meth) acrylamide, butoxymethoxymethyl (meth) acrylamide, N- Methylol (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, (meth) acrylic acid, fumaric acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, crotonic acid, 2- Acrylamide-2-methylpropanesulfonic acid, tert-butylacrylamidesulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) a Relate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (Meth) acryloyloxy-2-hydroxypropyl phthalate, glycerin mono (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, glycidyl (meth) acrylate, 2,2,2-trifluoroethyl ( And (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, and half (meth) acrylate of a phthalic acid derivative. These monofunctional monomers can be used alone or in combination of two or more.

(2) Copolymer resin having an ethylenically unsaturated group For the polymerizable resin component having an ethylenically unsaturated double bond, a copolymer resin having an ethylenically unsaturated double bond can also be used. Examples of such a copolymer resin having an ethylenically unsaturated double bond include, for example, an ethylenic double chain on the side chain of an acrylic resin skeleton composed of (meth) acrylic acid and (meth) acrylic acid ester. Examples thereof include (meth) acrylic resin into which a bond is introduced.

  Examples of the polymerizable resin component having an ethylenically unsaturated group include a carboxyl group of a resin obtained by copolymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, and an epoxy of an epoxy group-containing unsaturated compound. A resin obtained by reacting a group, or an epoxy group of a resin obtained by copolymerizing at least an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound with a carboxyl group of an unsaturated carboxylic acid. Examples thereof include resins obtained. That is, as a resin for copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, one form of the above-described acrylic resin (Aac) having an epoxy group can be exemplified.

  In addition, as a method of introducing an ethylenically unsaturated double bond into an acrylic resin skeleton, as described above, an ethylenically unsaturated double bond via a carboxylic acid that the acrylic resin skeleton has and an epoxy group It is not limited to the form which introduces. For example, an acrylic resin having a carboxylic acid group, a hydroxyl group, an amine group, an amide group, and a thiol group in the side chain, an ethylenically unsaturated double bond, a carboxylic acid group, a hydroxyl group, an amine group, an amide The structure which introduce | transduces an ethylenically unsaturated double bond may be sufficient by making a monomer provided with group, a thiol group, etc. react, for example with polyfunctional isocyanate or polyfunctional epoxy resin.

  Furthermore, the (meth) acrylic resin into which the ethylenic double bond is introduced may be a (meth) acrylate homopolymer or copolymer having an ethylenically unsaturated double bond and an epoxy group. Good.

  The proportion of the structural unit derived from the epoxy group-containing unsaturated compound (the structural unit having an epoxy group) in the polymerizable resin component having an ethylenically unsaturated double bond is preferably 5 to 90% by mass, More preferably, it is 15-75 mass%. By setting it as the said range, a separated layer can be hardened suitably.

  The mass average molecular weight of the polymerizable resin component having an ethylenically unsaturated double bond is preferably 2000 to 50000, and more preferably 5000 to 30000. By setting it as the said range, suitable coating workability | operativity of the composition for separated layer formation can be obtained.

[3. Crosslinkable group-containing siloxane]
The polymerizable resin component may be a crosslinkable group-containing siloxane (Asi).

In the present specification, the crosslinkable group-containing siloxane (Asi) is a compound having a crosslinkable group such as an epoxy group and a vinyl group in the side chain of the siloxane skeleton as shown in the following formula (Asi0). Indicates.
-(SiO _3/2 (R ¹ )) _m- (SiO _3/2 (R ² )) _n- (Asi0)
(Here, R ¹ is a crosslinkable group, R ² is selected from an alkyl group, an aryl group, or an aromatic group. M and n are the subscripts for all structural units in the polysiloxane. Represents the mole percentage of the attached structural unit, n + m = 100%, n> 0).

  Epoxy group siloxane can form a polymer by cross-linking polymerization in the epoxy group with a photocationic polymerization initiator or a thermal cationic polymerization initiator.

  From the viewpoint of producing a laminate having excellent physical properties such as laser reactivity and heat resistance of the separation layer, the crosslinkable group-containing siloxane is preferably a crosslinkable group-containing siloxane represented by the following general formula (Asi1). .

(Wherein R ^c1 is a group containing an epoxy group, oxetanyl group, vinyl group, (meth) acryloyl group, R ^c2 is an alkyl group or an aryl group, and the subscripts m and n are those in the polysiloxane. Represents the mole percentage of the structural unit to which the above-mentioned subscripts are attached relative to all the structural units, and m is 50 to 90 mol% and n is 10 to 50 mol%, provided that the sum of m and n is 100 mol. %.)

Specific examples of the crosslinkable group-containing siloxane include polymer E, polymer F represented by the following formula, and trade names X-22-2046 and KF-102 manufactured by Shin-Etsu Silicone Co., Ltd .:
Polymer E: Epoxy-modified siloxane represented by the following formula (Asi2) (mass average molecular weight: 1000 to 20000)

(In the formula (Asi2), the subscripts m1 and n1 represent the mole percentage of the structural unit to which the subscript is attached relative to all the structural units in the polymer E, m1 = 50 to 90 mol%, and n1 = 10 -50 mol%, provided that the sum of m1 and n1 is 100 mol%.)
Polymer F: Epoxy-modified siloxane represented by the following formula (Asi3) (mass average molecular weight: 1000 to 20000)

(In the formula (Asi3), the subscripts m2, n2, and n3 represent the mole percentage of the structural unit to which the subscript is attached relative to all the structural units in the polymer F, and m2 = 50 to 90 mol%, n2 = 1 to 10 mol%, n3 = 5 to 50 mol%, provided that the total of m2, n2 and n3 is 100 mol%).

(Polymerization initiator)
The polymerization initiator may be any one that can cure the polymerizable resin component having a polymerizable group such as an epoxy group or an ethylenically unsaturated double bond. Examples of the polymerization initiator that can cure the polymerizable resin component having the polymerizable group include a thermal cationic polymerization initiator and a photocationic polymerization initiator. Moreover, a thermal radical polymerization initiator and a photo radical polymerization initiator can be mentioned, for example. Hereinafter, the thermal cationic polymerization initiator, the photo cationic polymerization initiator, the thermal radical polymerization initiator, and the photo radical polymerization initiator will be described in detail.

(1) Thermal Cationic Polymerization Initiator The composition for forming a separation layer according to one embodiment contains a thermal cationic polymerization initiator as a polymerization initiator. Moreover, in such a thermal cationic polymerization initiator, a polymerization initiator that generates an acid by heat may be referred to as a thermal acid generator. The composition for forming a separation layer can promote polymerization of a polymerizable group by the action of a cation generated by heat during a heat curing treatment. Below, the compound which can be used as a thermal cationic polymerization initiator is demonstrated in detail.

(Cation)
Examples of the thermal cationic polymerization initiator include compounds having a cation moiety represented by the following general formula (h01) or (h02).

(In (h01), Rh ^{01 to} Rh ⁰⁴ are each independently an organic group selected from the group consisting of hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group, (It may have a substituent, and at least one of Rh ^{01 to} Rh ⁰⁴ is an aryl group.)

(In the above and (h02), Rh ^{05 to} Rh ⁰⁷ are each independently an organic group selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an aryl group, and the aryl group is substituted. And may have a group, and at least one of Rh ^{05 to} Rh ⁰⁷ is an aryl group.)
Here, when Rh ^{01 to} Rh ⁰⁷ are an aryl group, the aryl group is preferably a phenyl group represented by the following general formula (h01-1).

(In hr-1, R ^hc01 may be hydrogen, a hydroxyl group, or an alkyl group having 1 to 10 carbon atoms, and the alkyl group having 1 to 10 carbon atoms may be bonded via an ether bond or an ester bond ( hr-1) may be bonded to a phenyl group, and hr-1 in Rh ^{01 to} Rh ⁰⁷ may be each independently a different substituent.)
Preferable forms of the cation moiety represented by the general formula (h01) include the following cation moieties.

  Moreover, as a preferable form of the cation part shown in general formula (h02), the following cation part can be mentioned. Such an aromatic onium salt having a cation moiety is excellent in stability at room temperature and generates an acid by heat, and therefore can be preferably used as a thermal acid generator.

  Moreover, as a preferable form of the cation part shown in general formula (h02), the following cation part can be mentioned.

(Anion part)
Examples of the anion moiety in the thermal cationic polymerization initiator include a hexafluorophosphate anion, a tolyloromethane sulfonate anion, a perfluorobutane sulfonate anion, and a tetrakis (pentafluorophenyl) borate anion.

  Examples of commercially available thermal cationic polymerization initiators include Sun 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 (manufactured by Sanshin Chemical Industry Co., Ltd.) ) And the like. In addition, CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2624, CI-2039 (manufactured by Nippon Soda Co., Ltd.), CP-66, CP-77 ((shares) ADEKA), FC-520 (manufactured by 3M) K-PURE TAG-2396, TAG-2713S, TAG-2713, TAG-2172, TAG-2179, TAG-2168E, TAG-2722, TAG-2507, TAG- 2678, TAG-2681, TAG-2679, TAG-2690, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, C C-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60 (KING INDUSTRY Co., Ltd.). Among the above, trifluoromethanesulfonate or hexafluorophosphate is preferable, and trifluoromethanesulfonate is more preferable.

  The temperature for generating the acid in the thermal cationic polymerization initiator is preferably equal to or higher than the temperature for pre-baking the support coated with the composition for forming the separation layer, and specifically 110 ° C. or higher. Is preferable, and it is more preferable that it is 130 degreeC or more.

  The amount of the thermal cationic polymerization initiator is preferably 0.01% by weight or more and 20% by weight or less, preferably 1% by weight or more and 10% by weight or less, based on the total solid content of the composition for forming a separation layer. More preferably, it is 5 wt% or more and 10 wt% or less. If the blending amount of the thermal acid generator is 0.1% by weight or more, not only can the polymerizable resin component be suitably polymerized, but also by firing a cured product of the polymerizable resin component, for example, Further, it is possible to form a fired body that can suitably absorb light in a wavelength range of 600 nm or less.

(2) Photocationic polymerization initiator In the present invention, the photocationic polymerization initiator is selected from the group consisting of a compound represented by the following general formula (b0-1) and a compound represented by the following general formula (b0-2). One or more selected cationic polymerization initiators (B0) (hereinafter referred to as “(B0) component”) may be used.

( ^Wherein R ^{b01 to} R ^b04 are each independently a fluorine atom or an aryl group which may have a substituent. R ^b05 is a fluorine atom or a fluorine which may have a substituent) A plurality of R ^b05 may be the same or different from each other, q is an integer of 1 or more, and Q ^{q +} is each independently a q-valent organic cation. )
[(B0) component]
The component (B0) is at least one cationic polymerization initiator selected from the group consisting of the compound represented by the general formula (b0-1) and the compound represented by the general formula (b0-2). . These two compounds generate a relatively strong acid upon exposure. For this reason, the composition for forming a separation layer having the component (B0) can suitably cure the polymerizable resin component having an epoxy group by exposure.

