TW201807110A - Composition for forming release layer, laminate, and method for producing laminate - Google Patents

Abstract

The invention provides a composition for forming a release layer, a laminate, and a method for producing the laminate. Specifically, the invention provides a novel release layer forming composition which can successfully form a release layer by coating, and the release layer thus formed has high chemical resistance. The release layer forming composition is intended for forming a release layer in a laminate. The laminate is formed by laminating a substrate and a light-transmitting support body by means of an adhesive layer and the release layer which is modified by irradiating light. The release layer forming composition contains a polymeric resin component and a polymerization initiator.

Description

Composition for forming separation layer, laminate, and method for producing laminate

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, it is also necessary to use a thin semiconductor wafer for the incorporated semiconductor wafer. Therefore, although the thickness (film thickness) of a wafer substrate which is the basis of a semiconductor wafer is currently 125 μm to 150 μm, it is considered that it must be 25 μm to 50 μm in order to be applied to the next-generation wafer. Therefore, in order to obtain a wafer substrate having the above-mentioned film thickness, a step of thinning the wafer substrate is essential.

For wafer substrates, the strength is reduced due to thinning. Therefore, in order to prevent damage to the wafer substrate after thinning, during the manufacturing process, the wafer substrate is automatically conveyed while the support is attached to the wafer substrate. A structure such as a circuit is mounted on a wafer substrate. Then, after the manufacturing process, the wafer substrate is separated from the support. So, applied various Method to separate a wafer substrate from a support.

As a method of manufacturing a semiconductor wafer in which a support is attached to a semiconductor wafer, the semiconductor wafer is processed, and the support is separated, a method described in Patent Document 1 is known. In the method described in Patent Document 1, a light-transmitting support is bonded to a semiconductor wafer with a light-to-heat conversion layer and an adhesive layer provided on the support side interposed therebetween, the semiconductor wafer is processed, and then the support is passed through the support. Radiation energy is radiated from the side to decompose the light-to-heat conversion layer, and the semiconductor wafer is separated from the support.

[Prior technical literature] [Patent Literature]

[Patent Document 1] Japanese Laid-Open Patent Gazette "Japanese Patent Laid-Open No. 2004-64040 (published on February 26, 2004)"

However, in a laminate in which a substrate and a support are bonded to each other with a spacer adhesive layer and a separation layer, it is useful to form a novel separation layer with high chemical resistance in order to perform various processes on the substrate.

The inventors of the present application conducted intensive research, and as a result, found that a novel separation layer forming composition containing a polymerizable resin component and a polymerization initiator can smoothly form a separation layer with high chemical resistance, and completed the present application. Invention. That is, the present invention has been made in view of the problems described above, and an object thereof is to provide a novel composition for forming a separation layer capable of smoothly forming a separation layer with high chemical resistance through coating, and a composition therefor. Related technologies.

In order to solve the aforementioned problem, a composition for forming a separation layer according to the present invention is a composition for forming a separation layer for forming the above-mentioned separation layer in a laminate, the laminate system interposing an adhesive layer, and via irradiation. The light-modified separation layer is formed by laminating a substrate and a light-transmitting support, and is characterized by including a polymerizable resin component and a polymerization initiator.

In addition, in the laminated system of the present invention, a laminated body obtained by laminating a substrate and a light-transmitting support through a bonding layer and a separation layer modified by irradiation with light is characterized in that the separation layer is A fired body of a cured product obtained by polymerizing a polymerizable resin component via a polymerization initiator.

Moreover, in the manufacturing method of the laminated body of this invention, it is a manufacturing method of the laminated body which laminated | stacked the board | substrate and the light-transmitting support body through the adhesive layer and the separation layer modified by irradiation of light. It is characterized in that it includes a step of forming a separation layer, applying a composition for forming a separation layer containing a polymerizable resin component and a polymerization initiator on either of the substrate and the support, and heating or The polymerizable resin component is polymerized by exposure, and the polymerizable resin component after polymerization is fired to form the separation layer and a lamination step, the separation layer is formed with the separation layer and the adhesion layer interposed therebetween. The substrate or the support described above is laminated with the other of the substrate and the support not formed with the separation layer.

