JP6681762B2 - Laminated body and method for manufacturing laminated body - Google Patents

Description

  The present invention relates to a composition for forming a separation layer, a laminate, and a method for producing a 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 meet these requirements, a thin semiconductor chip must be used as a semiconductor chip to be incorporated. Therefore, the thickness (film thickness) of the wafer substrate which is the base 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 the next-generation chip. Therefore, in order to obtain a wafer substrate having the above film thickness, the step of thinning the wafer substrate is indispensable.

  Since the strength of the wafer substrate decreases due to the thinning of the wafer substrate, in order to prevent damage to the thinned wafer substrate, during the manufacturing process, the circuit is automatically transferred while the support is attached to the wafer substrate while the circuit is formed on the wafer substrate. Implement structures such as. 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 attached 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-transmissive support and a semiconductor wafer are bonded together via a photothermal conversion layer and an adhesive layer provided on the support side, the semiconductor wafer is processed, and then the support side The photothermal conversion layer is decomposed by irradiating the substrate with the radiant energy to separate the semiconductor wafer from the support.

Japanese Patent Laid-Open No. 2004-64040 (Published February 26, 2004)

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

  As a result of earnest studies, the inventors of the present application have shown that a novel separation layer-forming composition containing a polymerizable resin component and a polymerization initiator can successfully form a separation layer having high chemical resistance. Then, the present invention was completed. That is, the present invention has been made in view of the above problems, an object thereof is to form a separation layer having high chemical resistance, which can be successfully formed by coating, for forming a new separation layer. It is to provide a composition and its related technology.

  In order to solve the above 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 separating layer forming composition for forming the separating layer in a laminated body formed by stacking, comprising a polymerizable resin component and a polymerization initiator.

  The laminated body of the present invention is a laminated body in which a substrate and a support that transmits light are laminated via an adhesive layer and a separation layer that is altered by irradiation with light, The separation layer is characterized by being a fired product of a cured product obtained by polymerizing a polymerizable resin component with a polymerization initiator.

  Further, the method for producing a laminated body of the present invention is a method for producing a laminated body in which a substrate and a support that transmits light are laminated via an adhesive layer and a separation layer that is altered by irradiation with light. In the method, the polymerizable resin component and a composition for forming a separation layer containing a polymerization initiator are applied to any one of the substrate and the support, and the polymerizable resin is heated or exposed to light. A separation layer forming step of forming the separation layer by polymerizing components and firing the polymerized polymerizable resin component; the substrate or the support on which the separation layer is formed; and the separation layer. It is characterized by including a laminating step of laminating the substrate and the other one of the supports which are not present via the separation layer and the adhesive layer.

  Advantageous Effects of Invention According to the present invention, it is possible to provide a novel composition for forming a separation layer and a related technique thereof, which can successfully form a separation 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.

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

  The composition for forming a separation layer according to one embodiment is a laminate in which a substrate and a support that transmits light are laminated via 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, comprising a polymerizable resin component and a polymerization initiator. The composition for forming the 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 modified 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 ethylenically unsaturated double bonds and epoxy groups. . Such a compound group is widely known in the industrial field, and these can be used without particular limitation in the composition for forming a separation layer according to one embodiment.

  The polymerizable resin component having an epoxy group is not limited as long as it is a compound capable of cleaving the epoxy group by using a polymerization initiator and polymerizing each other. Further, the polymerizable resin component having an epoxy group may 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 having no epoxy group. It may be a resin obtained by polymerizing and introducing an epoxy group into the side chain.

  The polymerizable resin component having an ethylenically unsaturated double bond may be a low molecular weight compound as long as it has an ethylenically unsaturated double bond, and is a polymer such as a homopolymer or a copolymer resin. It 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 its unsaturated bond while using a polymerization initiator to grow a chain bond, and has a molecular weight of 2000 or less (more preferably Is a compound having a constant molecular weight of 1500 or less, and more preferably 900 or less (compound having substantially no molecular weight distribution). The molecular weight of the low molecular weight compound is usually 100 or more.

  Examples of the low molecular weight compound 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 their esters, Examples thereof include amides, and preferred examples include esters of unsaturated carboxylic acids and aliphatic polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and aliphatic polyhydric amine compounds.

  Further, the low molecular weight compound having an ethylenically unsaturated double bond is, for example, a monofunctional or polyfunctional unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group. It may be an addition reaction product added to isocyanates or epoxies. Further, the low molecular weight compound having an ethylenically unsaturated double bond, 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.

  Further, the copolymer resin having an ethylenically unsaturated double bond, for example, a hydroxyl group or an amino group, the functional group in the copolymer of unsaturated carboxylic acid ester or amide having a functional group such as a mercapto group, It may be a resin obtained 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. Further, the copolymer resin having an ethylenically unsaturated double bond is, for example, a copolymer of unsaturated carboxylic acid ester or amide having a functional group such as a hydroxyl group, an amino group, a mercapto group, a carboxylic acid and ethylene. It may be a resin obtained by condensing a compound having a polyunsaturated double bond.

  In addition, the polymerizable resin component includes, for example, a siloxane skeleton, and at least one of an end and a side chain of the siloxane skeleton has an epoxy group and / or an ethylenically unsaturated double bond and is crosslinked. It may be a siloxane containing a functional group.

  Two or more such polymerizable resin components may be used in combination.

[1. Polymerizable resin component having an epoxy group]
The polymerizable resin component having an epoxy group may be a resin component having a sufficient epoxy group in one molecule to be cured by heating or exposure. Among them, at least one resin selected from the group consisting of novolac type epoxy resin (Anv), bisphenol type epoxy resin (Abp), alicyclic epoxy resin, and acrylic resin (Aac) having an epoxy group may be contained. preferable. These polymerizable resin components having epoxy can be used alone 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, and na ¹¹ is an integer of 1 to 5. R ^EP is an epoxy group-containing group.)
In formula (anv0), the alkyl group having 1 to 5 carbon atoms 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, a neopentyl group, and the like. Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among them, a hydrogen atom or a methyl group is preferable as R ^a11 and R ^a12 .

In formula (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 And 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. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group. Further, 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, an epoxy group or an alicyclic epoxy group is attached via a divalent linking group bonded to an oxygen atom (-O-) in the formula. It is preferred that the groups are attached. Here, the divalent linking group is not particularly limited, but examples thereof include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a hetero atom.

Regarding the divalent hydrocarbon group which may have a substituent:
The 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. Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, and an aliphatic hydrocarbon group containing a ring in the structure.

The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms, and 1 to 3 carbon atoms. Is most preferred. As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like.

The branched chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms, further preferably 2 to 4 carbon atoms, and 2 or 3 carbon atoms. Is most preferred. As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{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 - , etc. And alkyl alkylene group such as an alkyl tetramethylene group. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

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

  The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 12 carbon atoms, and specifically, Examples include 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 aromatic ring has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; 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 heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

  Specific examples of the aromatic hydrocarbon group include a group obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); an aromatic containing two or more aromatic rings. Group obtained by removing two hydrogen atoms from a group compound (for example, biphenyl, fluorene, etc.); hydrogen atom in a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) One of which is 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 and a 2-naphthylethyl group). From which one more hydrogen atom is removed). The alkylene group bonded to the aryl group or the heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1.

  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, a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, a tert-butoxy group, and a methoxy group. Most preferred is the group ethoxy. 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 a part or all of the hydrogen atoms of the alkyl group are substituted with the halogen atom. In the alicyclic hydrocarbon group, some of the 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 the aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group and the like. 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, the halogen atom and the halogenated alkyl group as the substituent include those exemplified as the substituent for substituting the hydrogen atom of the alicyclic hydrocarbon group.

Regarding the divalent linking group containing a hetero atom:
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 -OC (= O). -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H is a substituent such as an alkyl group or an acyl group. it 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. Yes, O is an oxygen atom, and m ″ is 0 to Of an integer. And the like. 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 - ^{medium, Y 21} and ^{Y 22} each independently have a substituent The divalent hydrocarbon group may be a divalent hydrocarbon group, which may be a “divalent hydrocarbon group which may have a substituent” mentioned in the description of the divalent linking group. And the like. As Y ²¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 to 5 carbon atoms is further preferable, and a methylene group or an ethylene group is particularly preferable. preferable. As Y ²² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group or an alkylmethylene group is more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. Formula _{^{- [Y 21 -C (= O}} ) -O] m "-Y 22 - In the group represented by, m" is an integer of 0 to 3, preferably an integer of 0 to 2, 0 Or, 1 is more preferable, and 1 is particularly preferable. In other words, the formula ^- Examples of the group represented by the formula ^{-Y 21 -C (= O) -O} -Y 22 - - [Y 21 -C (= O) -O] m "-Y 22 represented by group is particularly preferred among them, the formula _{-. (CH 2) a '} -C (= O) -O- (CH 2) b' -. in the group represented by the formula in the formula, a 'is 1 It is an integer of 10, an integer of 1 to 8 is preferable, an integer of 1 to 5 is more preferable, 1 or 2 is further preferable, and 1 is most preferable.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.

  Further, as the novolac type epoxy resin (Anv), a resin containing a structural unit represented by the following general formula (anv1) can be preferably used.

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

(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 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 further preferably 1 or 2 carbon atoms. Specific examples thereof 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 chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a 1,1-diethylpropyl group, and a 2,2-dimethylbutyl group, and an isopropyl group is preferable.

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. The aliphatic hydrocarbon group which is a monocyclic group is preferably a group obtained by removing one hydrogen atom from monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof 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 preferably has 7 to 12 carbon atoms, and specifically Examples thereof include 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 has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, further preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; 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 heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group for R ^a24 include a group obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocycle (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 (eg, biphenyl, fluorene, etc.); a group in which one of the hydrogen atoms in the aromatic hydrocarbon ring or aromatic heterocycle has been replaced with an alkylene group (eg, benzyl Group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, arylalkyl group such as 2-naphthylethyl group, etc.) and the like. The alkylene group bonded to the aromatic hydrocarbon ring or aromatic heterocycle has preferably 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1.