In formula (b0-1), R ^{b01 to} R ^b04 each independently represent a fluorine atom or an aryl group which may have a substituent. The aryl group that may have a substituent of R ^{b01 to} R ^b04 preferably has 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and still more preferably 6 to 15 carbon atoms. 6 to 12 is particularly preferable. Specific examples include a naphthyl group, a phenyl group, and an anthracenyl group, and a phenyl group is preferable because it is easily available. The aryl group may have a substituent. Although it does not specifically limit as a substituent, A halogen atom, a hydroxyl group, and a hydrocarbon group (a linear or branched alkyl group is preferable, and C1-C5 is preferable), a halogen atom or A halogenated alkyl group having 1 to 5 carbon atoms is more preferable, and a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms is particularly preferable. It is preferable that the aryl group has a fluorine atom because the polarity of the anion portion is increased. Among ^these, as R ^{b01 to} R ^{b04 in the} formula (b0-1), a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

Preferable specific examples of the anion moiety of the compound represented by the formula (b0-1) 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. Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

In formula (b0-2), R ^b05 is a fluorine atom or a fluorinated alkyl group which may have a substituent, and a plurality of R ^b05 may be the same or different. Good.

The fluorinated alkyl group which may have a substituent for R ^b05 preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, and still more preferably 1 to 5 carbon atoms. Specifically, in the alkyl group having 1 to 5 carbon atoms described above in the description of R ^a22 and R ^a23, a group in which part or all of the hydrogen atoms are substituted with fluorine atoms can be given. Among them, R ^b05 is preferably a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and a fluorine atom, a trifluoromethyl group or pentafluoro. More preferred is an ethyl group.
What is represented by the following general formula (b0-2a) is preferable for the anion part of the compound represented by the formula (b0-2).

(In the formula, R ^bf05 is a fluorinated alkyl group which may have a substituent, and nb ¹ is an integer of ¹ to 5.)
Wherein (b0-2a), as good a fluorinated alkyl group optionally having a substituent ^R bf05, is the same as good a fluorinated alkyl group which may have a substituent cited above as R ^b05 . In formula (b0-2a), nb ¹ is preferably ¹ to 4, more preferably 2 to 4, and most preferably 3.

In the formulas (b0-1) to (b0-2), q is an integer of 1 or more, Q ^{q +} is a q-valent organic cation, and a sulfonium cation and an iodonium cation are preferable examples. The organic cations represented by (ca-1) to (ca-5) are particularly preferred.

(In the formula, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each independently represent an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent, and R ^{201 to} R ^203. , R ^{206 to} R ²⁰⁷ , R ^{211 to} R ²¹² may be bonded to each other to form a ring together with the sulfur atom in the formula, and R ^{208 to} R ²⁰⁹ are each independently a hydrogen atom or a carbon number of 1 to 5 R ²¹⁰ represents an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. and they may be -SO ₂ - containing cyclic ^{group, L 201} is -C (= O) - or C (= O) represents ^{-O-, Y 201} each independently represent an arylene group, an alkylene Group or alkenylene The stands, x is 1 or ^{2, W 201} represents the (x + 1) -valent linking group.)
As the aryl group in R ²⁰¹ to R ^207, and ^R 211 ^{to R 212,} include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group. The heteroaryl group in R ²⁰¹ to R ^207, and ^R 211 ^{to R 212,} part of the carbon atoms constituting the aryl group include those substituted with a heteroatom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene; examples of the substituted heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthen-9-one. The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is a chain or cyclic alkyl group, preferably having 1 to 30 carbon atoms. The alkenyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² preferably has 2 to 10 carbon atoms. Examples of the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, and an oxo group (= O), an aryl group, and groups represented by the following formulas (ca-r-1) to (ca-r-10).

(In the formula, each R ′ ²⁰¹ independently has a hydrogen atom, a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a substituent. It may be a chain alkenyl group.
R ′ ²⁰¹ is a cyclic group which may have a substituent, a chain alkyl group which may have a substituent, or a chain alkenyl group which may have a substituent. .

Cyclic group which may have a substituent:
The cyclic group is preferably a cyclic hydrocarbon group, and the cyclic hydrocarbon group may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated, and is usually preferably saturated.

The aromatic hydrocarbon group for R ′ ²⁰¹ is a hydrocarbon group having an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30 carbon atoms, still more preferably 5 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms. Most preferably, it is -10. However, the carbon number does not include the carbon number in the substituent. Specific examples of the aromatic ring of the aromatic hydrocarbon group in R ′ ²⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is a heteroatom. Examples thereof include substituted aromatic heterocycles, or rings in which a part of hydrogen atoms constituting these aromatic rings or aromatic heterocycles is substituted with an oxo group or the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specifically, the aromatic hydrocarbon group in R ′ ²⁰¹ is a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, anthracenyl group, etc.), Groups in which one of the hydrogen atoms is substituted with an alkylene group (for example, arylalkyl groups such as benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2-naphthylethyl group, etc. ), A group obtained by removing one hydrogen atom from a ring in which a part of hydrogen atoms constituting the aromatic ring is substituted with an oxo group (for example, anthraquinone), an aromatic heterocyclic ring (for example, 9H-thioxanthene, 9H- A group obtained by removing one hydrogen atom from thioxanthen-9-one and the like. The alkylene group (alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

Examples of the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ include an aliphatic hydrocarbon group containing a ring in the structure. As the aliphatic hydrocarbon group containing a ring in this structure, an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched Examples include a group bonded to the end of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is interposed in the middle of a linear or branched aliphatic hydrocarbon group. The alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The alicyclic hydrocarbon group may be a polycyclic group or a monocyclic group. 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 preferably has 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among these, the polycycloalkane includes polycycloalkanes having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; condensed ring systems such as a cyclic group having a steroid skeleton A polycycloalkane having a polycyclic skeleton is more preferable.

Among them, the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ is preferably a group obtained by removing one or more hydrogen atoms from a monocycloalkane or polycycloalkane, and a group obtained by removing one hydrogen atom from a polycycloalkane. More preferred are an adamantyl group and a norbornyl group, and most preferred is an adamantyl group.

The linear or branched aliphatic hydrocarbon group that may be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, It is more preferable that it is 1-4, and it is most preferable that it is 1-3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group [—CH ₂ —], an ethylene group [— (CH ₂ ) ₂ —], a trimethylene group [ — (CH ₂ ) ₃ —], tetramethylene group [— (CH ₂ ) ₄ —], pentamethylene group [— (CH ₂ ) ₅ —] and the like can be mentioned. As the branched aliphatic hydrocarbon group, a branched alkylene group is preferred, and specifically, —CH (CH ₃ ) —, —CH (CH ₂ CH ₃ ) —, —C (CH ₃ ). _{2 -, - C (CH 3} ) (CH 2 CH 3) -, - C (CH 3) (CH 2 CH 2 CH 3) -, - C (CH 2 CH 3) 2 - ; alkylethylene groups such as - _{CH (CH 3) CH 2 -} , - CH (CH 3) CH (CH 3) -, - C (CH 3) 2 CH 2 -, - CH (CH 2 CH 3) CH 2 -, - C (CH 2 CH _{3) 2} -CH ₂ - alkyl groups such _{as; -CH (CH 3) CH 2} CH 2 -, - CH 2 CH (CH 3) CH 2 - alkyl trimethylene groups such as; -CH _(CH 3) _{CH 2 CH 2 CH 2 -,} - CH 2 CH (CH 3) CH 2 CH 2 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. The alkyl group in the alkyl alkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

A chain-like alkyl group which may have a substituent:
The chain alkyl group for R ′ ²⁰¹ may be either linear or branched. The linear alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Specifically, for example, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decanyl group, undecyl group, dodecyl group, tridecyl group, isotridecyl group, tetradecyl group Group, pentadecyl group, hexadecyl group, isohexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, heicosyl group, docosyl group and the like.

  The branched alkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, for example, 1-methylethyl group, 1-methylpropyl group, 2-methylpropyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, Examples include 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group and the like.

A chain-like alkenyl group which may have a substituent:
The chain alkenyl group for R ′ ²⁰¹ may be either linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and 2 to 4 carbon atoms. More preferably, it is particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, a propenyl group (allyl group), and a butynyl group. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methylpropenyl group, 2-methylpropenyl group and the like. Among the above, the chain alkenyl group is preferably a linear alkenyl group, more preferably a vinyl group or propenyl group, and particularly preferably a vinyl group.

Examples of the substituent in the cyclic group, chain alkyl group or alkenyl group of R ′ ²⁰¹ include, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, a nitro group, an amino group, an oxo group, Examples thereof include a cyclic group for R ′ ²⁰¹ .

Among these, R ′ ²⁰¹ is preferably a cyclic group which may have a substituent, or a chain alkyl group which may have a substituent.

^{R 201 ~R 203, R 206 ~R} 207, R 211 ~R 212 , when bonded to each other to form a ring with the sulfur atom, a sulfur atom, an oxygen atom, or a hetero atom such as nitrogen atom, carbonyl _{group, -SO -, - SO 2 -} , - SO 3 -, - COO -, - CONH- , or N _(R N) - (. the _{R N} is an alkyl group having 1 to 5 carbon atoms), such as You may couple | bond through a functional group. As the ring to be formed, one ring containing a sulfur atom in the ring skeleton in the formula is preferably a 3 to 10-membered ring, particularly a 5 to 7-membered ring, including the sulfur atom. preferable. Specific examples of the ring formed include, for example, thiophene ring, thiazole ring, benzothiophene ring, thianthrene ring, benzothiophene ring, dibenzothiophene ring, 9H-thioxanthene ring, thioxanthone ring, thianthrene ring, phenoxathiin ring, tetrahydro A thiophenium ring, a tetrahydrothiopyranium ring, etc. are mentioned.

R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is preferable. A ring may be formed.

R ²¹⁰ may have an aryl group which may have a substituent, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. -SO ₂ - containing cyclic group. The aryl group in R ^210, include unsubstituted aryl group having 6 to 20 carbon atoms, a phenyl group, a naphthyl group. The alkyl group for R ²¹⁰ is preferably a chain or cyclic alkyl group having 1 to 30 carbon atoms. The alkenyl group for R ²¹⁰ preferably has 2 to 10 carbon atoms.

Y ²⁰¹ each independently represents an arylene group, an alkylene group or an alkenylene group.

Examples of the arylene group for Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group exemplified as the aromatic hydrocarbon group for R ′ ²⁰¹ . Examples of the alkylene group and alkenylene group for Y ²⁰¹ include groups in which one hydrogen atom has been removed from the groups exemplified as the chain alkyl group and chain alkenyl group for R ′ ²⁰¹ .

In the formula (ca-4), x is 1 or 2. W ²⁰¹ is a (x + 1) valence, that is, a divalent or trivalent linking group. Examples of the divalent linking group for W ^201, a divalent hydrocarbon group which may have a substituent are preferable, which may have a substituent exemplified for R ^EP of the formula (anv0) in A group similar to the divalent hydrocarbon group is preferred. The divalent linking group in W ²⁰¹ may be linear, branched or cyclic, and is preferably cyclic. Of these, a group in which two carbonyl groups are combined at both ends of the arylene group, or a group consisting only of the arylene group is preferable. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferable. ^Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , a group in which the divalent linking group is further bonded to the divalent linking group, and the like. Can be mentioned. The trivalent linking group in W ²⁰¹ is preferably a group in which two carbonyl groups are bonded to an arylene group.