In addition, in the method for manufacturing a laminated body of the present invention, it is a manufacturing method of a laminated body in which a sealing substrate is laminated on a support that supports the sealing substrate through a bonding layer and a separation layer modified by irradiation with light. In the method, the sealing substrate includes a wiring layer on which the component is mounted, the component, and a sealing material that seals the component. The sealing substrate includes a step of forming a separation layer, and coating the support with a polymerizable resin component. A composition for forming a separation layer with a polymerization initiator, polymerizes the polymerizable resin component through heating or exposure, and fires the polymerized resin component after polymerization to form the separation layer and an adhesive layer. In the step, a bonding layer is formed on the separation layer and a sealing substrate is formed, and a sealing substrate is formed on the bonding layer.

According to the present invention, it is possible to provide a novel composition for forming a separation layer capable of smoothly forming a separation layer with high chemical resistance through coating, and a related technique.

1‧‧‧ substrate

2‧‧‧ support plate (support: plate)

3‧‧‧ Adjacent layer

4‧‧‧ separation layer

10‧‧‧ laminated

FIG. 1 is a diagram for explaining an outline of a method for manufacturing a laminated body according to an embodiment of the present invention.

[Best Mode for Implementing Invention] <Composition for forming a separation layer>

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

A composition for forming a separation layer according to an embodiment of the present invention is used to form the above-mentioned separation layer in a laminate. The laminate system interposes an adhesive layer and a separation layer modified by irradiation with light. A composition for forming a separation layer formed by laminating a light-transmitting support, the composition for forming a separation layer including a polymerizable resin component and a polymerization initiator. In addition, in order to adjust the coating workability, the composition for forming a separation layer may contain a diluent solvent and a surfactant.

The composition for forming a separation layer can be formed by firing a cured product obtained by polymerizing a polymerizable resin component through a polymerization initiator, and can be formed to have high chemical resistance and can be irradiated with light of a predetermined wavelength. Modified separation layer.

[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 at least one ethylenically unsaturated double bond and an epoxy group. Such a compound group is widely known in the art, and these compounds can be used in the composition for forming a separation layer according to an embodiment of the present invention without any particular limitation.

The polymerizable resin component having an epoxy group is not limited as long as it is a compound capable of cleaving an epoxy group and polymerizing each other by using a polymerization initiator. The polymerizable resin component having an epoxy group is not limited by its molecular weight, and an epoxy group may be introduced into at least one of a side chain and a terminal. Therefore, the polymerizable resin component having an epoxy group may be a resin that, for example, combines an epoxy group with an ethylenically unsaturated double bond It is a resin formed by copolymerizing a compound having no epoxy group but having an ethylenically unsaturated double bond and introducing an epoxy group into a side chain.

The polymerizable resin component having an ethylenically unsaturated double bond may be a low-molecular compound or a polymer such as a homopolymer or a copolymer resin as long as it has an ethylenically unsaturated double bond.

The molecular weight of the low-molecular compound having an ethylenically unsaturated double bond is preferably 2000 or less, more preferably 1500 or less, and the optimum molecular weight is 900 or less. The so-called low-molecular compound in the present invention is a compound having a certain molecular weight (compound having substantially no molecular weight distribution) having a molecular weight of 2,000 or less (more preferably 1500 or less, and more preferably 900 or less), rather than polymerization through use An initiator is a so-called polymer or oligomer obtained by breaking unsaturated bonds and chain-expanding chemical bonds. The molecular weight of the low-molecular compound is usually 100 or more.

Examples of low-molecular compounds having ethylenically unsaturated double bonds include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, butenoic acid, methacrylic acid, and maleic acid) Examples of the esters with unsaturated carboxylic acids, and amidines of unsaturated carboxylic acids, and the like include esters of unsaturated carboxylic acids and aliphatic polyol compounds, and amidines of unsaturated carboxylic acids and aliphatic polyamine compounds. Amines.

In addition, the low-molecular compound having an ethylenically unsaturated double bond may be, for example, a compound in which an unsaturated carboxylic acid ester or amidoamine having a nucleophilic substituent such as a hydroxyl group, an amino group, or a mercapto group is added to a monofunctional group. Or polyfunctional isocyanate or epoxy. In addition, a low-molecular compound having an ethylenically unsaturated double bond can also be suitably used. Substituted reaction products of unsaturated carboxylic acid esters or amidoamines with detachable substituents such as halogen groups or fluorenyl groups, and monofunctional or polyfunctional alcohols, amines, and thiols.