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

In 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 constitutional units represented by the above formulas (anv2) to (anv3), a polycycloalkane constitutional unit may be used as another constitutional unit capable of substituting the constitutional unit represented by the general formula (anv1). Can be mentioned. As such a polycycloalkane constitutional unit, those having 7 to 12 carbon atoms are preferable, and specifically, adamantane constitutional unit, norbornane constitutional unit, isobornane constitutional unit, tricyclodecane constitutional unit, tetracyclododecane constitutional unit. Etc. can be mentioned.

  When the novolac type epoxy resin (Anv) has another structural unit 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 The total of structural units having an epoxy group is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and more preferably 30 to 70 mol%, based on the total of all structural units constituting Is more preferable.

  Examples of commercially available novolac type epoxy resin (Anv) include JER-152, JER-154, JER-157S70, JER-157S65 (manufactured by Mitsubishi Chemical Corporation), EPICLON N-740, and 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, Epicon 695, Epicon N-695. , EPICLON HP7200 (above, manufactured by DIC Corporation), EOCN-1020 (above, 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 them, a hydrogen atom or a methyl group is preferable as R ^a31 and R ^a32 . 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 (above, manufactured by Mitsubishi Chemical Co., Ltd.), EPICLON 860, EPICLON 1050, EPICLON 1051, EPICLON 1055 (above, manufactured by DIC Co., Ltd.) and the like; as the bisphenol F type epoxy resin, JER-806, JER-807. , JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON830, EPICLON835 (above, manufactured 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, may be 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 which may have an alicyclic epoxy group, and at least ^one of R ¹ and R ² has an alicyclic epoxy group. And 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 which may have 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 which may have an alicyclic epoxy group” means not only a combination of an alicyclic epoxy group and an organic group but also a group consisting of an alicyclic epoxy group (organic group Group) is also included.

  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 group which may have a substituent. Examples thereof include an aryl group, an aralkyl group which may have a substituent, or 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 for R ¹ and R ² may be different from each other or may be the same. Both R ¹ and R ² are preferably an organic group having an alicyclic epoxy group, more preferably both are groups having 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. The divalent linking group is not particularly limited, and examples thereof include a linear, branched, or aliphatic hydrocarbon group containing a ring in the structure, or an aromatic hydrocarbon group. 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. Further, in the aliphatic hydrocarbon group or 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)-, -OC-(= 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 and 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 each independently represents a divalent hydrocarbon group which may have a substituent, and is a linear or branched chain; Alkylene groups are preferred, where O is an oxygen atom, "It is an integer of 0 to 3. And the like.

Y ¹ and Y ² may be the same or different. 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 group 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. Is more preferable. The aliphatic hydrocarbon group and alkylene group have preferably 1 to 30 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 3 carbon atoms. Each of Y ¹ and Y ² is 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 a single bond of Y ¹ and a methylene group of Y ² .

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

(In the formula, 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 an organic group having an alicyclic epoxy group, and both are an alicyclic epoxy group. Is more preferable. In formulas (A1-1) to (A1-2), Y ⁰² is a single bond or a divalent linking group, and examples of the divalent linking group include the same groups as Y ¹ and Y ² . Among them, an aliphatic hydrocarbon group having a single bond or a linear or branched chain optionally having a substituent, or having 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 formula below, n ²¹ is an integer of 1 to 10.

  As a commercial product of the alicyclic epoxy compound, Celoxide 2021, 2021P, 2081, 2083, 2085 (manufactured by Daicel Chemical Industries, Ltd.) and the like can be mentioned as suitable ones.

(4) Multifunctional alicyclic epoxy resin (A2)
As the polymerizable resin component having an epoxy group, a polyfunctional alicyclic epoxy resin (A2) (hereinafter sometimes referred to as “(A2) component”) can be used. The polyfunctional alicyclic epoxy resin (A2) is a compound that does not correspond to the component (A1). The component (A2) may be a low molecular weight compound or a high molecular weight compound, but is preferably a high molecular weight 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 it has excellent chemical resistance and light resistance.

(In the formula, R ¹¹ is a residue excluding active hydrogen groups in an organic compound having q active hydrogen groups. N ¹¹ , n ¹² , ..., N ^q each independently represent 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 is 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 the formula (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 bond of the wavy line and at the bond of * mark. (It binds to a hydrogen atom (H) in the compound represented by 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) in the wavy bond. Bound to a group.)
In the above formula (A2-1), R ¹¹ is a residue obtained by removing the active hydrogen group from the organic compound having an active hydrogen group, and as the precursor “organic compound having an active hydrogen group”, , 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, and 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, phenol resin, and 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. , Terephthalic acid and the like. In addition, compounds having both a hydroxyl group and a carboxyl group, such as lactic acid, citric acid, and oxycaproic acid, are also included. Examples of the amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4′-diaminodiphenylmethane, isophorone. Examples thereof include diamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine and ethanolamine. Examples of the thiols include mercaptos such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan; ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, pentaerythritol tetramercaptopropionate, and mercapto. Propionic acid or a polyhydric alcohol ester of mercaptopropionic acid; and the like.

  Furthermore, as the organic compound having an active hydrogen group, 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, etc. may 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 each independently represent an integer of 0 to 100, and the sum thereof is 1 to 100. Moreover, q shows the integer of 1-100. Among them, n ¹¹ , n ¹² , ..., N ^q are each independently preferably an integer of 2 to 10, and more preferably an integer of 3 to 6. Further, the sum of n ¹¹ , n ¹² , ..., N ^q is preferably 4 to 30, and more preferably 4 to 20. By setting the sum to 4 or more, the crosslink density after curing can be increased and the hardness can be increased. Further, by setting the sum to 30 or less, the solubility in a solvent can be enhanced and the handling property can be enhanced.

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) It A is preferably represented by the above formula (a1). The q A's may be the same or different.

  It is essential that the epoxy compound represented by the formula (A2-1) contains at least one group represented by the formula (a11), and the larger the number, the more preferable. On the other hand, the smaller the number of groups represented by the formula (a13), the more preferable.

The epoxy compound represented by the formula (A2-1) is prepared by using an organic compound having an active hydrogen group as an initiator and 4-vinylcyclohexene-1-oxide or an organic compound having an active hydrogen group as an initiator, as described in JP-B-7-119270. 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 It is produced by epoxidizing a polyether resin having a cyclohexane skeleton or a vinyl group side chain and a norbornene skeleton with peracetic acid, hydrogen peroxide or the like. 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.

  Further, by using the alicyclic epoxy resin (A1) and the polyfunctional alicyclic epoxy resin (A2) together, the component (A1) and the component (A2) when the composition for forming a separation layer is prepared. The compounding ratio with is (A1) / (A2) = 70/30 to 51/49 (mass ratio), and more preferably 70/30 to 60/40 (mass ratio). By setting the blending ratio, the melt viscosity of the obtained composition for forming a separation layer can be set within the preferable range described later. Thereby, the composition for forming the separation layer can be applied so that the film thickness becomes uniform. In addition, a separation layer having high chemical resistance can be formed. As a commercial product of the epoxy resin in which the alicyclic epoxy resin (A1) and the polyfunctional alicyclic epoxy resin (A2) are used in combination, for example, EHPE3150CE manufactured by Daicel Chemical Industries, Ltd. is preferable.

(5) Epoxy group-containing acrylic resin (Aac)
The polymerizable resin component having an epoxy group includes, for example, an unsaturated carboxylic acid, and an acrylic resin having an epoxy group obtained by copolymerizing at least 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. To be Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, availability, and the like. These unsaturated carboxylic acids can be used alone or in combination of two or more.

  In addition, in this specification, "(meth) acrylic acid" means both acrylic acid and methacrylic acid.

  Further, in the present specification, the “compound having an ethylenically unsaturated double bond” may be referred to as “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. To be Among these, (meth) acrylic acid and maleic anhydride are preferable from the viewpoints of copolymerization reactivity, alkali solubility of the obtained 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 be one having no alicyclic epoxy group, or one having an alicyclic epoxy group, Those having an epoxy group are more preferable.

  Examples of the compound having an epoxy group which 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 epoxyalkyl esters such as 6,7-epoxyheptyl (meth) acrylate and 3,4-epoxycyclohexyl (meth) acrylate; α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α Α-alkyl acrylic acid epoxyalkyl esters such as glycidyl-n-butyl acrylate and 6,7-epoxyheptyl α-ethyl acrylate; o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl Ether, etc. Glycidyl ethers; and the like. Among these, glycidyl (meth) acrylate, 2-methylglycidyl (meth) acrylate, 6,7-epoxyheptyl (meth) acrylate, o-vinylbenzyl, from the viewpoint of copolymerization reactivity and the strength of the resin after curing. 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. Further, examples of the polycyclic alicyclic group include a norbornyl group, an isobornyl group, a tricyclononyl group, a tricyclodecyl group, and a tetracyclododecyl group.

  Specific examples of the compound having an epoxy group which 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) is preferable. ) 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 aliphatic saturated hydrocarbon group having 1 to 6 carbon atoms, and R ^a5 represents a divalent hydrocarbon having 1 to 10 carbon atoms. Shows a group and n shows the integer of 0-10. As R ^a4 , 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 is preferable. Examples of R ^a5 include 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 ratio of the constituent unit derived from the unsaturated compound having an epoxy group (the constituent unit having an epoxy group) in the acrylic resin having an epoxy group is preferably 5 to 90% by mass, and 15 to 85% by mass. Is more preferable and 50 to 85 mass% is particularly preferable. By setting the content within the above range, the acrylic resin having an epoxy group can be suitably cured.

  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. In addition, 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 and the following formula (a5-3) is preferable in order to make the curability of the composition for forming a separation layer appropriate. ) And (a5-4) are more preferred.

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. Is an alkyl group. R ^a7 is preferably a single bond, 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. R ^a8 is preferably, for example, a methyl group or an ethyl group.

  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.

  Further, the acrylic resin having an epoxy group may be one obtained by further copolymerizing a compound other than the above. Examples of such other compounds include (meth) acrylic acid esters, (meth) acrylamides, allyl compounds, vinyl ethers, vinyl esters, and styrenes. These compounds may be used alone or in combination of two or more.