  Specific examples of suitable cations represented by the formula (ca-1) include cations represented by the following formulas (ca-1-1) to (ca-1-24), respectively.

(In the formula, R ″ ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as those exemplified as the substituent that R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. .)
Moreover, as a cation represented by the said formula (ca-1), the cation represented by each of the following general formula (ca-1-25)-(ca-1-36) is also preferable.

(In the formula, R ′ ²¹¹ is an alkyl group, and R ^hal is a hydrogen atom or a halogen atom.)
Specific examples of suitable cations represented by the formula (ca-2) include diphenyliodonium cation and bis (4-tert-butylphenyl) iodonium cation.

  Specific examples of suitable cations represented by the formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

  Moreover, as a cation represented by the said formula (ca-5), the cation represented by each of the following general formula (ca-5-1)-(ca-5-2) is also preferable.

(In the formula, R ′ ²¹¹ is an alkyl group.)
Among the above, the cation part [(Q ^{q +} ) _{1 / q} ] is preferably a cation represented by the general formula (ca-1), and each represented by the formulas (ca-1-1) to (ca-1-36). The represented cation is more preferred.

  In such a cationic photopolymerization initiator, the polymerization initiator that generates an acid by light may be referred to as a photoacid generator.

  As the component (B0), the above-described photoacid generators may be used alone or in combination of two or more. The content ratio of the component (B0) in the composition for forming a separation layer of the present invention is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable resin component having an epoxy group. Is more preferable, 0.2 to 5 parts by mass is further preferable, and 0.5 to 2 parts by mass is particularly preferable. In the composition for forming a separation layer of the present invention, the content ratio of the component (B0) in the photocationic polymerization initiator is not particularly limited, and the structure derived from the component (B0) and the acid derived from the anion moiety. It can be appropriately determined according to the above. Specifically, the content ratio of the component (B0) in the photocationic polymerization initiator is preferably 20 to 99.999% by mass, more preferably 30 to 99.99% by mass, and 40 to 40%. It is more preferably 99.9% by mass, particularly preferably 60 to 99.9% by mass, and most preferably 90 to 99.6% by mass. By setting the content ratio of the component (B0) within the above range, the strength of the plurality of acids generated from the polymerization initiator by exposure can be moderated as a whole, and the polymerizable resin component is suitably cured. be able to.

  The content of the photocationic polymerization initiator in the composition for forming a separation layer is preferably 0.01 to 60 parts by mass with respect to 100 parts by mass of the polymerizable resin component having an epoxy group, and 0.05 to 30 It is more preferably part by mass, further preferably 0.05 to 20 parts by mass, and particularly preferably 0.1 to 10 parts by mass. If the content of the cationic photopolymerization initiator is 0.01 to 60 parts by mass, the light transmittance in the separation layer can be lowered after the polymerizable resin component is cured and baked. Sex can be obtained.

(3) Thermal radical polymerization initiator Examples of the thermal radical polymerization initiator include peroxides and azo polymerization initiators. These thermal radical polymerization initiators polymerize a polymerizable monomer by radicals generated by heating.

  Examples of the peroxide include ketone peroxide, peroxy ketal, hydroperoxide, dialkyl peroxide, peroxy ester, peroxy carbonate, and peroxy ketal. Specifically, acetyl peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl cumyl peroxide, propionyl peroxide, benzoyl peroxide (BPO), 2-chlorobenzoyl peroxide, 3-chlorobenzoyl peroxide, 4-chlorobenzoyl peroxide, 2,4-dichlorobenzoyl peroxide, 4-bromomethylbenzoyl peroxide, lauroyl peroxide, potassium persulfate, diisopropyl peroxycarbonate, tetralin hydroperoxide, 1-phenyl-2-methylpropyl-1 Hydroperoxide, tert-butyl perphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, 4-methoxyacetic acid tert-butyl And N- (3-toluyl) carbamate tert-butyl, dicumyl-peroxide, tert-butyl-peroxy-2-ethylhexyl-monocarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, 2,5 Examples include -dimethyl-2,5-di (tert-butylperoxy) hexane and 1,1-di (tert-butylperoxy) cyclohexane.

  Commercially available peroxides include, for example, trade names “Park Mill (registered trademark)”, trade names “Perbutyl (registered trademark)”, trade names “Perocta (registered trademark)”, and “Parroyl” manufactured by NOF Corporation. (Registered trademark) "and" Perhexa (registered trademark) ".

  Examples of the azo polymerization initiator include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2 ' -Azobisisobutyronitrile, methyl 2,2'-azobis-2-methylpropionate, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2′-azobisisobutyrate, 1,1′-azobis (sodium 1-methylbutyronitrile-3-sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile , 4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalonodinitrile, 2,2'-azobis-2-methylvaleronitrile, 4,4'-azobis-4- Dimethyl cyanovalerate, 2,2′-azobis-2,4-dimethylvaleronitrile, 1,1′-azobiscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azo Biscyclohexanenitrile, 2,2′-azobis-2-propylbutyronitrile, 1,1′-azobis-1-chlorophenylethane, 1,1′-azobis-1-cyclohexanecarbonitrile, 1,1′-azobis- 1-cycloheptanenitrile, 1,1′-azobis-1-phenylethane, 1,1′-azobiscumene, 4-nitrophenylazo Ethyl cyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenylmethane, 1,1'-azobis-1,2-diphenylethane, poly (bisphenol A-4,4'-azobis-4 -Cyanopentanoate) and poly (tetraethylene glycol-2,2'-azobisisobutyrate).

  The blending amount of the thermal radical polymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polymerizable monomer. Is more preferable. Thereby, the polymerizable resin component having an ethylenically unsaturated double bond can be suitably polymerized. In addition, it is good to mix | blend a thermal radical polymerization initiator with the composition for separation layer formation by a well-known method immediately before using the composition for separation layer formation. Moreover, after diluting a thermal radical polymerization initiator in the additive solvent mentioned later, you may mix | blend with the composition for separated layer formation.

  The one-minute half temperature of the thermal radical polymerization initiator is preferably 90 ° C. or higher and 200 ° C. or lower, and more preferably 120 ° C. or higher and 180 ° C. or lower.

  The one-hour half-life temperature of the thermal radical polymerization initiator is preferably 50 ° C. or higher and 140 ° C. or lower, more preferably 80 ° C. or higher and 140 ° C. or lower.

  After blending the thermal radical polymerization initiator, the half-temperature for 1 minute of the thermal radical polymerization initiator is 90 ° C. or more and 200 ° C. or less, and the one-hour half-life temperature is 50 ° C. or more and 140 ° C. or less. The time until the polymerizable resin component having an ethylenically unsaturated double bond is polymerized and gelled can be lengthened. Thereby, the work possible time when apply | coating an adhesive composition on a support body can be lengthened. In addition, the one-minute half-temperature of the thermal radical polymerization initiator is 90 ° C. or more and 200 ° C. or less, and the one-hour half-temperature is 50 ° C. or more and 140 ° C. or less. When the diluted solvent is removed by coating and heating, radicals can be simultaneously generated to preliminarily start polymerization of the polymerizable resin component. From the viewpoint that the workable time can be lengthened, it is preferable that the one minute half temperature and the one hour half temperature of the thermal radical polymerization initiator are higher. Further, from the viewpoint of gelling quickly, the one-minute half temperature and the one-hour half temperature of the thermal radical polymerization initiator are preferably lower.

  The theoretically active oxygen amount of the thermal radical polymerization initiator is preferably 3.0% or more and 13.0% or less, and the blending amount of the thermal radical polymerization initiator is appropriately adjusted according to the theoretically active oxygen amount. Good.

(4) Photoradical polymerization initiator The composition for forming the separation layer may be configured to polymerize the polymerizable resin component with a photoradical polymerization initiator. When using a radical photopolymerization initiator as a polymerization initiator, if the adhesive composition is packaged so that the light-shielding state can be maintained, the separation layer is formed with the radical photopolymerization initiator blended. The composition for use can be commercialized.

  Specific examples of the radical photopolymerization initiator include 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- [4- (2-hydroxyethoxy). Phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)- 2-hydroxy-2-methylpropan-1-one, 2,2-dimethoxy-1,2-diphenylethane-1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- ( Methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane 1-one, ethanone 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), 2,4,6-trimethylbenzoyldiphenylphosphine oxide 4-benzoyl-4′-methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2- Ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethyl acetal, benzyldimethyl ketal, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, o- Methyl benzoylbenzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4-propoxythioxanthone, thioxanthene, 2-chlorothioxanthene, 2,4-diethylthioxanthene, 2-methylthioxanthene, 2-isopropylthioxanthene, 2 -Ethyl anthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzoimidar, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-di (methoxyphenyl) imidazole dimer, 2 (O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxyphenyl) -4,5-diphenyl Imidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4′-bisdimethylaminobenzophenone (ie, Michler's ketone), 4,4′-bisdiethylaminobenzophenone (ie, , Ethyl Michler's ketone), 4,4′-dichlorobenzophenone, 3,3-dimethyl-4-methoxybenzophenone, benzyl, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin iso Tilether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, p-t-butylacetophenone, p-dimethylaminoacetophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, dibenzosuberone, pentyl-4-dimethylaminobenzoate 9-phenylacridine, 1,7-bis- (9-acridinyl) heptane, 1,5-bis- (9-acridinyl) pentane, 1,3-bis- (9- Cridinyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5 -Methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (trichloromethyl)- s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl ] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Toxistyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-bis-trichloromethyl -6- (3-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) phenyl-s-triazine, 2,4-bis- And trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. It is done. Moreover, as a radical photopolymerization initiator, commercially available products “IRGACURE OXE02”, “IRGACURE OXE01”, “IRGACURE 369”, “IRGACURE 651” and “IRGACURE 907” (trade names: all manufactured by BASF) and “NCI” -831 "(trade name: manufactured by ADEKA) or the like can also be used.

  The amount of the radical photopolymerization initiator is preferably 0.1 parts by weight or more and 20 parts by weight or less, and preferably 1 part by weight or more and 5 parts by weight or less with respect to 100 parts by weight of the polymerizable monomer. Is more preferable.

[3. Other ingredients
The composition for forming a separation layer according to one embodiment may contain a surfactant and a diluent solvent in addition to the above-described polymerizable component and polymerization initiator.

(1) Surfactant The composition for forming a separation layer may contain a surfactant. Examples of the surfactant include a silicone-based surfactant and a fluorine-based surfactant. Specific examples of the silicone surfactant include BYK-077, BYK-085, BYK-300, BYK-301, BYK-302, BYK-306, BYK-307, BYK-310, BYK-320, BYK. -322, BYK-323, BYK-325, BYK-330, BYK-331, 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 (manufactured by BYK Chemie) or the like can be used. Specific examples of the fluorosurfactant include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F -445, F-446, F-470, F-471, F-472SF, F-474, F-475, F-477, F-478, F-479, F-480SF, F-482, F-483 , F-484, F-486, F-487, F-172D, MCF-350SF, 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 (manufactured by DIC); Polyfox series P -636, it is possible to use the PF-6320, PF-656, PF-6520 (manufactured by OMNOVA Solutions Inc.), and the like.

  Surfactant may be used individually by 1 type and may use 2 or more types together. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 2 parts by mass with respect to 100 parts by mass in total of the polymerizable resin components. More preferably, it is 03-1 mass part. By setting it as the said range, when the composition for separating layer formation is apply | coated on a support body, a separating layer with high flatness can be formed.

(2) Diluting solvent The composition for forming a separation layer according to an embodiment preferably contains a diluting solvent. A diluent will not be limited if it is a solvent which can melt | dissolve a polymeric resin component and a polymerization initiator, The solvent shown below can be used suitably.

  Examples of the diluent solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane, branched hydrocarbons having 4 to 15 carbon atoms, such as cyclohexane. Cyclic hydrocarbons such as cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, Norbornane, Pinan, Tujan, Karan, Longifolene, Geraniol, Nerol, Linalool, Citral, Citronellol, Menthol, Isomenthol, Neomenthol, α-Terpineol, β-Terpineol, γ-Terpineol, Terpinene-1-ol, Ter Terpene solvents such as nen-4-ol, dihydroterpinyl acetate, 1,4-cineol, 1,8-cineole, borneol, carvone, yonon, thuyon, camphor, d-limonene, l-limonene, dipentene; -Lactones such as butyrolactone; Ketones such as acetone, methyl ethyl ketone, cyclohexanone (CH), methyl-n-pentyl ketone, methyl isopentyl ketone, 2-heptanone; many such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol A compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate or dipropylene glycol monoacetate, the polyvalent alcohol Derivatives of polyalcohols such as alcohols or compounds having an ester bond such as monoalkyl ethers such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether or monophenyl ether Among them, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME) are preferable; cyclic ethers such as dioxane, methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate , Esters such as methoxybutyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, cresyl methyl ester Ether, diphenyl ether, can be mentioned dibenzyl ether, phenetole, the aromatic organic solvent such as butyl phenyl ether.

  In addition, the composition for forming a separation layer may appropriately include a sensitizer according to the composition of the polymerizable resin component and the polymerization initiator.

<Laminated body 10 (first embodiment)>
As shown in FIG. 1, the laminated body 10 which concerns on one Embodiment (1st embodiment) of this invention laminates | stacks the board | substrate 1 and the support plate 2 via the contact bonding layer 3 and the separation layer 4. As shown in FIG. Here, the separation layer 4 is formed using the composition for forming a separation layer according to one embodiment. For this reason, the separation layer with high chemical resistance is provided. Therefore, the laminated body manufactured using the composition for separation layer formation which concerns on one Embodiment is also the category of this invention.

[Substrate 1]
The substrate 1 can be subjected to processes such as thinning and mounting while being supported by the support plate 2. The substrate 1 can be mounted with a structure such as an integrated circuit or a metal bump. The substrate 1 can typically be a silicon wafer substrate, but is not limited, and a substrate made of any material such as a ceramic substrate, a thin film substrate, or a flexible substrate may be used.

[Support plate 2]
The support plate (support) 2 is a support that supports the substrate 1, and is attached to the substrate 1 through the adhesive layer 3. Therefore, the support plate 2 only needs to have a strength necessary for preventing damage or deformation of the substrate 1 during processes such as thinning, transporting, and mounting of the substrate 1. Moreover, the support plate 2 should just transmit the light for changing the isolation | separation layer 4. From these viewpoints, the support plate 2 may be a support made of glass, silicon, or acrylic resin.

[Adhesive layer 3]
The adhesive layer 3 is a layer for attaching the substrate 1 and the support plate 2, and is formed of an adhesive used for attaching the substrate 1 and the support plate 2.

  The adhesive for forming the adhesive layer 3 contains other components such as a thermoplastic resin, a diluent, and an additive. Here, the thermoplastic resin contained in the adhesive, that is, the thermoplastic resin contained in the adhesive layer 3 may be any resin having adhesiveness, such as a hydrocarbon resin or an acrylic-styrene resin. A maleimide resin, an elastomer resin, a polysulfone resin, or a combination thereof can be used more preferably. Hereinafter, the thermoplastic resin contained in the adhesive layer 3 in the present embodiment will be described.

(Hydrocarbon resin)
The hydrocarbon resin is a resin that has a hydrocarbon skeleton and is obtained by polymerizing a monomer composition. As the hydrocarbon resin, cycloolefin polymer (hereinafter sometimes referred to as “resin (A)”), and at least one resin selected from the group consisting of terpene resin, rosin resin and petroleum resin (hereinafter referred to as “resin (A)”). Resin (B) ”), and the like, but is not limited thereto.

  The resin (A) may be a resin obtained by polymerizing a monomer component containing a cycloolefin monomer. Specific examples include a ring-opening (co) polymer of a monomer component containing a cycloolefin monomer, and a resin obtained by addition (co) polymerization of a monomer component containing a cycloolefin monomer.

  Examples of the cycloolefin monomer contained in the monomer component constituting the resin (A) include bicyclic compounds such as norbornene and norbornadiene, tricyclic compounds such as dicyclopentadiene and hydroxydicyclopentadiene, and tetracyclodone. Tetracycles such as decene, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, or alkyl (methyl, ethyl, propyl, butyl, etc.) substitutes of these polycycles, alkenyl (vinyl) Etc.) Substitutes, alkylidene (ethylidene, etc.) substitutes, aryl (phenyl, tolyl, naphthyl, etc.) substitutes and the like. Among these, norbornene-based monomers selected from the group consisting of norbornene, tetracyclododecene, and alkyl-substituted products thereof are particularly preferable.

  The monomer component constituting the resin (A) may contain another monomer copolymerizable with the above-described cycloolefin-based monomer, and preferably contains, for example, an alkene monomer. Examples of the alkene monomer include ethylene, propylene, 1-butene, isobutene, 1-hexene, α-olefin and the like. The alkene monomer may be linear or branched.

  Moreover, it is preferable from a viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property) to contain a cycloolefin monomer as a monomer component which comprises resin (A). The ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. Further, the ratio of the cycloolefin monomer to the whole monomer component constituting the resin (A) is not particularly limited, but is preferably 80 mol% or less from the viewpoint of solubility and stability over time in a solution, More preferably, it is 70 mol% or less.

  Moreover, you may contain a linear or branched alkene monomer as a monomer component which comprises resin (A). The ratio of the alkene monomer to the whole monomer component constituting the resin (A) is preferably 10 to 90 mol%, more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. 30 to 80 mol% is more preferable.

  The resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin monomer and an alkene monomer, at high temperatures. It is preferable for suppressing generation of gas.

  The polymerization method and polymerization conditions for polymerizing the monomer components are not particularly limited, and may be set as appropriate according to conventional methods.

  For example, a cycloolefin copolymer which is a copolymer of a repeating unit represented by the following chemical formula (ad1) and a repeating unit represented by the following chemical formula (ad2) can be used as the adhesive component resin (A).

(In the chemical formula (ad2), n is 0 or an integer of 1 to 3)
As such cycloolefin copolymer, APL 8008T, APL 8009T, APL 6013T (all manufactured by Mitsui Chemicals, Inc.) and the like can be used.

  Examples of commercially available products that can be used as the resin (A) include “TOPAS” manufactured by Polyplastics Co., Ltd., “APEL” manufactured by Mitsui Chemicals, Inc., “ZEONOR” manufactured by Nippon Zeon Co., Ltd., and “ “ZEONEX”, “ARTON” manufactured by JSR Corporation, and the like.

  The glass transition temperature (Tg) of the resin (A) is preferably 60 ° C. or higher, and particularly preferably 70 ° C. or higher. When the glass transition temperature of the resin (A) is 60 ° C. or higher, softening of the adhesive layer 3 can be further suppressed when the laminate is exposed to a high temperature environment.

  The resin (B) is at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins. Specifically, examples of the terpene resin include terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins, hydrogenated terpene phenol resins, and the like. Examples of the rosin resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, coumarone-indene petroleum resins, and the like. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  Although the softening point of resin (B) is not specifically limited, It is preferable that it is 80-160 degreeC. When the softening point of the resin (B) is 80 to 160 ° C., the laminate can be prevented from being softened when exposed to a high-temperature environment, and adhesion failure does not occur.

  Although the weight average molecular weight of resin (B) is not specifically limited, It is preferable that it is 300-3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance is sufficient, and the degassing amount is reduced in a high temperature environment. On the other hand, when the weight average molecular weight of the resin (B) is 3,000 or less, the dissolution rate of the adhesive layer in the hydrocarbon solvent is good. For this reason, the residue of the adhesive layer on the substrate after separating the support can be quickly dissolved and removed. In addition, the weight average molecular weight of resin (B) in this embodiment means the molecular weight of polystyrene conversion measured by gel permeation chromatography (GPC).

  In addition, you may use what mixed resin (A) and resin (B) as resin. By mixing, heat resistance becomes good. For example, the mixing ratio of the resin (A) and the resin (B) is (A) :( B) = 80: 20 to 55:45 (mass ratio), and heat resistance in a high temperature environment, and It is preferable because of its excellent flexibility.

(Acrylic-styrene resin)
Examples of the acrylic-styrene resin include a resin obtained by polymerization using styrene or a styrene derivative and (meth) acrylic acid ester as monomers.

  Examples of the (meth) acrylic acid ester include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid ester having an aromatic ring. . Examples of the (meth) acrylic acid alkyl ester having a chain structure include an acrylic long-chain alkyl ester having an alkyl group having 15 to 20 carbon atoms and an acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms. . As acrylic long-chain alkyl esters, acrylic or methacrylic acid whose alkyl group is n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, etc. Examples include alkyl esters. The alkyl group may be branched.

  Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include known acrylic alkyl esters used in existing acrylic adhesives. For example, an alkyl group of acrylic acid or methacrylic acid in which the alkyl group is a methyl group, ethyl group, propyl group, butyl group, 2-ethylhexyl group, isooctyl group, isononyl group, isodecyl group, dodecyl group, lauryl group, tridecyl group, etc. Examples include esters.

  Examples of (meth) acrylic acid ester having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, and tricyclodecanyl. (Meth) acrylate, tetracyclododecanyl (meth) acrylate, dicyclopentanyl (meth) acrylate and the like can be mentioned, and isobornyl methacrylate and dicyclopentanyl (meth) acrylate are more preferable.

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited. Examples of the aromatic ring include a phenyl group, a benzyl group, a tolyl group, a xylyl group, a biphenyl group, a naphthyl group, and an anthracenyl group. A phenoxymethyl group, a phenoxyethyl group, and the like. The aromatic ring may have a linear or branched alkyl group having 1 to 5 carbon atoms. Specifically, phenoxyethyl acrylate is preferable.