  Examples of (meth) acrylic acid esters include linear or branched chains such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and t-octyl (meth) acrylate. Alkyl (meth) acrylate of chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (Meth) acrylate; and the like.

  Examples of the (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 can be mentioned.

  As the allyl compound, allyl esters such as allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate and allyl lactate; allyloxyethanol; Can be mentioned.

  Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl 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 and tetrahydrofurfuryl vinyl ether; vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophene And the like; ethers, vinyl naphthyl ether, vinyl aryl ethers such as vinyl anthranyl ether.

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

  Styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, diethylstyrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxy. Alkyl styrene such as methyl styrene and acetoxymethyl styrene; alkoxy styrene such as methoxy styrene, 4-methoxy-3-methyl styrene and dimethoxy styrene; chloro styrene, dichloro styrene, trichloro styrene, tetrachloro styrene, pentachloro styrene, bromo styrene, 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 2,000 to 50,000, and more preferably 3,000 to 30,000.

[2. Polymerizable resin component having an ethylenically unsaturated double bond]
The polymerizable resin component having an ethylenically unsaturated double bond is a low molecular weight compound as long as it has sufficient ethylenically unsaturated double bond for curing 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 more preferable polymerizable resin component having an ethylenically unsaturated double bond are shown below.

(1) Low molecular weight compound having an ethylenically unsaturated double bond The low molecular weight compound having an ethylenically unsaturated double bond is typically (meth) acrylic acid and a polyhydric alcohol or a polyvalent carboxylic acid. A condensate obtained by condensing with, or a hydroxyl group, an amino group, an unsaturated carboxylic acid ester or amide having a functional group such as a mercapto group, a polyhydric alcohol or a polycarboxylic acid, an isocyanate group or an epoxy group Examples thereof include a polyfunctional monomer that is an addition polymer obtained by addition-polymerization via, and a monofunctional monomer having an ethylenically unsaturated double bond.

  As the polyfunctional monomer, 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) ac Rate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (meth) acryloxydiene 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, phthalic acid diglycidyl ester di (meth) acrylate, glycerin triacrylate, glycerin polyglycidyl ether poly (meth Acrylate, urethane (meth) acrylate (that is, tolylene diisocyanate), reaction product of trimethylhexamethylene diisocyanate, hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate, methylenebis (meth) acrylamide, (meth) acrylamide methylene ether, Examples thereof include polyfunctional monomers such as condensates of polyhydric alcohols and N-methylol (meth) acrylamide, and triacrylformal. These polyfunctional monomers may be used alone or in combination of two or more.

  Further, as the monofunctional monomer, (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- Acrylamido-2-methylpropanesulfonic acid, tert-butyl acrylamidosulfonic 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 ( Examples thereof include (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 A copolymer resin having an ethylenically unsaturated double bond may be used as the polymerizable resin component having an ethylenically unsaturated double bond. Examples of such a copolymer resin having an ethylenically unsaturated double bond include, for example, an ethylenic double bond in a side chain of an acrylic resin skeleton composed of (meth) acrylic acid and (meth) acrylic acid ester. Examples thereof include (meth) acrylic resin having a bond introduced therein.

  Examples of the polymerizable resin component having an ethylenically unsaturated group include, for example, 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 group-containing unsaturated compound epoxy. Resin obtained by reacting a group, or an epoxy group of a resin obtained by at least copolymerizing an unsaturated carboxylic acid and an epoxy group-containing unsaturated compound, by reacting a carboxyl group of an unsaturated carboxylic acid The obtained resin etc. can be mentioned. That is, as the resin for copolymerizing the unsaturated carboxylic acid and the epoxy group-containing unsaturated compound, one form of the above-mentioned acrylic resin (Aac) having an epoxy group can be mentioned.

  As a method of introducing an ethylenically unsaturated double bond into the acrylic resin skeleton, as described above, the carboxylic acid which the acrylic resin skeleton has, and the ethylenically unsaturated double bond via the epoxy group Is not limited to the form in which is introduced. For example, an acrylic resin having a carboxylic acid group, a hydroxyl group, an amine group, an amide group, and a thiol group in its side chain, an ethylenically unsaturated double bond, a carboxylic acid group, a hydroxyl group, an amine group, and an amide. A monomer having a group and a thiol group or the like may be reacted with, for example, a polyfunctional isocyanate or a polyfunctional epoxy resin to introduce an ethylenically unsaturated double bond.

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

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

  The weight average molecular weight of the polymerizable resin component having an ethylenically unsaturated double bond is preferably 2,000 to 50,000, more preferably 5,000 to 30,000. When the content is in the above range, suitable coating workability of the composition for forming a separation layer can be obtained.

[3. Crosslinkable group-containing siloxane]
Further, 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 the structural units in the polysiloxane. Represents the molar percentage of the attached structural unit, n + m = 100%, n> 0).

  The epoxy group siloxane can form a polymer by cross-linking and polymerizing at 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). .

(In the formula, R ^c1 is a group containing an epoxy group, an oxetanyl group, a vinyl group, and a (meth) acryloyl group, R ^c2 is an alkyl group or an aryl group, and the subscripts m and n are the polysiloxane. Represents the mole percentage of the structural unit with the above subscript to all the structural units of, m is 50 to 90 mol%, and n is 10 to 50 mol%, provided that the total of m and n is 100 mol. %.).

Specific examples of the crosslinkable group-containing siloxane include polymer E and polymer F represented by the following formulas, 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 with the subscript with respect to all the structural units in the polymer E, m1 = 50 to 90 mol%, and n1 = 10. ˜50 mol%, provided that the total 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 with the subscript with respect to all the structural units in the polymer F, m2 = 50 to 90 mol%, n2 = 1-10 mol% and n3 = 5-50 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 an epoxy group or a polymerizable group such as 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, for example, a thermal radical polymerization initiator and a photo radical polymerization initiator can be mentioned. The thermal cationic polymerization initiator, photocationic polymerization initiator, thermal radical polymerization initiator, and photoradical polymerization initiator will be described in detail below.

(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. In addition, 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 the separation layer can accelerate the polymerization of the polymerizable group by the action of the cation generated by heat during the heat curing treatment. The compounds that can be used as the thermal cationic polymerization initiator will be described in detail below.

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

(In the above (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, and the aryl group is 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. It 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 aryl groups, 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 is bonded via an ether bond or an ester bond ( It may be bonded to a phenyl group in hr-1). Note that hr-1 in Rh ^{01 to} Rh ⁰⁷ may be different substituents each independently.
The following cation moieties can be mentioned as preferred forms of the cation moiety represented by general formula (h01).

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

  Moreover, the following cation moieties can be mentioned as a preferable form of the cation moiety represented by the general formula (h02).

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

  Examples of thermal cationic polymerization initiators that are commercially available include San-Aid SI-45, SI-47, SI-60, SI-60L, SI-80, SI-80L, SI-100, SI-100L, SI-. 110, SI-110L, SI-145, I-150, SI-160, SI-180L, SI-B3, SI-B2A, SI-B3A, SI-B4, SI-300 (manufactured by Sanshin Chemical Industry Co., Ltd.) ) And the like. In addition, CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (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-2689, TAG-2690, TAG-2700, TAG-2710, TAG-2100, CDX-3027, CXC-1615, CXC-1616, CXC-1750, CXC-1738, CXC-1614, CXC-1742, CXC-1743, 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 an acid in the thermal cationic polymerization initiator is preferably a temperature for pre-baking the support coated with the composition for forming a separation layer or more, and specifically 110 ° C. or more. Is preferable, and 130 ° C. or higher is more preferable.

  The blending amount of the thermal cationic polymerization initiator is preferably 0.01% by weight or more and 20% by weight or less, and 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. Is more preferable and 5% by weight or more and 10% by weight or less is most preferable. When the blending amount of the thermal acid generator is 0.1% by weight or more, not only the polymerizable resin component can be suitably polymerized, but also by baking the cured product of the polymerizable resin component, for example, It is possible to form a fired body capable of suitably absorbing light in the wavelength range of 600 nm or less.

(2) Photocationic Polymerization Initiator In the 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). It is preferable to use at least one selected cationic polymerization initiator (B0) (hereinafter referred to as “(B0) component”).

(In the formula, R ^{b01 to} R ^b04 each independently represent a fluorine atom or an aryl group which may have a substituent. R ^b05 represents a fluorine atom or a fluorine which may have a substituent. R ^b05 may be the same or different, and ^q is an integer of 1 or more, and Q ^{q +} is 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. Therefore, the composition for forming a separation layer having the component (B0) can suitably cure the polymerizable resin component having an epoxy group by exposing.

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, which may have a substituent, of R ^{b01 to} R ^b04 has preferably 5 to 30 carbon atoms, more preferably 5 to 20 carbon atoms, and further preferably 6 to 15 carbon atoms. , 6 to 12 is particularly preferable. Specific examples thereof 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. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, a hydrocarbon group (preferably a linear or branched alkyl group, and preferably has 1 to 5 carbon atoms), 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 ^them, as R ^{b01 to} R ^{b04 in the} formula (b0-1), a fluorinated phenyl group is preferable, and a perfluorophenyl group is particularly preferable.

Specific preferred examples of the anion portion of the compound represented by the formula (b0-1), 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. Among them, tetrakis (pentafluorophenyl) borate _{([B (C 6 F 5} ) 4] -) is especially preferred.

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 further 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 some or all of hydrogen atoms are substituted with fluorine atoms can be mentioned. 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, a fluorine atom, a trifluoromethyl group or pentafluoro. The ethyl group is more preferred.
The anion part of the compound represented by the formula (b0-2) is preferably represented by the following general formula (b0-2a).

(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 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, and the following general formulas are given. The organic cations represented by (ca-1) to (ca-5) are particularly preferable.