(Maleimide resin)
Examples of maleimide resins include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Male having an aliphatic hydrocarbon group such as maleimide having an alkyl group, N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide A resin obtained by polymerizing an aromatic maleimide having an aryl group such as N, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, and Np-methylphenylmaleimide. It is done.

(Elastomer)
The elastomer preferably contains a styrene unit as a constituent unit of the main chain, and the “styrene unit” may have a substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkoxyalkyl group having 1 to 5 carbon atoms, an acetoxy group, and a carboxyl group. Further, the content of the styrene unit is more preferably in the range of 14 wt% or more and 50 wt% or less. Furthermore, the elastomer preferably has a weight average molecular weight in the range of 10,000 to 200,000.

  If the content of the styrene unit is in the range of 14% by weight or more and 50% by weight or less, and the weight average molecular weight of the elastomer is in the range of 10,000 or more and 200,000 or less, the hydrocarbon solvent described later Since it dissolves easily in (solvent), the adhesive layer can be removed more easily and quickly. Further, since the content of the styrene unit and the weight average molecular weight are within the above ranges, the resist solvent (eg, PGMEA, PGME, etc.), acid (fluorinated) exposed when the wafer substrate is subjected to the resist lithography process. Hydroxic acid etc.) and alkali (TMAH etc.) exhibit excellent resistance.

  In addition, you may further mix the (meth) acrylic acid ester mentioned above with the elastomer.

  The content of styrene units is more preferably 17% by weight or more, and more preferably 40% by weight or less.

  A more preferable range of the weight average molecular weight is 20,000 or more, and a more preferable range is 150,000 or less.

  As the elastomer, various elastomers can be used as long as the content of styrene units is in the range of 14% by weight to 50% by weight and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000. Can be used. For example, polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), styrene-butadiene-styrene block copolymer (SBS), styrene-butadiene-butylene-styrene block copolymer (SBBS). And hydrogenated products thereof, styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene-ethylene-propylene-styrene block copolymer (styrene-isoprene-styrene block copolymer) (SEPS), styrene-ethylene-ethylene- Propylene-styrene block copolymer (SEEPS), styrene-ethylene-ethylene-propylene-styrene block copolypropylene in which styrene block is reactively crosslinked -(Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), Septon V9827 (Co., Ltd., which has a reactive polystyrene-based hard block) Kuraray)), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification), etc., and the content of styrene units and weight average molecular weight of the elastomer are within the above-mentioned ranges. Can be used.

  Of the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, the stability to heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Further, among elastomers, those having both ends of a styrene block polymer are more preferable. This is because styrene having high thermal stability is blocked at both ends, thereby exhibiting higher heat resistance.

  More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and conjugated diene. Stability against heat is improved, and degradation such as decomposition and polymerization hardly occurs. Moreover, higher heat resistance is exhibited by blocking styrene having high thermal stability at both ends. Furthermore, it is more preferable from the viewpoint of solubility in hydrocarbon solvents and resistance to resist solvents.

  Examples of commercially available products that can be used as an elastomer included in the adhesive constituting the adhesive layer 3 include “Kepte (trade name)” manufactured by Kuraray Co., Ltd., “Hibler (trade name)” manufactured by Kuraray Co., Ltd. “Tuff Tech (trade name)” manufactured by JSR Corporation, “Dynalon (trade name)” manufactured by JSR Corporation, and the like can be mentioned.

  The content of the elastomer contained in the adhesive constituting the adhesive layer 3 is, for example, preferably in the range of 50 parts by weight or more and 99 parts by weight or less, with the total amount of the adhesive composition being 100 parts by weight, and 60 parts by weight or more. The range of 99 parts by weight or less is more preferable, and the range of 70 parts by weight or more and 95 parts by weight or less is most preferable. By making it within these ranges, the substrate and the support can be suitably bonded together while maintaining the heat resistance.

  A plurality of types of elastomers may be mixed. That is, the adhesive constituting the adhesive layer 3 may include a plurality of types of elastomers. And at least 1 should just contain the styrene unit as a structural unit of a principal chain among several types of elastomers. Further, at least one of the plurality of types of elastomers has a styrene unit content in the range of 14 wt% or more and 50 wt% or less, or a weight average molecular weight of 10,000 or more and 200,000 or less. If it is within the range, it is within the scope of the present invention. Moreover, when the adhesive agent which comprises the contact bonding layer 3 contains several types of elastomer, you may adjust so that content of a styrene unit may become in the said range as a result of mixing. For example, Septon 4033 of Septon (trade name) manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon 2063 of Septon (trade name) having a styrene unit content of 13% by weight is 1 weight ratio. When mixed in a one-to-one relationship, the styrene content with respect to the total elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. For example, when a styrene unit of 10% by weight and 60% by weight are mixed at a weight ratio of 1: 1, it becomes 35% by weight, which is within the above range. The present invention may be in such a form. It is most preferable that the plurality of types of elastomers contained in the adhesive constituting the adhesive layer 3 all contain styrene units within the above range and have a weight average molecular weight within the above range.

  Note that the adhesive layer 3 is preferably formed using a resin other than a photocurable resin (for example, a UV curable resin). By using a resin other than the photocurable resin, it is possible to prevent a residue from being generated around the minute unevenness of the substrate 1 after the adhesive layer 3 is peeled or removed. In particular, the adhesive constituting the adhesive layer 3 is preferably not soluble in any solvent but soluble in a specific solvent. This is because the adhesive layer 3 can be removed by dissolving it in a solvent without applying physical force to the substrate 1. When removing the adhesive layer 3, the adhesive layer 3 can be easily removed without damaging or deforming the substrate 1 even from the substrate 1 whose strength has been reduced.

(Polysulfone resin)
The adhesive for forming the adhesive layer 3 may contain a polysulfone resin. By forming the adhesive layer 3 with a polysulfone-based resin, even if the laminate is processed at a high temperature, the adhesive layer is dissolved in the subsequent steps, and a laminate that can peel the support from the substrate is manufactured. Can do. If the adhesive layer 3 contains a polysulfone resin, the laminate can be suitably used even in a high temperature process in which the laminate is processed at a high temperature of 300 ° C. or higher by annealing or the like.

  The polysulfone-based resin has a structure composed of at least one structural unit selected from a structural unit represented by the following general formula (ad3) and a structural unit represented by the following general formula (ad4).

(Here, R ^C3 , R ^C4 and R ^{C5 in} the general formula (ad3) and R ^C3 and R ^C4 in the general formula (ad4) are each independently selected from the group consisting of a phenylene group, a naphthylene group and an anthrylene group. And X ′ is an alkylene group having 1 to 3 carbon atoms.)
The polysulfone-based resin includes at least one of a polysulfone constituent unit represented by the formula (ad3) and a polyethersulfone constituent unit represented by the formula (ad4), whereby the substrate 1 and the support plate 2 are provided. Then, even if the substrate 1 is processed under a high temperature condition, a laminate that can prevent the adhesive layer 3 from being insolubilized due to decomposition, polymerization, or the like can be formed. In addition, the polysulfone-based resin is stable even when heated to a higher temperature as long as it is a polysulfone resin composed of a polysulfone structural unit represented by the formula (ad3). For this reason, it can prevent that the residue resulting from an contact bonding layer arises in the board | substrate 1 after washing | cleaning.

  The weight average molecular weight (Mw) of the polysulfone-based resin is preferably in the range of 30,000 to 70,000, and more preferably in the range of 30,000 to 50,000. If the weight average molecular weight (Mw) of the polysulfone-based resin is within a range of 30,000 or more, an adhesive composition that can be used at a high temperature of 300 ° C. or more can be obtained. Moreover, if the weight average molecular weight (Mw) of polysulfone-type resin is in the range of 70,000 or less, it can melt | dissolve suitably with a solvent. That is, an adhesive composition that can be suitably removed with a solvent can be obtained.

(Other ingredients)
The adhesive constituting the adhesive layer 3 may further contain other miscible materials as long as the essential properties are not impaired. For example, various conventional additives such as additional resins, plasticizers, adhesion aids, stabilizers, colorants, thermal polymerization inhibitors and surfactants for improving the performance of the adhesive may be further used. it can. In addition, the adhesive may be used after being diluted with the diluent described in the column of (1) Diluent.

[Separation layer 4]
The separation layer 4 is a layer that can be formed using the composition for forming a separation layer according to one embodiment, and a polymerizable resin component contained in the composition for forming a separation layer is cured with a polymerization initiator. It is a layer formed by a fired body formed by firing a cured product. Since the separation layer 4 is a fired body formed using the composition for forming the separation layer, it can be suitably altered by absorbing light irradiated through the support plate 2.

  Here, in the present specification, the fired body is a fired body formed by firing a cured product cured by polymerizing the polymerizable resin component described above with a polymerization initiator. The fired body is formed by firing a cured product of a polymerizable resin component and a polymerization initiator in an atmospheric environment, that is, in an environment where oxygen is present, and at least a part of the cured product is carbonized. ing. The inventors of the present application have found that such a fired body can form a separation layer that has high chemical resistance and can suitably absorb light having a wavelength in the range of 600 nm.

  For example, the thickness of the separation layer 4 is more preferably in the range of 0.05 μm or more and 50 μm or less, and further preferably in the range of 0.3 μm or more and 1 μm or less. If the thickness of the separation layer 4 is in the range of 0.05 μm or more and 50 μm or less, desired alteration can be caused in the separation layer 4 by short-time light irradiation and low-energy light irradiation. . The thickness of the separation layer 4 is particularly preferably within a range of 1 μm or less from the viewpoint of productivity.

  In this specification, the “deterioration” of the separation layer means a phenomenon in which the separation layer can be broken by receiving a slight external force, or a state in which the adhesive force with the layer in contact with the separation layer is reduced. To do. As a result of the alteration of the separation layer caused by absorbing light, the separation layer loses its strength or adhesion prior to light irradiation. In other words, the separation layer becomes brittle by absorbing light. The alteration of the separation layer may mean that the separation layer causes decomposition due to absorbed light energy, a change in configuration, dissociation of a functional group, or the like. The alteration of the separating layer occurs as a result of absorbing light.

  Therefore, for example, it is possible to easily separate the support plate and the substrate by changing the quality so that the separation layer is broken only by lifting the support plate. More specifically, for example, one of the substrate and the support plate in the stacked body is fixed to the mounting table by a support separating device or the like, and the other is held and lifted by a suction pad (suction part) provided with suction means. Thus, the support plate and the substrate are separated, or a force is applied by gripping the chamfered portion of the end portion of the peripheral portion of the support plate with the separation plate provided with a clamp (claw portion) or the like. And should be separated. Further, for example, the support plate may be peeled from the substrate in the laminated body by a support separating apparatus provided with a peeling means for supplying a peeling liquid for peeling the adhesive. The peeling means supplies the peeling liquid to at least a part of the peripheral end portion of the adhesive layer in the laminate, and the adhesive layer in the laminate is swollen so that the force concentrates on the separation layer from where the adhesive layer swells. In this way, a force can be applied to the substrate and the support plate. For this reason, a board | substrate and a support plate can be isolate | separated suitably.

  The force applied to the laminated body may be appropriately adjusted depending on the size of the laminated body, and is not limited. For example, if the laminated body has a diameter of about 300 mm, a force of about 0.1 to 5 kgf is applied. By adding, a board | substrate and a support plate can be isolate | separated suitably.

  In the laminate 10, another layer may be further formed between the separation layer 4 and the support plate 2. In this case, the other layer should just be comprised from the material which permeate | transmits light. Thereby, a layer imparting preferable properties and the like to the laminate 10 can be appropriately added without hindering the incidence of light on the separation layer 4. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 4. Therefore, the materials constituting the other layers do not need to transmit light of all wavelengths, and can be appropriately selected from materials capable of transmitting light of wavelengths that can alter the material constituting the separation layer 4.

  The separation layer 4 is preferably formed only from a material having a structure that absorbs light, but the material does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired. May be added to form the separation layer 4.

  In addition, it is preferable that the surface of the separation layer 4 facing the adhesive layer 3 is flat (no irregularities are formed), so that the separation layer 4 can be easily formed and even when pasted. It becomes possible to paste on.

The light applied to the separation layer 4 is a solid such as a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, or a fiber laser, depending on the wavelength that can be absorbed by the fired body forming the separation layer 4. A liquid laser such as a laser or a dye laser, a gas laser such as a CO ₂ laser, an excimer laser, an Ar laser, or a He—Ne laser, a laser beam such as a semiconductor laser or a free electron laser, or a non-laser beam may be used as appropriate. The wavelength at which the fired body can be altered is not limited to this, but for example, light having a wavelength in the range of 600 nm or less can be used.

<Manufacturing method of laminated body (second embodiment)>
The manufacturing method of the laminated body which concerns on one Embodiment (1st embodiment) of this invention is demonstrated in detail using FIG. As shown in FIG. 1, the manufacturing method of the laminated body 10 according to the present invention includes a separation layer forming step of forming a separation layer 4 on a support plate 2 and an adhesive layer forming step of forming an adhesive layer 3 on a substrate 1. And a laminating step of laminating the substrate 1 and the support plate 2 via the adhesive layer 3 and the separation layer 4. Moreover, the separation process which isolate | separates the support plate 2 from the laminated body 10 is performed to the laminated body 10 formed with the manufacturing method of the laminated body which concerns on one Embodiment as another process.

[Separation layer forming step]
The separation layer forming step is a step of forming the separation layer 4 that is altered by absorbing light. In the separation layer forming step, the support layer 2 is formed by applying the composition for forming a separation layer according to one embodiment. The method for applying the composition for forming a separation layer on the support plate 2 is not particularly limited, and examples thereof include spin coating, dipping, roller blades, spray coating, and slit coating.

  In the separation layer forming step, the diluting solvent is removed from the composition for forming a separation layer applied on the support plate 2 by placing it in a heating environment or a reduced pressure environment. Thereafter, in the separation layer forming step, the polymerizable resin component contained in the composition for forming the separation layer is polymerized with a polymerization initiator by exposure or heating in an inert gas environment such as nitrogen gas or in an atmospheric environment. By doing so, a cured product of the polymerizable resin component is formed. Thereafter, the cured product of the polymerizable resin component is fired in an atmospheric environment. The temperature for firing the cured product is 250 ° C. or higher, preferably 300 ° C. or higher, and more preferably 400 ° C. or higher. When the temperature for firing the cured product is 250 ° C. or higher, a separation layer capable of absorbing light in the wavelength range of 600 nm or shorter can be suitably formed. The upper limit of the firing temperature is not particularly limited, but is 800 ° C. or lower, preferably 600 ° C. or lower.

  The firing time is 5 minutes or more and 3 hours or less, preferably 10 minutes or more and 1 hour or less. Thereby, a separation layer capable of absorbing light in a wavelength range of 600 nm or less can be suitably formed.

[Adhesive layer forming step]
In the adhesive layer forming step, the adhesive layer 3 is formed on the substrate 1. As shown in FIG. 1, the above-described adhesive is applied on the substrate 1. Then, the adhesive layer 3 is formed by removing the diluting solvent from the adhesive by baking in stages while raising the temperature.

[Lamination process]
A lamination process is a process of laminating | stacking the board | substrate 1, the contact bonding layer 3, the isolation | separation layer 4, and the support plate 2 in this order. As a specific method of the laminating process, as shown in FIG. 1, the surface on which the adhesive layer 3 is formed on the substrate 1 and the surface on which the separation layer 4 is formed on the support plate 2 are bonded together to form a vacuum. There is a method of laminating by baking and pressure bonding below.

  In addition, in the manufacturing method of the laminated body which concerns on one Embodiment, the order of each process will not be specifically limited if a board | substrate, an adhesive layer, a separation layer, and a support body are laminated | stacked in this order.

[Other processes]
The substrate 1 in the stacked body 10 manufactured in the stacking process can be mounted with an element by performing an etching process, a lithography process, and the like after performing a thinning process, for example. Since the separation layer 4 is composed of a fired body formed using the composition for forming a separation layer according to one embodiment, the separation layer 4 has high chemical resistance. For this reason, it can prevent suitably that the separation layer 4 is damaged by chemical | medical agents etc. in an etching process, a lithography process, etc.

  Moreover, the laminated body 10 in which the element is mounted on the substrate 1 is irradiated with light of a predetermined wavelength via the support plate 2 as shown in FIG. Thereby, since the separation layer 4 formed of the fired body can be suitably altered by absorbing the laser light, the substrate 1 and the support plate 2 in the stacked body 10 can be successfully separated. .

<Laminated body according to another embodiment (second embodiment)>
The laminated body which concerns on this invention is not limited to the above-mentioned embodiment. For example, a laminate according to one embodiment (second embodiment) is a laminate in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order, and the substrate is made of an element by a sealing material. The sealing substrate has a wiring layer (rewiring layer).

  In semiconductor packages, fan-in technology such as fan-in WLP (Fan-in Wafer Level Package) that rearranges the terminals at the end of the bare chip within the chip area, and rearranges the terminals outside the chip area. Fanout type technologies such as fanout type WLP (Fan-out Wafer Level Package) are known. In particular, fan-out technology has been applied to fan-out type PLP (Fan-out Panel Level Package), in which semiconductor elements are placed on a panel and packaged. Integration, thinning, and miniaturization of semiconductor devices, etc. In order to achieve this, fan-out technologies such as these are attracting attention. The laminate according to one embodiment includes a separation layer having high chemical resistance against various chemicals for forming a wiring layer on a sealing substrate. For this reason, the laminated body in fan-out type | mold WLP and fan-out type | mold PLP is also the category of this invention.

〔substrate〕
The sealing substrate includes a wiring layer on which the element is mounted, the element, and a sealing material that seals the element. The sealing substrate preferably includes a plurality of elements, and a plurality of electronic components can be obtained by dicing such a sealing substrate.

(Wiring layer)
The wiring layer is also referred to as RDL (Redistribution Layer), and is a thin-film wiring body that forms a wiring connected to an element, and may have a single-layer structure or a multi-layer structure. In one embodiment, the wiring layer is made of a dielectric material (eg, photosensitive resin such as silicon oxide (SiOx) or photosensitive epoxy) and a conductor (eg, aluminum, copper, titanium, nickel, gold, silver, etc.). The wiring may be formed of a metal and an alloy such as a silver-tin alloy), but is not limited thereto.

(element)
The element is a semiconductor element or other element, and may have a single-layer or multi-layer structure. Note that in the case where the element is a semiconductor element, an electronic component obtained by dicing the sealing substrate is a semiconductor device.

(Encapsulant)
As the sealing material, for example, a sealing material containing an epoxy resin can be used. It is preferable that the sealing material is not provided for each element but integrally seals all of the plurality of elements mounted on the wiring layer.

[Support]
The support body should just have intensity | strength required in order to prevent the failure | damage or deformation | transformation of each component of a sealing substrate at the time of formation of a sealing substrate. The support is formed of a material that transmits light having a wavelength that can alter the separation layer formed on the support. In the technical field of semiconductor devices, in addition to increasing the size of the circular support plate 2, in addition to increasing the size of the circular support plate 2, a large panel having a quadrangular shape when viewed from above is supported. It is being considered for use as a body. A method of manufacturing a semiconductor device by using such a large rectangular panel as a support is known as a PLP (Panel level Package) technique and can be implemented by a fan-out technique. In the PLP technique, a panel formed of a material such as glass or silicon can be suitably used as a panel used as a support.

<The manufacturing method (2nd embodiment) of the laminated body which concerns on another embodiment>
The method for producing a laminate according to the present invention is not limited to the method for producing a laminate according to the above-described embodiment (first embodiment) based on the so-called WLP (Wafer Level Package) technique as shown in FIG. For example, in a method for manufacturing a laminate according to another embodiment, a sealing substrate including a wiring layer on which an element is mounted, the element, and a sealing material that seals the element is used for the sealing. A method for producing a laminate formed by laminating an adhesive layer and a separation layer that is altered by irradiation with light on a support that supports the substrate, the polymerizable resin component and the support Then, a composition for forming a separation layer comprising a polymerization initiator is applied, the polymerizable resin component is polymerized by heating or exposure, and the polymerized resin component is baked to form the separation layer. A separation layer forming step for forming, an adhesive layer forming step for forming an adhesive layer on the separation layer, and a sealing substrate forming step for forming a sealing substrate on the adhesive layer. .

  In addition, since the separation layer forming step is the same as the separation layer forming step in the method for manufacturing the laminate according to the above-described embodiment, description thereof is omitted. Moreover, since the adhesive layer forming step is the same as the above-described embodiment except that the adhesive layer is formed on the separation layer formed on the support, the description thereof is omitted.

[Sealing substrate formation process]
In the sealing substrate forming step, a wiring substrate forming step, a mounting step, a sealing step, and a thinning step are performed in this order to form a sealing substrate on the adhesive layer.

[Wiring layer forming process]
In the wiring layer forming step, a wiring layer is formed on the adhesive layer.

  In one embodiment, the wiring layer is formed by first forming a dielectric layer such as silicon oxide (SiOx) or photosensitive resin on the adhesive layer. The dielectric layer made of silicon oxide can be formed by, for example, a sputtering method, a vacuum deposition method, or the like. The dielectric layer made of a photosensitive resin can be formed by applying the photosensitive resin by a method such as spin coating, dipping, roller blade, spray coating, and slit coating.

  Subsequently, wiring is formed on the dielectric layer using a conductor such as metal. As a method for forming the wiring, for example, a known semiconductor process method such as lithography processing such as photolithography (resist lithography) or etching processing can be used.

  Thus, when performing photolithography processing, etching processing, and the like, the separation layer is exposed to an acid such as hydrofluoric acid, an alkali such as TMAH, and a resist solvent. In particular, in the fan-out type technique, cyclopentanone, cyclohexanone, or the like is used as a resist solvent in addition to PGMEA. However, the separation layer has high chemical resistance by forming the separation layer using the composition for forming a separation layer according to one embodiment. For this reason, it can prevent that a separated layer melt | dissolves or peels by being exposed not only to an acid and an alkali but to a resist solvent. Therefore, the wiring layer can be suitably formed on the support.