(In the formula, R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² each independently represent an aryl group which may have a substituent, a heteroaryl group, an alkyl group or an alkenyl group, 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 it 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.)
Examples of the aryl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable. Examples of the heteroaryl group for R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² include those in which some of the carbon atoms constituting the aryl group have been substituted with heteroatoms. Examples of the hetero atom include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and a group obtained by removing one hydrogen atom from 9H-thioxanthen-9-one as the substituted heteroaryl group. The alkyl group in R ^{201 to} R ²⁰⁷ and R ^{211 to} R ²¹² is preferably a chain or cyclic alkyl group 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, for example, an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amino group, 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 of 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. The aliphatic hydrocarbon group means a hydrocarbon group having no aromaticity. Moreover, 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 has 5 to 30 carbon atoms, further preferably has 5 to 20 carbon atoms, and particularly preferably has 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 ^contained in the aromatic hydrocarbon group for R ′ ²⁰¹ include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting these aromatic rings is a hetero atom. Examples thereof include a substituted aromatic heterocycle, or a ring in which a part of hydrogen atoms constituting these aromatic rings or aromatic heterocycles are substituted with an oxo group or the like. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom and a nitrogen atom. Specific examples of the aromatic hydrocarbon group for R ′ ²⁰¹ include a group obtained by removing one hydrogen atom from the aromatic ring (aryl group: for example, phenyl group, naphthyl group, anthracenyl group, etc.), A group in which one of hydrogen atoms is substituted with an alkylene group (for example, 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. ), A group obtained by removing one hydrogen atom from a ring (for example, anthraquinone or the like) in which a part of hydrogen atoms constituting the aromatic ring is substituted with an oxo group or the like, an aromatic heterocycle (for example, 9H-thioxanthene, 9H- (Thioxanthen-9-one, etc.) and the like, a group in which one hydrogen atom has been removed. 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 in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), an alicyclic hydrocarbon group is linear or branched. Examples thereof include a group bonded to the end of a chain-like aliphatic hydrocarbon group and a group in which an alicyclic hydrocarbon group is present 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. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from monocycloalkane. The monocycloalkane preferably has 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, as the polycycloalkane, a polycycloalkane having a polycyclic skeleton of a bridged ring system such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; a condensed ring system such as a cyclic group having a steroid skeleton A polycycloalkane having a polycyclic skeleton of is more preferable.

Among them, the cyclic aliphatic hydrocarbon group for R ′ ²⁰¹ is preferably a group in which one or more hydrogen atoms have been removed from monocycloalkane or polycycloalkane, and a group in which one hydrogen atom has been removed from polycycloalkane. More preferred, adamantyl group and norbornyl group are particularly preferred, and adamantyl group is most preferred.

The linear or branched aliphatic hydrocarbon group which 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 preferably 1 to 4, and most preferably 1 to 3. As the linear aliphatic hydrocarbon group, preferably a linear alkylene group, and specific examples include a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], trimethylene [ _{- (CH 2) 3 -]} , a tetramethylene group _{[- (CH 2) 4 -} ], a pentamethylene group _{[- (CH 2) 5 -} ] , and the like. As the branched aliphatic hydrocarbon group, preferably a branched chain alkylene group, _{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 Alkylethylene group such as CH ₃ ) ₂ —CH ₂ —; 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 - And the like alkyl alkylene group such as an alkyl tetramethylene group of. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

Chain-like alkyl group which may have a substituent:
The chain alkyl group for R ′ ²⁰¹ may be 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, henicosyl group, docosyl group and the like.

  The branched-chain 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, A 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 4-methylpentyl group and the like can be mentioned.

A chain alkenyl group which may have a substituent:
The chain alkenyl group for R ′ ²⁰¹ may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms, and 2 to 4 carbon atoms. Is more preferable, and 3 is particularly preferable. 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 straight chain alkenyl group, more preferably a vinyl group or a 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 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, and the above. Examples thereof include the cyclic group for R ′ ²⁰¹ .

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

When R ^{201 to} R ²⁰³ , R ^{206 to} R ²⁰⁷ , and R ^{211 to} R ²¹² are bonded to each other to form a ring together with the sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, or a nitrogen atom, or 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 formula in its ring skeleton is preferably a 3 to 10-membered ring including a sulfur atom, and particularly preferably a 5 to 7-membered ring. 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. Examples thereof include a thiophenium ring and a tetrahydrothiopyranium ring.

R ^{208 to} R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and when they become an alkyl group, they are bonded to each other. You may form a ring.

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 an substituent. -SO ₂ - containing cyclic group. ^Examples of the aryl group for R ²¹⁰ include an unsubstituted aryl group having 6 to 20 carbon atoms, and a phenyl group and a naphthyl group are preferable. 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's each independently represent 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 obtained by removing one hydrogen atom 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) -valent, that is, a divalent or trivalent linking group. The divalent linking group for W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and may have the substituent exemplified for R ^EP in the formula (anv0). A group similar to the divalent hydrocarbon group is preferable. The divalent linking group for 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 an arylene group, or a group consisting only of an 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 for W ²⁰¹ include a group in which one hydrogen atom is removed from the divalent linking group for 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 for W ²⁰¹ is preferably an arylene group to which two carbonyl groups are bonded.

  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).

(In the formula, R ″ ²⁰¹ is a hydrogen atom or a substituent, and the substituent is the same as the substituent which R ^{201 to} R ²⁰⁷ and R ^{210 to} R ²¹² may have. It is.)
Further, as the cation represented by the formula (ca-1), cations represented by the following general formulas (ca-1-25) to (ca-1-36) are 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 the suitable cation represented by the formula (ca-2) include a diphenyliodonium cation and a 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).

  Further, as the cation represented by the formula (ca-5), cations represented by the following general formulas (ca-5-1) to (ca-5-2) are also preferable.

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

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

  As the component (B0), one type of the above-mentioned photo-acid generator may be used alone, or two or more types may be used in combination. 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 a 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. Further, 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 of the component (B0) and the acid derived from the anion part It can be appropriately determined according to the above. Specifically, the content ratio of the component (B0) in the cationic photopolymerization initiator is preferably 20 to 99.999 mass%, more preferably 30 to 99.99 mass%, and 40 to. The content 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, it is possible to make the strength of plural kinds of acids generated from the polymerization initiator upon exposure to be appropriate as a whole, and to cure the polymerizable resin component suitably. be able to.

  The content of the photocationic polymerization initiator in the composition for forming the separation layer is preferably 0.01 to 60 parts by mass, and 0.05 to 30 parts by mass with respect to 100 parts by mass of the polymerizable resin component having an epoxy group. 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. When the content of the photocationic polymerization initiator is 0.01 to 60 parts by mass, the light transmittance of the separation layer can be lowered after the polymerizable resin component is cured and baked, which is suitable for the laser reaction. Sex can be obtained.

(3) Thermal Radical Polymerization Initiator Examples of thermal radical polymerization initiators include peroxides and azo polymerization initiators. These thermal radical polymerization initiators polymerize the polymerizable monomer by radicals generated by being heated.

  Examples of peroxides include ketone peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, peroxyesters, peroxycarbonates and peroxyketals. 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 pertriphenylacetate, tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peracetate, tert-butyl perbenzoate, tert-butyl perphenylacetate, per-4-methoxyacetic acid tert-butyl And per-N- (3-toluyl) carbamate tert-butyl, dicumyl-peroxide, tert-butyl-peroxy-2-ethylhexyl-monocarbonate, di (4-tert-butylcyclohexyl) peroxydicarbonate, 2,5 -Dimethyl-2,5-di (tert-butylperoxy) hexane, 1,1-di (tert-butylperoxy) cyclohexane and the like can be mentioned.

  Examples of commercially available peroxides include, for example, trade name “Parkmill (registered trademark)”, trade name “Perbutyl (registered trademark)”, trade name “Perocta (registered trademark)” and “Perloyl” manufactured by NOF CORPORATION. (Registered trademark) ”and“ Perhexa (registered trademark) ”.

  Examples of the azo-based polymerization initiator include 2,2′-azobispropane, 2,2′-dichloro-2,2′-azobispropane, 1,1′-azo (methylethyl) diacetate, 2, 2'-azobis (2-amidinopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2'-azobisisobutane, 2,2'-azobisisobutyramide, 2,2 ' -Azobisisobutyronitrile, 2,2'-azobis-2-methylpropionate methyl, 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis-2-methylbutyronitrile, Dimethyl 2,2'-azobisisobutyrate, 1,1'-azobis (1-methylbutyronitrile-3-sodium sulfonate), 2- (4-methylphenylazo) -2-methylmalonodinitrile , 4'-azobis-4-cyanovaleric acid, 3,5-dihydroxymethylphenylazo-2-allylmalononitrile, 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-cycloheptane nitrile, 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 part by weight or more and 20 parts by weight or less, and 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. The thermal radical polymerization initiator may be added to the composition for forming the separation layer by a known method immediately before using the composition for forming the separation layer. The thermal radical polymerization initiator may be added to the additive solvent described below and then added to the composition for forming the separation layer.

  The one-minute half-life 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 1-hour half-life temperature of the thermal radical polymerization initiator is preferably 50 ° C. or higher and 140 ° C. or lower, and more preferably 80 ° C. or higher and 140 ° C. or lower.

  Since the 1-minute half-life temperature of the thermal radical polymerization initiator is 90 ° C. or higher and 200 ° C. or lower and the 1-hour half-life temperature is 50 ° C. or higher and 140 ° C. or lower, after the thermal radical polymerization initiator is blended, The time until the polymerizable resin component having an ethylenically unsaturated double bond is polymerized and gelled can be lengthened. This can prolong the workable time when the adhesive composition is applied on the support. Further, the 1-minute half-life temperature of the thermal radical polymerization initiator is 90 ° C. or higher and 200 ° C. or lower, and the 1-hour half-life temperature is 50 ° C. or higher and 140 ° C. or lower, so that the adhesive composition When the diluent solvent is removed by applying and heating, radicals can be simultaneously generated to preliminarily initiate the polymerization of the polymerizable resin component. From the viewpoint that the workable time can be lengthened, it is preferable that the 1-minute half-life temperature and the 1-hour half-life temperature of the thermal radical polymerization initiator are higher. From the viewpoint of prompt gelation, it is preferable that the 1-minute half-life temperature and the 1-hour half-life temperature of the thermal radical polymerization initiator are lower.