[Mounting process]
In the mounting process, an element is mounted on the wiring layer. The element can be mounted on the wiring layer using, for example, a chip mounter.

[Sealing process]
In the sealing step, the element is sealed with a sealing material. The sealing material is not particularly limited, and as a reference, for example, the sealing material is injection-molded using a mold while maintaining a high viscosity state while being heated to 100 ° C. or higher.

[Thinning process]
In the thinning step, the sealing material is thinned. Thereby, the sealing substrate provided with the wiring layer can be suitably formed on the adhesive layer.

  In the method for manufacturing a laminate according to the present embodiment, after the thinning process, a process such as formation of a bump on the sealing material and formation of an insulating layer may be further performed.

[Method for Producing Laminate According to One Modification]
The manufacturing method of the laminated body which concerns on this invention is not limited to said embodiment. For example, in the manufacturing method of the laminated body according to the modification, in the sealing substrate forming process included in the manufacturing method of the laminated body according to the second embodiment, the mounting process, the sealing process, the thinning process, and the wiring In this configuration, the layer forming steps are performed in this order. Also in this configuration, the sealing substrate can be suitably formed on the separation layer having high chemical resistance.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

<Evaluation of light transmittance and laser reactivity in separation layer>
[Example 1]
First, as Example 1, a composition for forming a separation layer having a different composition was prepared using a polymerizable resin component and a polymerization initiator, and visible light in the separation layer formed using each composition for forming a separation layer was used. The transmittance was evaluated. Subsequently, the separation property of the support in each laminate was evaluated by irradiating the separation layer in the laminate produced using each separation layer forming composition with laser light.

(Preparation of separation layer forming composition)
First, in a mixed solvent of PGMEA and PGME (1: 1 (weight ratio)) so that the concentration of the polymerizable resin component JER157S70 (Novolac type epoxy resin, manufactured by Mitsubishi Chemical Corporation) is 30% by weight. To prepare a solution. Next, 10 parts by weight of PAG290 was blended with 100 parts by weight of JER157S70 in the solution under light-shielding conditions to prepare the composition for forming a separation layer of Example 1.

(Formation of separation layer)
The composition for forming a separation layer of Example 1 was spin-coated on two bare glass supports (12 inches, thickness 0.7 mm). Next, each of the bare glass supports coated with the composition for forming a separation layer is heated at 90 ° C. for 180 seconds, and then heated at 150 ° C. for 180 seconds, so that it is contained in the separation layer. Solvent was removed. Next, the separation layer from which the solvent was removed was exposed and cured at 1000 mJ / cm ² . One of the cured separation layers was fired under conditions of 250 ° C. and 15 minutes in an atmospheric environment. Further, the remaining one piece was fired under conditions of 400 ° C. and 15 minutes in an atmospheric environment. Thereby, about Example 1, two types of separated layers having different firing conditions were formed. In addition, about the separation layer of Example 1, the film thickness was 1.8 μm.

(Evaluation of transmittance)
For each of the separation layers of Example 1 having different firing conditions, a spectral analysis measuring device UV-3600 (manufactured by Shimadzu Corporation) was used to irradiate light having a wavelength of 380 to 780 nm, and the separation formed on the bare glass support. The transmittance of light having a wavelength of 532 nm in the layer was evaluated.

[Evaluation of laser reactivity]
Laser reactivity was evaluated by irradiating a separation layer fired at 400 ° C. with a laser beam having a wavelength of 532 nm under conditions of a scanning speed of 6500 mm / second, a frequency of 40 kHz, an output of 20 A, and an irradiation pitch of 140 μm. The laser reactivity was evaluated by evaluating the state of the trace of the laser light irradiated on the separation layer with a microscope VHX-600 (manufactured by Keyence). The criteria for evaluating the laser reactivity are “A” when the area occupied by the trace of the laser beam is 50% or more, and “B” when it is less than 50%. If not, it was evaluated as “C”. Thereby, the separability of the support in the laminate was evaluated in a simulated manner.

[Examples 2 to 17]
In the same procedure as in Example 1, compositions for forming a separation layer in Examples 2 to 17 were prepared. The details of the polymerizable resin component and the polymerization initiator used in Examples 2 to 17 are as follows. Moreover, the composition of the polymerizable resin component, the polymerization initiator, and the surfactant in the adhesive compositions of Examples 1 to 17 is as shown in Tables 1 to 9 below.

(Polymerizable resin component)
A novolak type epoxy resin represented by the following formula (1) (JER157S70, manufactured by Mitsubishi Chemical Corporation)

-Bisphenol type epoxy resin represented by the following formula (2) (JER828, manufactured by Mitsubishi Chemical Corporation)

-An epoxy resin (EHPE3150CE, represented by the following formula (3)) and a cycloaliphatic epoxy resin represented by formula (4) in a weight ratio of 50:50 Daicel Chemical Industries, Ltd.)

-Epoxy resin (EPICLON HP7200 (manufactured by DIC Corporation)) represented by the following formula (5)

-Epoxy-modified siloxane represented by the following formula (6) (SP02, manufactured by Nagase ChemteX Corporation)

・ Novolac type epoxy resin with naphthalene skeleton (EPICLON HP5000, manufactured by DIC Corporation)
Acrylic monomer (DPHA, manufactured by Shin-Nakamura Chemical Co., Ltd.) represented by the following formula (7)

Acrylic resin 1: Acrylic resin 1 having an epoxy group represented by the following formula (8) (Mw = 5000, solid content concentration 31.8 wt%, 3-methoxybutyl acetate, and 3-methoxybutanol mixed solution) )

(Polymerization initiator)
-Photocationic polymerization initiator represented by the following formula (9) (PAG290, manufactured by BASF)

-Photocationic polymerization initiator represented by the following formula (10) (210CS, manufactured by San Apro)

-Photocationic polymerization initiator represented by the following formula (11) (410CS, manufactured by San Apro)

・ Thermal cationic polymerization initiator TAG2689 (thermal acid generator: quaternary ammonium salt block type, manufactured by KING INDUSTRY)
-Thermal cationic polymerization initiator TAG2690 (thermal acid generator: quaternary ammonium salt block species, manufactured by KING INDUSTRY)
-Thermal cationic polymerization initiator TAG2678 (thermal acid generator: quaternary ammonium salt block species, manufactured by KING INDUSTRY)
Dialkyl peroxide (thermal radical polymerization initiator: manufactured by NOF Corporation, “Park Mill D (trade name))
From the composition and evaluation results of the composition for forming a separation layer shown in Tables 1 to 6 below, the tendency due to the difference in the composition of each composition for forming a separation layer, firing conditions, and laser light irradiation conditions was confirmed.

[Evaluation of Photocationic Polymerization Initiator]
In the composition for forming a separated layer of Examples 1 to 3, the photocationic polymerization initiator (photopolymerization initiator) was evaluated. The evaluation results are shown in Table 1 below.

  As shown in Table 1, in the separation layer forming compositions of Examples 1 to 3, the light transmittance at a wavelength of 532 nm is low and the laser reactivity is excellent even when any of the cationic photopolymerization initiators is used. It was confirmed that a separation layer could be formed. In each of the separation layers of Examples 1 to 3, the separation layer fired at 400 ° C. has lower light transmittance of 532 nm and laser reactivity than the case of firing at 250 ° C. It showed a high tendency.

[Evaluation of thermal polymerization initiator]
In the composition for forming a separated layer in Examples 4 to 6, the thermal polymerization initiator was evaluated. In the composition for forming a separation layer of Example 7, the thermal polymerization initiator was evaluated using epoxy-modified siloxane as the polymerizable resin component. Table 2 below shows the evaluation results of Examples 4 to 7.

  As shown in Table 2, the composition for forming a separation layer of Examples 4 to 6 is a composition obtained by changing the radical photopolymerization initiator in the composition for forming a separation layer of Examples 1 to 3 to a thermal polymerization initiator. It was also confirmed that the transmittance of light having a wavelength of 532 nm could be reduced and a separation layer with high laser reactivity could be formed. In the separation layer forming compositions of Examples 4 to 6, it was confirmed that by adding the surfactant PF656, the coating workability was improved and a smooth separation layer could be formed on the glass support. did it.

[Evaluation of epoxy resin]
About Examples 7-12, the composition for separated layer formation containing the epoxy resin from which a kind differs was evaluated. Table 3 below shows the evaluation results of Examples 7 to 12.

  As shown in Table 3, in the separation layers of Examples 7 to 11, when using a bisphenol type epoxy resin, an oxetane type epoxy resin, a dicyclopentadiene type epoxy resin, and an epoxy resin having a naphthalene skeleton, regardless of JER157S70 It was also confirmed that a separation layer having high laser reactivity could be formed. Therefore, in the composition for forming the separation layer, it was confirmed that an epoxy resin having various skeletons such as an aromatic side skeleton and an aliphatic skeleton can be used as the polymerizable resin component. Also, in the composition for forming a separation layer of Example 12 in which the composition of the polymerizable resin composition was changed to epoxy-modified siloxane, although the transmittance at a wavelength of 532 nm showed a higher value than other examples, It was confirmed that a separation layer having laser reactivity could be formed.

[Evaluation of blending amount of thermal polymerization initiator]
For the separation layer forming compositions of Examples 4 and 13 to 15, the blending amount of the thermal polymerization initiator TAG-2688 was changed, and the light transmittance and laser reactivity in the separation layer were evaluated. Table 4 below shows the evaluation results of the blending amount of the thermal polymerization initiator.

  As shown in Table 4, in the composition for forming a separated layer of Example 4 and Examples 13 to 15, the transmittance of light having a wavelength of 532 nm is higher as the blending amount of TAG-2687 which is a thermal polymerization initiator is lower. Showed a tendency to become. Moreover, the distance between the traces of laser light tended to increase as the blending amount of TAG-2688 decreased. From these tendencies, it was confirmed that in the composition for forming a separation layer, the polymerization initiator is an important element for forming a fired body having high laser reactivity.

[Evaluation of transmittance and laser reactivity depending on the thickness of the separation layer]
As Examples 9-1 to 9-3, a separation layer having a thickness different from that of the separation layer of Example 9 is formed using the composition for forming a separation layer of Example 9, and light is transmitted through each separation layer. The rate and laser reactivity were evaluated. Table 5 below shows the evaluation results.

  As shown in Table 5, for the separation layers of Examples 9 and 9-1 to 9-3, the transmittance of light having a wavelength of 532 nm tended to increase as the film thickness decreased. It was also confirmed that high laser reactivity could be obtained.

[Evaluation of laser reactivity by changing laser output]
Regarding the separation layers of Examples 4, 7, and 9-2, the laser reactivity was evaluated by changing the output of the irradiated laser beam. The firing condition for each separation layer is 400 ° C. The laser irradiation conditions are the same as the laser reactivity evaluation conditions except that the laser output is changed under the conditions of 20A, 22A, and 24A. The evaluation results are shown in Table 6 below.