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

(4) Photo-Radical Polymerization Initiator The composition for forming the separation layer may be configured to polymerize the polymerizable resin component with the photo-radical polymerization initiator. In the case of using a photo-radical polymerization initiator as the polymerization initiator, if the adhesive composition is packaged so that the light-shielding state can be maintained, the separation layer is formed in the state where the photo-radical polymerization initiator is blended. The composition for use can be commercialized.

  Specific examples of the photo radical polymerization 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'-methyldimethyl sulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, butyl 4-dimethylaminobenzoate, 4-dimethylamino-2- Ethylhexylbenzoic acid, 4-dimethylamino-2-isoamylbenzoic acid, benzyl-β-methoxyethylacetal, benzyldimethylketal, 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 -Ethylanthraquinone, octamethylanthraquinone, 1,2-benzanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzoyl peroxide, cumene peroxide, 2-mercaptobenzimidazole, 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-triaryl imidazole 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. Chill ether, benzoin-t-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylaminopropiophenone, dichloroacetophenone, trichloroacetophenone, pt-butylacetophenone, p-dimethylaminoacetophenone, p-t-butyltrichloroacetophenone, p-t-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- Clydinyl) 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-e 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- Examples thereof include trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-s-triazine and 2,4-bis-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-s-triazine. To be In addition, as the photo-radical polymerization 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 compounding amount of the photo radical polymerization initiator is preferably 0.1 part by weight or more and 20 parts by weight or less, and 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 diluting solvent in addition to the above-mentioned polymerizable component and polymerization initiator.

(1) Surfactant The composition for forming a separation layer may contain a surfactant. Examples of the surfactant include silicone-based surfactants and fluorine-based surfactants. 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) and the like can be used. Specific examples of the fluorine-based surfactant include F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444 and 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.

  As the surfactant, one type may be used alone, or two or more types may be used in combination. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 2 parts by mass, and 0.1% by mass based on 100 parts by mass of the total amount of the polymerizable resin components. More preferably, it is from 03 to 1 part by mass. By setting it as the said range, when a 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 one embodiment preferably contains a diluting solvent. The diluent is not limited as long as it is a solvent capable of dissolving the polymerizable resin component and the polymerization initiator, and the solvent shown below can be preferably used.

  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, for example, cyclohexane. , Cycloheptane, cyclooctane, naphthalene, decahydronaphthalene, tetrahydronaphthalene and like cyclic hydrocarbons, p-menthane, o-menthane, m-menthane, diphenylmenthane, 1,4-terpine, 1,8-terpine, bornane, Norbornane, Pinan, Tujan, Karan, Longifolene, Geraniol, Nellore, Linalool, Citral, Citronellol, Menthol, Isomenthol, Neomenthol, α-Terpineol, β-Terpineol, γ-Terpineol, Terpinen-1-ol, Ter Terpene-based solvents such as ene-4-ol, dihydroterpinyl acetate, 1,4-cineole, 1,8-cineole, borneol, carvone, yonone, tsuyon, camphor, d-limonene, l-limonene, dipentene; γ -Lactones such as butyrolactone; ketones such as acetone, methylethylketone, cyclohexanone (CH), methyl-n-pentylketone, methylisopentylketone, 2-heptanone; many such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol A polyhydric alcohol; a compound having an ester bond such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; Derivatives of polyhydric alcohols such as rucols or compounds having an ester bond such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether and other monoalkyl ethers or compounds having an ether bond such as monophenyl ether (these 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, ethylbenzyl ether, cresylmethyl ether 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 contain a sensitizer depending on the composition of the polymerizable resin component and the polymerization initiator.

<Laminate 10 (first embodiment)>
As shown in FIG. 1, a laminated body 10 according to one embodiment (first embodiment) of the present invention is formed by laminating a substrate 1 and a support plate 2 via an adhesive layer 3 and a separation layer 4. Here, the separation layer 4 is formed using the composition for forming a separation layer according to one embodiment. Therefore, it has a separation layer having high chemical resistance. Therefore, a laminate manufactured using the composition for forming a separation layer according to one embodiment is also included in the scope of the present invention.

[Substrate 1]
The substrate 1 can be subjected to processes such as thinning and mounting while being supported by the support plate 2. Further, on the substrate 1, for example, a structure such as an integrated circuit or a metal bump can be mounted. The substrate 1 can typically be a silicon wafer substrate, but is not limited thereto, 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 via the adhesive layer 3. Therefore, the support plate 2 only needs to have sufficient strength to prevent damage or deformation of the substrate 1 during the processes such as thinning, carrying, and mounting of the substrate 1. Further, the support plate 2 may be one that transmits light for changing the quality of the separation layer 4. From these viewpoints, the support plate 2 may be made of glass, silicon, or a support made of 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 by an adhesive used for attaching the substrate 1 and the support plate 2.

  The adhesive for forming the adhesive layer 3 contains a thermoplastic resin, a diluent, and other components such as additives. Here, the thermoplastic resin contained in the adhesive, that is, the thermoplastic resin contained in the adhesive layer 3 may be one having adhesiveness, and examples thereof include a hydrocarbon resin and an acrylic-styrene resin. A maleimide resin, an elastomer resin, a polysulfone resin, or a combination thereof can be more preferably used. 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 having a hydrocarbon skeleton and obtained by polymerizing a monomer composition. As the hydrocarbon resin, a cycloolefin polymer (hereinafter sometimes referred to as "resin (A)"), and at least one resin selected from the group consisting of terpene resins, rosin resins and petroleum resins (hereinafter, " Resin (B) ”) and the like, but are not limited thereto.

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

  Examples of the cycloolefin-based 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 tetracyclodode. Tetracycles such as decene, pentacycles such as cyclopentadiene trimer, heptacycles such as tetracyclopentadiene, and alkyl (methyl, ethyl, propyl, butyl, etc.) substitution products of these polycycles, alkenyl (vinyl) Etc.) substitution products, alkylidene (ethylidene, etc.) substitution products, aryl (phenyl, tolyl, naphthyl, etc.) substitution products, and the like. Of 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-mentioned cycloolefin-based monomer, and preferably contains an alkene monomer, for example. 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.

  Further, it is preferable to contain a cycloolefin monomer as a monomer component constituting the resin (A) from the viewpoint of high heat resistance (low thermal decomposition and thermal weight reduction property). The ratio of the cycloolefin monomer to the total monomer components constituting the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, and further preferably 20 mol% or more. preferable. The ratio of the cycloolefin monomer to the entire monomer components 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, It is more preferably 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 entire monomer components constituting the resin (A) is preferably 10 to 90 mol% and more preferably 20 to 85 mol% from the viewpoint of solubility and flexibility. , 30 to 80 mol% is more preferable.

  It should be noted that the resin (A) is a resin having no polar group, such as a resin obtained by polymerizing a monomer component composed of a cycloolefin-based monomer and an alkene monomer, under high temperature. It is preferable for suppressing the generation of the gas.

  There are no particular restrictions on the polymerization method, polymerization conditions, etc. when polymerizing the monomer components, and they may be appropriately set according to a conventional method.

  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 resin (A) of the adhesive component.

(In chemical formula (ad2), n is 0 or an integer of 1 to 3.)
As such a 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” and “ZEONOR” manufactured by Zeon Corporation. Examples thereof include “ZEONEX” and “ARTON” manufactured by JSR Corporation.

  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-based resin include terpene resin, terpene phenol resin, modified terpene resin, hydrogenated terpene resin, hydrogenated terpene phenol resin, and the like. Examples of the rosin-based resin include rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, and modified rosin. Examples of the petroleum resin include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and coumarone / indene petroleum resins. Among these, hydrogenated terpene resins and hydrogenated petroleum resins are more preferable.

  The softening point of the resin (B) is not particularly limited, but it is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 to 160 ° C., it is possible to prevent the laminated body from softening when exposed to a high temperature environment, and no defective adhesion occurs.

  The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. When the weight average molecular weight of the resin (B) is 300 or more, the heat resistance becomes sufficient, and the degassing amount decreases 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 will be good. Therefore, the residue of the adhesive layer on the substrate after the support is separated can be quickly dissolved and removed. The weight average molecular weight of the resin (B) in the present embodiment means a polystyrene equivalent molecular weight measured by gel permeation chromatography (GPC).

  The resin may be a mixture of the resin (A) and the resin (B). 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), the heat resistance in a high temperature environment, and It is preferable because it has excellent flexibility.

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

  Examples of the (meth) acrylic acid ester include (meth) acrylic acid alkyl ester having a chain structure, (meth) acrylic acid ester having an aliphatic ring, and (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. . Examples of the acrylic long-chain alkyl ester include acrylic acid 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 or the like. Examples include alkyl esters. The alkyl group may have a branched chain structure.

  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 such as 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. Esters can be mentioned.

  Examples of the (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. Examples thereof include (meth) acrylate, tetracyclododecanyl (meth) acrylate, and dicyclopentanyl (meth) acrylate, with isobornyl methacrylate and dicyclopentanyl (meth) acrylate being more preferable.

  The (meth) acrylic acid ester having an aromatic ring is not particularly limited, but 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. , Phenoxymethyl group, phenoxyethyl group and the like. Moreover, 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 the maleimide-based resin include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide and N-sec as monomers. -Butylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Maleimide having an alkyl group of N, cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc. Resins obtained by polymerizing aromatic maleimides having an aryl group such as N, N-phenylmaleimide, Nm-methylphenylmaleimide, N-o-methylphenylmaleimide, Np-methylphenylmaleimide and the like. To be

(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, a carboxyl group and the like. Further, the content of the styrene unit is more preferably in the range of 14% by weight or more and 50% by weight or less. Further, the elastomer preferably has a weight average molecular weight of 10,000 or more and 200,000 or less.

  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, a hydrocarbon solvent described later. Since it is easily dissolved in (solvent), the adhesive layer can be removed more easily and quickly. Further, when 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 (fluoride, etc.) exposed when the wafer substrate is subjected to the resist lithography step is exposed. It exhibits excellent resistance to hydrogen acid, etc.) and alkalis (TMAH, etc.).

  The elastomer may be further mixed with the above-mentioned (meth) acrylic acid ester.

  The content of styrene units is more preferably 17% by weight or more, and further 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 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. 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 block is a reaction-crosslinking type styrene-ethylene-ethylene-propylene-styrene block copolymer -(Septon V9461 (manufactured by Kuraray Co., Ltd.), Septon V9475 (manufactured by Kuraray Co., Ltd.)), styrene block is a reaction crosslinking type styrene-ethylene-butylene-styrene block copolymer (Septon V9827 (reactive polystyrene-based hard block-containing) Kuraray Co., Ltd.), polystyrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl group modification), and the like, and the styrene unit content and the weight average molecular weight of the elastomer are within the above ranges. Can be used.

  Further, among the elastomers, hydrogenated products are more preferable. If it is a hydrogenated product, its stability against heat is improved, and deterioration such as decomposition and polymerization hardly occurs. It is also more preferable from the viewpoint of solubility in a hydrocarbon solvent and resistance to a resist solvent.

  Further, among the elastomers, those having a styrene block polymer at both ends are more preferable. This is because styrene, which has high heat stability, is blocked at both ends to exhibit higher heat resistance.

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

  Examples of commercially available products that can be used as the elastomer contained in the adhesive that constitutes the adhesive layer 3 include "Septon (trade name)" manufactured by Kuraray Co., Ltd., "High Blur (trade name)" manufactured by Kuraray Co., Ltd., and Asahi Kasei Corporation. "Tuftec (trade name)" manufactured by JSR Co., "Dynaron (trade name)" manufactured by JSR Co.

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

  Further, the elastomer may be a mixture of a plurality of types. That is, the adhesive forming the adhesive layer 3 may include a plurality of types of elastomers. Then, it is sufficient that at least one of the plurality of types of elastomers contains a styrene unit as a constituent unit of the main chain. In addition, at least one of the plurality of types of elastomers has a styrene unit content of 14% by weight or more and 50% by weight or less, or a weight average molecular weight of 10,000 or more and 200,000 or less. Within the range, it is within the scope of the present invention. When the adhesive constituting the adhesive layer 3 contains a plurality of types of elastomers, the content of styrene units may be adjusted within the above range as a result of mixing. For example, Septon (trade name) Septon 4033 manufactured by Kuraray Co., Ltd. having a styrene unit content of 30% by weight and Septon (trade name) Septon 2063 having a styrene unit content of 13% by weight are used in a weight ratio of 1 When mixed in a ratio of 1, the styrene content with respect to the entire elastomer contained in the adhesive is 21 to 22% by weight, and therefore 14% by weight or more. Further, for example, when a styrene unit having a styrene unit content of 10% by weight and a styrene unit having a styrene unit content of 60% by weight are mixed at a weight ratio of 1: 1, the content is 35% by weight, which is within the above range. The present invention may have such a form. Further, it is most preferable that all of the plurality of types of elastomers contained in the adhesive constituting the adhesive layer 3 contain styrene units within the above range and have a weight average molecular weight within the above range.

  In addition, it is preferable to form the adhesive layer 3 using a resin other than a photocurable resin (for example, a UV curable resin). By using a resin other than the photo-curable resin, it is possible to prevent a residue from being generated around the minute irregularities of the substrate 1 after peeling or removing the adhesive layer 3. In particular, the adhesive forming the adhesive layer 3 is preferably one that does not dissolve in any solvent, but one that dissolves in a specific solvent. This is because the adhesive layer 3 can be removed by dissolving it in a solvent without applying a 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 decreased.

(Polysulfone resin)
The adhesive for forming the adhesive layer 3 may include a polysulfone-based resin. By forming the adhesive layer 3 with a polysulfone-based resin, it is possible to manufacture a laminate capable of dissolving the adhesive layer in a subsequent step and peeling the support from the substrate even if the laminate is treated at a high temperature. You can If the adhesive layer 3 contains the polysulfone resin, the laminate can be preferably used even in a high temperature process in which the laminate is treated at a high temperature of 300 ° C. or higher by annealing or the like.

  The polysulfone-based resin has a structure including a structural unit represented by the following general formula (ad3) and at least one 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 a group consisting of a phenylene group, a naphthylene group and an anthrylene group. Selected, X'is an alkylene group having 1 to 3 carbon atoms.)
The polysulfone-based resin is provided with at least one of the polysulfone structural unit represented by the formula (ad3) and the polyether sulfone structural unit represented by the formula (ad4), so that the substrate 1 and the support plate 2 are Even if the substrate 1 is treated under a high temperature condition after attaching and, it is possible to form a laminate that can prevent the adhesive layer 3 from becoming insoluble due to decomposition, polymerization, or the like. Further, the polysulfone-based resin is stable even if heated to a higher temperature as long as it is a polysulfone resin composed of the polysulfone constitutional unit represented by the formula (ad3). Therefore, it is possible to prevent the residue resulting from the adhesive layer from being generated on the substrate 1 after cleaning.

  The weight average molecular weight (Mw) of the polysulfone resin is preferably in the range of 30,000 or more and 70,000 or less, more preferably in the range of 30,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polysulfone resin is within the range of 30,000 or more, it is possible to obtain an adhesive composition that can be used at a high temperature of 300 ° C. or more, for example. Further, when the weight average molecular weight (Mw) of the polysulfone resin is within the range of 70,000 or less, the polysulfone resin can be suitably dissolved in the solvent. That is, it is possible to obtain an adhesive composition that can be suitably removed with a solvent.

(Other components)
The adhesive forming the adhesive layer 3 may further contain another miscible substance as long as the essential properties are not impaired. For example, it is possible to further use various conventionally used additives such as an additional resin for improving the performance of the adhesive, a plasticizer, an adhesion aid, a stabilizer, a colorant, a thermal polymerization inhibitor and a surfactant. it can. Further, the adhesive may be diluted with the diluting solvent described in the section of the above (1) Diluting solvent and used.

[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 the polymerizable resin component contained in the composition for forming a separation layer is cured by a polymerization initiator. It is a layer formed by a fired body formed by firing a cured product. The separation layer 4 is a fired body formed by using the composition for forming a separation layer, and thus can be appropriately altered in quality by absorbing the 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 obtained by polymerizing the above-mentioned polymerizable resin component 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 present inventors have found that such a fired body can form a separation layer having high chemical resistance and capable of suitably absorbing light having a wavelength in the range of 600 nm.

  The thickness of the separation layer 4 is more preferably, for example, 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 within 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. . In addition, the thickness of the separation layer 4 is particularly preferably within the range of 1 μm or less from the viewpoint of productivity.

  In the present specification, the term “deteriorates” 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 between the separation layer and a 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 adhesiveness before being exposed to light. That is, by absorbing light, the separation layer becomes brittle. The alteration of the separation layer may be that the separation layer undergoes decomposition due to energy of absorbed light, changes in configuration, dissociation of functional groups, or the like. Degradation of the separation layer occurs as a result of absorbing light.

  Therefore, for example, the support plate and the substrate can be easily separated by changing the quality so that the separation layer is destroyed 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 separation device or the like, and the other is held and lifted by a suction pad (suction unit) equipped with suction means. By separating the support plate from the substrate, or by gripping the chamfered portion at the peripheral edge of the support plate with a separation plate equipped with a clamp (claw), a force is applied to the substrate and the support plate. It is good to separate and. In addition, for example, the support plate may be peeled from the substrate in the laminate by using a support separation device including a peeling unit that supplies a peeling liquid for peeling the adhesive. By supplying a peeling liquid to at least a part of the peripheral end portion of the adhesive layer in the laminate by the peeling means to swell the adhesive layer in the laminate, the force concentrates from the swelled portion of the adhesive layer to the separation layer. In this way, a force can be applied to the substrate and the support plate. Therefore, the substrate and the support plate can be preferably separated.

  The force applied to the laminated body may be appropriately adjusted according to the size of the laminated body and the like and is not limited. For example, in the case of a laminated body having a diameter of about 300 mm, a force of about 0.1 to 5 kgf is applied. By adding, the substrate and the support plate can be suitably separated.

  In addition, in the laminated body 10, another layer may be further formed between the separation layer 4 and the support plate 2. In this case, the other layers may be made of a material that transmits light. This makes it possible to appropriately add a layer that imparts preferable properties and the like to the stacked body 10 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 forming the separation layer 4. Therefore, the material forming the other layers does 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 forming the separation layer 4.

  Further, the separation layer 4 is preferably formed only of a material having a light absorbing structure, but a material having no light absorbing structure within a range not impairing the essential characteristics of the present invention. May be added to form the separation layer 4.

  Further, it is preferable that the surface of the separation layer 4 facing the adhesive layer 3 is flat (no unevenness is formed), so that the separation layer 4 can be easily formed and even when attached. Can be pasted on.

The light irradiating the separation layer 4 may be a solid such as YAG laser, ruby laser, glass laser, YVO ₄ laser, LD laser, fiber laser, etc., 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 CO ₂ laser, an excimer laser, an Ar laser, a gas laser such as a He—Ne laser, a laser light such as a semiconductor laser or a free electron laser, or a non-laser light may be used as appropriate. The wavelength that can change the quality of the fired body is not limited to this, but for example, light having a wavelength in the range of 600 nm or less can be used.

<Method for manufacturing laminated body (second embodiment)>
A method for manufacturing a laminated body according to one embodiment (first embodiment) of the present invention will be described in detail with reference to FIG. As shown in FIG. 1, a method for manufacturing a 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 adhesion layer forming step of forming an adhesion layer 3 on a substrate 1. And a step of laminating the substrate 1 and the support plate 2 with the adhesive layer 3 and the separation layer 4 interposed therebetween. In addition, a separation step of separating the support plate 2 from the stack 10 is performed as another step on the stack 10 formed by the method for manufacturing a stack according to the embodiment.