  As shown in Table 6, high laser reactivity could be obtained in any of the separation layers of Examples 4, 7 and 9-2. Here, in each of the separation layers of Examples 4, 7, and 9-2, the higher the output of the irradiated laser light, the larger the trace of the laser light formed on the separation layer. The tendency for the width of the to become smaller was confirmed. In addition, the separation layer of Example 7 having a relatively low transmittance of light having a wavelength of 532 nm has a larger width (pitch) between the traces than the separation layers of Example 4 and Example 9-2. became. From these results, it was confirmed that in the separation layer having a high transmittance, the laser reactivity can be adjusted by adjusting the output of the laser beam and the irradiation pitch.

[Evaluation of firing temperature of separation layer]
Using the composition for forming a separated layer of Example 4, the firing temperature was changed to form a separated layer, and the laser reactivity in each separated layer was evaluated. Table 7 below shows the evaluation results.

  As shown in Table 7, in the separation layers of Examples 4 and 4-1, sufficient traces of laser light irradiation could be confirmed in both cases. However, comparing the separation layers of Examples 4 and 4-1, the separation layer of Example 4 having a higher firing temperature had a lower light transmittance, and a larger trace of laser light irradiation was observed. Therefore, when considering the temperature at which the separation layer is baked, including the result of the transmittance of Reference Example 4-2, it is preferable that the temperature is higher, and that it is preferable that the temperature is higher than 300 ° C. did it.

[Evaluation of acrylic resin components]
As Examples 16 and 17, a composition for forming a separation layer was prepared using an acrylic monomer and an acrylic polymer (acrylic resin component), and a wavelength 532 in the separation layer formed using the composition for forming a separation layer. The light transmittance and laser reactivity were evaluated.

  In addition, the separation layer using the acrylic resin 1 of Example 17 in the following Table 8 was produced as follows. By blending 8% by weight of a TAG-2689 PM solution so that the concentration of TAG-2689 is 5% by weight with respect to 100% by weight of the acrylic resin 1 solid content, the solid content concentration of the acrylic resin 1 is 26. A base for the composition for forming a separating layer, which was 0.5% by weight, was prepared. Next, the composition for forming a separation layer of Example 17 was prepared by blending PF656 so as to be 0.05 parts by weight with respect to 100 parts by weight of the base.

The composition for forming a separation layer of Example 17 was applied to the bare glass support same as Example 1, 1000
Spin coating was performed for 10 seconds under rpm conditions, and then the bare glass support was baked at 400 ° C. for 15 minutes under atmospheric conditions to form the separation layer of Example 17. The laser irradiation conditions are the same as those in the first embodiment. The evaluation results are shown in Table 8 below.

  As shown in Table 8, it was confirmed that an acrylic monomer and an acrylic polymer can be used as the polymerizable resin component in the composition for forming a separation layer of Example 16 and Example 17. Moreover, in the composition for separated layer formation of Example 16, it has confirmed that an organic peroxide could be used as a polymerization initiator. From this, in any case of radical polymerization and cationic polymerization based polymerizable resin components, it is highly laser-reactive by polymerizing and baking with a polymerization initiator suitable for each polymerizable resin component. It was confirmed that a separation layer could be formed.

[Evaluation of chemical resistance]
Using the separation layer forming compositions of Example 4 and Example 11, separation layers having different firing temperatures were formed, and the chemical resistance of each separation layer was evaluated. As an evaluation of chemical resistance, chemical resistance to propylene glycol monomethyl ether (PGMEA), N-methyl-2-pyrrolidone and cycloheptanone under conditions of 25 ° C. and 10 minutes, and conditions of 60 ° C. and 30 minutes The chemical resistance to resist stripping solution ST120 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was evaluated.

Further, as Comparative Example 1, a fluorocarbon separation layer was formed on a glass support, and the same chemical resistance evaluation as in Example 4 and Example 11 was performed. The separation layer of Comparative Example 1 was formed by performing a CVD method using C ₄ F ₈ as a reaction gas under the conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high frequency power of 2500 W, and a film formation temperature of 240 ° C. (thickness). 1 μm).

  Chemical resistance is evaluated by visual observation, and the separation layer formed on the glass support is evaluated as “A” when the separation layer is not swollen and peeled, and at least one of swelling and peeling is observed. Evaluated as “C”. Table 9 below shows the evaluation results of chemical resistance in the separation layers of Example 4, Example 11, and Comparative Example 1.

  As shown in Table 9, it was confirmed that the separation layer formed using the composition for forming a separation layer of Examples 4 and 9 can obtain high chemical resistance regardless of the firing temperature. In addition, the separation layer formed using the composition for forming the separation layer of Examples 4 and 9 obtains high chemical resistance regardless of the type of the stripping solution or the like as compared with the separation layer of Comparative Example 1. I was able to confirm that

  Moreover, the chemical resistance was evaluated under the same conditions as in Examples 4 and 9 for the separation layers formed using the separation layer forming compositions of Examples 1 to 3, 5 to 8, and 10 to 17. As a result, the separation layers of Examples 1 to 3, 5 to 8 and 10 to 17 are similar to the separation layers of Examples 4 and 9, compared to the separation layer of Comparative Example 1, and the type of the stripping solution or the like. Regardless, it was confirmed that high chemical resistance could be obtained.

[Evaluation of adhesion]
For the separation layer of Example 4 and the separation layer of Comparative Example 1, the adhesion of the adhesive layer was evaluated. The evaluation conditions are as shown below.

(Sample preparation)
The composition for forming a separation layer of Example 4 was applied on a 12-inch silicon substrate and baked at a temperature of 400 ° C. to form a separation layer (thickness 1.8 μm). It was formed on a 12-inch silicon substrate (thickness 1 μm) under the same conditions as the fluorocarbon separation layer of Comparative Example 1. Thereafter, TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) is spin-coated on each of these separation layers, and baked at 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each. Then, an adhesive layer was formed (thickness 50 μm). In addition, an adhesive layer was formed on each of the separation layers of Example 4 and Comparative Example 1 in the same procedure except that the adhesive was changed to TZNR (registered trademark) -A4017 (manufactured by Tokyo Ohka Kogyo Co., Ltd.). .

  Next, for each sample, the adhesive layer was cut into a 10 mm wide strip with a cutter. Subsequently, the belt-like adhesive layer is pulled perpendicularly to the silicon substrate at a speed of 200 mm / second while the angle between the adhesive layer and the substrate (also referred to as a peel angle) is always maintained at 90 °. Thus, the adhesive layer was peeled off from the silicon substrate. The adhesion between the separation layer and the adhesive layer was evaluated based on the adhesive strength (g / cm, also referred to as peel strength) at this time. If the adhesive strength is 20 g / cm or more, it is determined that the adhesive strength is sufficient. After that, after irradiating with laser light under the same conditions as in the above-mentioned [Evaluation of laser reactivity], each separation layer is altered, the adhesive strength is measured, and the adhesive strength before irradiating with laser light. Compared with. The evaluation results are shown in Table 10 below.

  As shown in Table 10, the separation layer of Example 4 was higher in adhesion than the separation layer of Comparative Example 1 with the adhesive layer formed with each adhesive. Further, the separation layer of Example 4 has an adhesive strength after laser irradiation of 0 g / cm, and it is determined that the adhesive layer was substantially peeled off by irradiation with laser light.

  Moreover, adhesiveness was evaluated on the same conditions as Example 4 about the separation layer formed using the composition for separation layer formation of Examples 1-3 and 5-17. As a result, the separation layers of Examples 1 to 3 and 5 to 9 have higher adhesion to TZNR (registered trademark) -A4012 and A4017 than the separation layer of Comparative Example 1. It could be confirmed.

  From the results of the above Examples and Comparative Examples, by forming a separation layer using a composition for forming a separation layer containing a polymerizable resin composition and a polymerization initiator, laser reactivity and chemical resistance are formed. It was confirmed that a high separation layer could be formed.

  The present invention can be suitably used in the manufacturing process of a miniaturized semiconductor device.

1 Substrate 2 Support plate (support)
3 Adhesive layer 4 Separation layer 10 Laminate

Claims (13)

For forming a separation layer for forming the separation layer in a laminate formed by laminating a substrate and a support that transmits light through an adhesive layer and a separation layer that is altered by irradiation with light. A composition comprising:
A composition for forming a separation layer, comprising a polymerizable resin component and a polymerization initiator.   The polymerizable resin component is at least one selected from the group consisting of a polymerizable resin component having an epoxy group, an epoxy-modified siloxane, and a polymerizable resin component having an ethylenically unsaturated double bond. The composition for forming a separation layer according to claim 1.   The composition for forming a separation layer according to claim 2, wherein the polymerizable resin component is an epoxy resin.   The composition for forming a separated layer according to any one of claims 1 to 3, wherein the polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator. A laminate comprising a substrate and a support that transmits light, laminated via an adhesive layer and a separation layer that is altered by irradiation with light,
The separated layer is a fired product of a cured product obtained by polymerizing a polymerizable resin component with a polymerization initiator.   6. The polymerizable resin component according to claim 5, wherein the polymerizable resin component is at least one selected from the group consisting of an epoxy resin, an epoxy-modified siloxane, and a polymerizable resin component having an ethylenically unsaturated double bond. The laminated body of description.   The laminate according to claim 5 or 6, wherein the polymerizable resin component is an epoxy resin.   The laminate according to any one of claims 5 to 7, wherein the polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator. A method for producing a laminate comprising: laminating a substrate and a support that transmits light through an adhesive layer and a separation layer that is altered by irradiation with light;
Applying a composition for forming a separation layer comprising a polymerizable resin component and a polymerization initiator to any of the substrate and the support, and heating or exposing to polymerize the polymerizable resin component, A separation layer forming step of forming the separation layer by firing the polymerized polymerizable resin component;
A laminating step of laminating the substrate or the support on which the separation layer is formed, and the other of the substrate and the support on which the separation layer is not formed via the separation layer and an adhesive layer; The manufacturing method of the laminated body characterized by including. A sealing substrate including a wiring layer on which an element is mounted, the element, and a sealing material that seals the element is disposed on a support that supports the sealing substrate, and an optical layer. Is a method for producing a laminate formed by laminating through a separation layer that is altered by irradiation,
The polymerizable resin component obtained by polymerizing the polymerizable resin component by applying a composition for forming a separation layer comprising a polymerizable resin component and a polymerization initiator on the support, and heating or exposing the support. A separation layer forming step of forming the separation layer by firing components;
An adhesive layer forming step of forming an adhesive layer on the separation layer;
And a sealing substrate forming step of forming a sealing substrate on the adhesive layer.   11. The polymerizable resin component is at least one selected from the group consisting of an epoxy resin, an epoxy-modified siloxane, and a polymerizable resin component having an ethylenically unsaturated double bond. The manufacturing method of the laminated body as described in any one of.   The method for producing a laminate according to any one of claims 9 to 11, wherein the polymerizable resin component is an epoxy resin.   The method for producing a laminate according to any one of claims 9 to 12, wherein the polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator.

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