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

  In the separation layer forming step, the diluting solvent is removed from the composition for forming the separation layer applied on the support plate 2 by placing it in a heating environment or a reduced pressure environment. Then, in the separation layer forming step, under an inert gas environment such as nitrogen gas or in an atmospheric environment, the polymerizable resin component contained in the composition for forming the separation layer is polymerized by a polymerization initiator by exposure or heating. By doing so, a cured product of the polymerizable resin component is formed. Then, the cured product of the polymerizable resin component is fired in the 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, the separation layer capable of absorbing light in the wavelength range of 600 nm or less can be preferably 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, the separation layer capable of absorbing light in the wavelength range of 600 nm or less can be preferably 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-mentioned adhesive is applied onto the substrate 1. Then, the adhesive layer 3 is formed by removing the diluting solvent from the adhesive by performing the baking stepwise while increasing the temperature.

[Lamination process]
The laminating step is a step of laminating the substrate 1, the adhesive layer 3, the separation layer 4, and the support plate 2 in this order. As a specific method of the laminating step, as shown in FIG. 1, the surface of the substrate 1 on which the adhesive layer 3 is formed and the surface of the support plate 2 on which the separation layer 4 is formed are bonded together, and a vacuum is formed. A method of laminating by baking under pressure and pressure bonding is mentioned.

  In the method for manufacturing a laminated body according to one embodiment, the order of each step is not particularly limited as long as the substrate, the adhesive layer, the separation layer, and the support are laminated in this order.

[Other steps]
The element can be mounted on the substrate 1 in the laminated body 10 manufactured in the laminating step by, for example, performing a thinning step and then performing an etching process, a lithographic process, and the like. The separation layer 4 has a high chemical resistance because it is composed of a fired body formed using the composition for forming a separation layer according to one embodiment. Therefore, it is possible to preferably prevent the separation layer 4 from being damaged by chemicals or the like in the etching process, the lithography process, and the like.

  Further, the laminated body 10 in which the elements are mounted on the substrate 1 is irradiated with light of a predetermined wavelength via the support plate 2 as shown in FIG. As a result, the separation layer 4 formed by the fired body can be appropriately transformed by absorbing the laser light, and thus the substrate 1 and the support plate 2 in the laminated body 10 can be successfully separated. .

<Laminate according to another embodiment (second embodiment)>
The laminate according to the present invention is not limited to the above embodiment. For example, the laminated body according to one embodiment (second embodiment) is a laminated body in which a substrate, an adhesive layer, a separation layer, and a support are laminated in this order, and the substrate is an element formed by a sealing material. Is a sealing substrate having a wiring layer (rewiring layer).

  For semiconductor packages, the terminals at the ends of bare chips are relocated in the chip area, and fan-in technology such as fan-in WLP (Fan-in Wafer Level Package) and terminals are relocated outside the chip area. Fan-out technology such as fan-out WLP (Fan-out Wafer Level Package) is known. In particular, the fan-out type technology is applied to a fan-out type PLP (Fan-out Panel Level Package) in which semiconductor elements are arranged on a panel for packaging, and integration, thinning and miniaturization of semiconductor devices, etc. In order to achieve the above, fan-out type technologies such as these have attracted attention. The laminated body according to one embodiment includes a separation layer having high chemical resistance to various chemicals for forming a wiring layer on a sealing substrate. Therefore, the laminated body in the fan-out type WLP and the fan-out type PLP is also within the scope of the present 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 has 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 called an RDL (Redistribution Layer) and is a thin film wiring body that constitutes a wiring connected to an element, and may have a single-layer or multi-layer structure. In one embodiment, the wiring layer includes a dielectric (eg, silicon oxide (SiOx), a photosensitive resin such as photosensitive epoxy, etc.) and a conductor (eg, aluminum, copper, titanium, nickel, gold, silver, etc.). The wiring may be formed of a metal or an alloy such as a silver-tin alloy), but is not limited thereto.

(element)
The device is a semiconductor device or other device and may have a single-layer or multi-layer structure. When the element is a semiconductor element, the electronic component obtained by dicing the sealing substrate becomes a semiconductor device.

(Sealing material)
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 may have a strength necessary to prevent damage or deformation of each component of the sealing substrate when forming the sealing substrate. In addition, the support is formed of a material that transmits light having a wavelength that can change the quality of the separation layer formed on the support. In addition, in the technical field of semiconductor devices, in order to further increase the integration density and improve production efficiency, in addition to increasing the size of the circular support plate 2, a large panel having a quadrangular shape in a top view is supported. It is being considered for use as a body. A method of manufacturing a semiconductor device by using such a large quadrangular panel as a support is known as a PLP (Panel level Package) technique and can be implemented by a fan-out type technique. In addition, in the PLP technology, a panel formed of a material such as glass or silicon can be preferably used as a panel used as a support.

<The manufacturing method of the laminated body which concerns on another embodiment (2nd embodiment)>
The method for manufacturing the laminated body according to the present invention is not limited to the method for manufacturing the laminated body according to the above-described embodiment (first embodiment), which is based on the so-called WLP (Wafer Level Package) technology as shown in FIG. 1. 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 sealed with the sealing substrate. A method for producing a laminate comprising a support for supporting a substrate, an adhesive layer, and a separation layer that is altered by irradiation with light, to form a laminate, wherein the support has a polymerizable resin component and , A composition for forming a separation layer containing a polymerization initiator is applied, and the polymerizable resin component is polymerized by heating or exposure, and the separation layer is formed by firing the polymerized polymerizable resin component. The structure includes a separation layer forming step of forming, an adhesion layer forming step of forming an adhesion layer on the separation layer, and a sealing substrate forming step of forming a sealing substrate on the adhesion layer. .

  The separation layer forming step is the same as the separation layer forming step in the method for manufacturing a laminated body according to the above-described embodiment, and thus the description thereof will be omitted. Further, the adhesive layer forming step is the same as that of the above-described embodiment except that the adhesive layer is formed on the separation layer formed on the support, and therefore the description thereof will be omitted.

[Sealing substrate forming process]
In the sealing substrate forming step, the wiring layer forming step, the mounting step, the sealing step, and the thinning step are performed in this order to form the 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, as a procedure for forming the wiring layer, first, a dielectric layer such as silicon oxide (SiOx) or a photosensitive resin is formed 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 with a conductor such as metal. As a method of forming the wiring, for example, a known semiconductor process method such as lithography processing such as photolithography (resist lithography), etching processing, or the like can be used.

  Thus, when performing the photolithography process, the etching process, 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, and the like are used as the resist solvent in addition to PGMEA. However, by forming the separation layer using the composition for forming a separation layer according to one embodiment, the separation layer has high chemical resistance. Therefore, it is possible to prevent the separation layer from being dissolved or peeled off by being exposed to the resist solvent as well as the acid and the alkali. Therefore, the wiring layer can be preferably formed on the support.

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

[Sealing process]
In the sealing step, the element is sealed with a sealing material. The sealing material is not particularly limited and, for reference, the sealing material is injection-molded using a molding die 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 including the wiring layer can be preferably formed on the adhesive layer.

  In the method for manufacturing a laminated body according to this embodiment, after the thinning step, processing such as bump formation on the encapsulant and formation of an insulating layer may be further performed.

[Method for manufacturing laminated body according to one modified example]
The method for manufacturing a laminate according to the present invention is not limited to the above embodiment. For example, in the method for manufacturing a laminated body according to a modification, in the sealing substrate forming step included in the method for manufacturing a laminated body according to the second embodiment, a mounting step, a sealing step, a thinning step, and a wiring The layer forming process is performed in this order. Also in this structure, the sealing substrate can be preferably formed on the separation layer having high chemical resistance.

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

<Evaluation of light transmittance and laser reactivity in the 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 a separation layer formed using each composition for forming a separation layer The transmittance was not evaluated. Next, the separation layer of the laminate prepared by using the composition for forming each separation layer was irradiated with a laser beam to evaluate the separability of the support in each laminate.

[Preparation of composition for forming separation layer]
First, in a mixed solvent of PGMEA and PGME (1: 1 (weight ratio)) so that the concentration of the polymerizable resin component JER157S70 (Novolak type epoxy resin, manufactured by Mitsubishi Chemical Corporation) was 30% by weight. The solution was prepared by diluting with. Then, under light-shielding conditions, 100 parts by weight of JER157S70 in the solution was mixed with 10 parts by weight of PAG290 to prepare a 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 at 150 ° C. for 180 seconds to be contained in the separation layer. The solvent that had formed 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 the atmospheric environment at 250 ° C. for 15 minutes. Further, the remaining one sheet was baked under the atmospheric environment at 400 ° C. for 15 minutes. As a result, two types of separation layers having different firing conditions were formed in Example 1. The separation layer of Example 1 had a thickness of 1.8 μm.

[Evaluation of transmittance]
Each of the separation layers of Example 1 having different firing conditions was irradiated with light having a wavelength of 380 to 780 nm by using a spectroscopic analysis measurement device UV-3600 (manufactured by Shimadzu Corporation), and 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]
The laser reactivity was evaluated by irradiating the separation layer fired at 400 ° C. with a laser beam having a wavelength of 532 nm under the conditions of a scanning speed of 6500 mm / sec, 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 traces of the laser light with which the separation layer was irradiated with a microscope VHX-600 (manufactured by Keyence). The criteria for the laser reactivity evaluation is that if the area occupied by the traces of laser light is 50% or more, it is evaluated as "A", and if it is less than 50%, it is evaluated as "B". If not, it was evaluated as "C". This simulatedly evaluated the separability of the support in the laminate.

[Examples 2 to 17]
By the same procedure as in Example 1, the separation layer forming compositions of 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 shown below. The compositions of the polymerizable resin component, the polymerization initiator and the surfactant in the adhesive compositions of Examples 1 to 17 are as shown in Tables 1 to 9 below.

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

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

An epoxy resin (EHPE3150CE, in which the polyfunctional alicyclic epoxy resin represented by the following formula (3) and the alicyclic epoxy resin represented by the formula (4) are mixed in a weight ratio of 50:50. (Manufactured by 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 Chemitex)

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

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

(Polymerization initiator)
-A cationic photopolymerization initiator represented by the following formula (9) (PAG290, manufactured by BASF)

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

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

[Evaluation of cationic photopolymerization initiator]
In the composition for forming a separation 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 transmittance of light having a wavelength of 532 nm was low and the laser reactivity was excellent regardless of which photocationic polymerization initiator was used. It was confirmed that the separated layer could be formed. In each of the separation layers of Examples 1 to 3, the separation layer fired at 400 ° C. had a lower transmittance of light having a wavelength of 532 nm and a laser reactivity higher than that of firing at 250 ° C. It showed a high tendency.

[Evaluation of thermal polymerization initiator]
In the compositions for forming a separation layer of Examples 4 to 6, the thermal polymerization initiator was evaluated. Further, 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. The evaluation results of Examples 4 to 7 are shown in Table 2 below.

  As shown in Table 2, the composition for separating layer formation of Examples 4 to 6, which is a composition in which the photoradical polymerization initiator in the compositions for forming separation layer of Examples 1 to 3 is changed to a thermal polymerization initiator. Also in the above, it was confirmed that the transmittance of light having a wavelength of 532 nm can be reduced and a separation layer having high laser reactivity can be formed. In addition, in the separation layer forming compositions of Examples 4 to 6, it was confirmed that by incorporating 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]
With respect to Examples 7 to 12, compositions for forming a separation layer containing different kinds of epoxy resins were evaluated. The evaluation results of Examples 7 to 12 are shown in Table 3 below.

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

[Evaluation of blending amount of thermal polymerization initiator]
With respect to the compositions for forming the separation layer of Examples 4 and 13 to 15, the light transmittance in the separation layer and the laser reactivity were evaluated by changing the blending amount of the thermal polymerization initiator TAG-2689. Table 4 below shows the evaluation results of the blending amount of the thermal polymerization initiator.

  As shown in Table 4, in the separation layer forming compositions of Example 4 and Examples 13 to 15, the lower the blending amount of TAG-2689 which is the thermal polymerization initiator, the higher the transmittance of light having a wavelength of 532 nm. Showed a tendency to become. Further, there was a tendency that the smaller the compounding amount of TAG-2689 was, the larger the distance between the traces of the laser light was. From these tendencies, it was confirmed that in the composition for forming a separation layer, the polymerization initiator is an important factor for forming a fired product having high laser reactivity.

[Evaluation of transmittance and laser reactivity according to the thickness of the separation layer]
As Examples 9-1 to 9-3, the composition for forming a separation layer of Example 9 was used to form a separation layer having a film thickness different from that of the separation layer of Example 9, and the transmission of light in each separation layer. The rate and the laser reactivity were evaluated. The evaluation results are shown in Table 5 below.

  As shown in Table 5, in 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 confirmed that even high laser reactivity could be obtained.

[Evaluation of laser reactivity due to change in laser light output]
With respect to the separation layers of Examples 4, 7, and 9-2, the laser reactivity was evaluated by changing the output of the irradiated laser light. 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 was 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 traces of the laser light formed in the separation layer, and between the traces. It was confirmed that the width of the was smaller. 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 laser light output and the irradiation pitch.

[Evaluation of firing temperature of separation layer]
The composition for forming a separation layer of Example 4 was used to form a separation layer by changing the firing temperature, and the laser reactivity in each separation layer was evaluated. The evaluation results are shown in Table 7 below.

  As shown in Table 7, in all of the separation layers of Examples 4 and 4-1, sufficient traces of laser light irradiation could be confirmed. However, when the separation layers of Examples 4 and 4-1 were compared, 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, regarding the temperature for firing the separation layer, considering the results of the transmittance of Reference Example 4-2 as well, it is possible to confirm that the temperature is preferably higher and is preferably higher than 300 ° C. did it.

[Evaluation of acrylic resin components]
In 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 of 532 in a separation layer formed using the composition for forming a separation layer was set. The light transmittance and laser reactivity were evaluated.

  The separation layer using the acrylic resin 1 of Example 17 in Table 8 below was prepared as follows. By adding 8 wt% of a PM solution of TAG-2689 so that the concentration of TAG-2689 is 5 wt% with respect to 100 wt% of the solid content of acrylic resin 1, the solid concentration of acrylic resin 1 is 26%. A base of the composition for forming a separation layer, which is 0.5% by weight, was prepared. Then, PF656 was added to the base in an amount of 0.05 parts by weight based on 100 parts by weight of the base to prepare a composition for forming a separation layer of Example 17.

The composition for forming a separation layer of Example 17 was applied to the same bare glass support as in Example 1 and 1000
The separation layer of Example 17 was formed by spin coating for 10 seconds under the condition of rpm and then baking the bare glass support at 400 ° C. for 15 minutes under atmospheric conditions. The laser irradiation conditions are the same as in Example 1. 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 compositions for forming a separation layer of Example 16 and Example 17. Further, it was confirmed that in the composition for forming a separation layer of Example 16, an organic peroxide can be used as a polymerization initiator. From this, in both cases of radical polymerization type and cationic polymerization type polymerizable resin components, by polymerizing with a polymerization initiator suitable for each polymerizable resin component and firing, high laser reactivity is obtained. It was confirmed that the separation layer could be formed.

[Evaluation of chemical resistance]
Separation layers having different firing temperatures were formed using the compositions for forming separation layers of Examples 4 and 11, and the chemical resistance of each separation layer was evaluated. As 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 the 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 Examples 4 and 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 forming temperature of 240 ° C. (thickness). 1 μm).

  The chemical resistance was visually evaluated, and when the separation layer formed on the glass support was not swollen and peeled off, it was evaluated as "A", and at least one of swollenness and peeling was recognized. It was evaluated as "C". Table 9 below shows the evaluation results of the chemical resistance of 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. Further, the separation layer formed using the composition for forming a separation layer of Examples 4 and 9 has higher chemical resistance than the separation layer of Comparative Example 1 regardless of the type of the stripping solution or the like. I was able to confirm that

  Further, the chemical resistance of the separation layer formed using the composition for forming a separation layer of Examples 1 to 3, 5 to 8 and 10 to 17 was evaluated under the same conditions as in Examples 4 and 9. 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 in comparison with the separation layer of Comparative Example 1 and have different types of stripping solutions. Therefore, it was confirmed that high chemical resistance could be obtained.

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

(Preparation of sample)
The composition for forming a separation layer of Example 4 was applied onto 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 under the same conditions as the fluorocarbon separation layer of Comparative Example 1 (thickness 1 μm). Then, TZNR (registered trademark) -A4012 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) was spin-coated on each of these separation layers, and baked at temperatures of 90 ° C., 160 ° C., and 220 ° C. for 4 minutes each. , And 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 by 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 strip having a width of 10 mm by a cutter. Then, while maintaining the angle (also referred to as peel angle) sandwiched between the adhesive layer and the substrate at 90 °, the belt-shaped adhesive layer is pulled vertically to the silicon substrate at a speed of 200 mm / sec. The adhesive layer was peeled off from the silicon substrate. The adhesive strength (g / cm, also called peel strength) at this time was used to evaluate the adhesiveness between the separation layer and the adhesive layer. When the adhesive strength is 20 g / cm or more, it is determined that the adhesive strength is sufficient. Further, after that, by irradiating with laser light under the same conditions as the above-mentioned [Evaluation of laser reactivity], after changing the quality of each separation layer, the adhesive strength is measured, and the adhesive strength before irradiating with laser light is measured. Compared with. The evaluation results are shown in Table 10 below.

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

  Further, the adhesiveness of the separation layer formed using the composition for forming a separation layer of Examples 1 to 3 and 5 to 17 was evaluated under the same conditions as in Example 4. 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, the polymerizable resin composition, and by using the composition for forming a separation layer containing a polymerization initiator, by forming the separation layer, laser reactivity, and chemical resistance It was confirmed that a high separation layer could be formed.

  INDUSTRIAL APPLICATION This invention can be utilized suitably in the manufacturing process of the miniaturized semiconductor device.

1 substrate 2 support plate (support)
3 Adhesive layer 4 Separation layer 10 Laminated body

Claims (11)

A substrate, and a support that transmits light, an adhesive layer, a laminate formed by laminating via a separation layer that is altered by irradiation of light,
The separation layer is a fired product in which at least a part of a cured product obtained by polymerizing a polymerizable resin component with a polymerization initiator is carbonized , and becomes brittle by absorbing light having a wavelength of 600 nm or less. And a laminate.   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 laminate described.   The laminate according to claim 1 or 2, wherein the polymerizable resin component is an epoxy resin.   The said superposition | polymerization initiator is a thermal-polymerization initiator or a photoinitiator, The laminated body in any one of Claims 1-3 characterized by the above-mentioned. A method for producing a laminate, comprising a substrate and a support that transmits light, an adhesive layer, and a separation layer that is altered by irradiation with light via a layer,
On one of the substrate and the support, a polymerizable resin component and a composition for forming a separation layer containing a polymerization initiator are applied, and the polymerizable resin component is polymerized by heating or exposure, A separation layer forming step of forming the separation layer by firing the polymerized polymerizable resin component in an atmospheric environment ,
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. A method for producing a laminate, which comprises:   The method for producing a laminate according to claim 5, wherein in the separation layer forming step, the polymerized polymerizable resin component is baked at 250 ° C or higher. A wiring layer on which an element is mounted, the element, and a sealing substrate including a sealing material that seals the element, an adhesive layer, and an optical layer on a support that supports the sealing substrate. A method for producing a laminated body, which is formed by laminating a separation layer that is altered by irradiation with
The support is coated with a composition for forming a separation layer containing a polymerizable resin component and a polymerization initiator, and the polymerizable resin component is polymerized by heating or exposure, and the polymerized polymerizable resin. A separation layer forming step of forming the separation layer by baking the components in an atmospheric environment ,
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.   The method for producing a laminate according to claim 7, wherein, in the separation layer forming step, the polymerized polymerizable resin component is fired at 250 ° C or higher.   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 method for manufacturing the laminate according to any one of 1.   The method for producing a laminate according to claim 5, wherein the polymerizable resin component is an epoxy resin.   The method for producing a laminate according to any one of claims 5 to 10, wherein the polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator.

Images