The copolymer resin having an ethylenically unsaturated double bond may be, for example, a resin having an isocyanate group or an epoxy group and an ethylenically unsaturated double bond with a compound having a hydroxyl group, an amine group, An unsaturated carboxylic acid ester having a functional group such as a mercapto group or an ammonium-based copolymer reacts with the functional group to introduce a resin formed by an ethylenically unsaturated double bond. The copolymer resin having an ethylenically unsaturated double bond may be, for example, a resin including a compound having a carboxylic acid and an ethylenically unsaturated double bond, and an unsaturated carboxylic acid having a functional group such as a hydroxyl group, an amino group, or a mercapto group. A resin formed by the condensation of an acid ester or an amidine copolymer.

In addition, the polymerizable resin component may be, for example, a component having a siloxane skeleton and having an epoxy group and an ethylenically unsaturated double bond in at least one of a terminal and a side chain of the siloxane skeleton. At least one of the silicones containing a crosslinkable group.

The polymerizable resin component may be used in combination of two or more.

[1. Polymerizable resin component having epoxy group]

The polymerizable resin component having an epoxy group may be a resin component having an epoxy group sufficient in one molecule to be cured by heating or exposure. Among them, the polymerizable resin component having an epoxy group preferably contains at least one resin selected from the group consisting of an epoxy resin and an acrylic resin (Aac) having an epoxy group. Here, with respect to the epoxy resin, Language, for example, preferably selected from Novolacs epoxy resin (Anv), bisphenol epoxy resin (Abp), and at least one epoxy resin in the group formed by alicyclic epoxy resin. These polymerizable resin components having an epoxy group can be used alone or in combination of two or more. Specific examples of more preferable epoxy resins among these resins are shown below.

(1) Novolacs epoxy resin (Anv)

As the Novolacs 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 the 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 methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl Examples of the cyclic alkyl group include a cyclobutyl group and a cyclopentyl group. Among them, R ^a11 and R ^{a12 are} preferably a hydrogen atom or a methyl group.

In the formula (anv0), R ^EP is an epoxy group-containing group. The ^EP group that is an epoxy group-containing group is not particularly limited, and examples thereof include a group formed of only an epoxy group; a group formed of only an alicyclic epoxy group; and an epoxy group or an alicyclic epoxy Base, a base linked to a divalent radical. The alicyclic epoxy group means an alicyclic group having an oxeane structure as a 3-membered cyclic ether, and specifically, a group having an alicyclic group and an oxeane structure. The alicyclic group as a basic skeleton of an alicyclic epoxy group may be a monocyclic ring or a polycyclic ring. Examples of the monocyclic alicyclic group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Examples of the polycyclic alicyclic group include norbornyl, isobornyl, tricyclononyl, tricyclodecyl, and tetracyclododecyl. In addition, the hydrogen atom of these alicyclic groups may be substituted with an alkyl group, an alkoxy group, a hydroxyl group, or the like. In the case of a group having an epoxy group or an alicyclic epoxy group and a divalent linking group, it is preferable to bond through a divalent linking group bonded to an oxygen atom (-O-) in the formula. Epoxy or alicyclic epoxy. Here, the divalent linking group is not particularly limited, and suitable examples include a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, and the like.

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 it is usually preferably saturated. Specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, or a fat containing a ring in the structure. Group hydrocarbon groups and the like.

The carbon number of the linear aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. The linear aliphatic hydrocarbon group is preferably a linear alkylene group. Specific examples include a methylene group [-CH _2- ], an ethylene group [-(CH ₂ ) _2- ], and a trimethylene group. Methyl [-(CH ₂ ) _3- ], tetramethylene [-(CH ₂ ) _4- ], pentamethylene [-(CH ₂ ) _5- ], and the like.

The carbon number of the branched aliphatic hydrocarbon group is preferably 2 to 10, more preferably 2 to 6, still more preferably 2 to 4, and most preferably 2 or 3. The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specific examples include -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -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 -and other alkyl methylene groups; -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 -isoalkylethylene; -CH (CH ₃ ) CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ -isoalkyltrimethylene; -CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- , alkyl alkylene such as alkyl tetramethylene, and the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

Examples of the aliphatic hydrocarbon group containing a ring in the structure include an alicyclic hydrocarbon group (a group obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group bonded to a linear or branched chain. The group obtained by the terminal of an aliphatic hydrocarbon group, the group which an alicyclic hydrocarbon group exists in the chain of a linear or branched aliphatic hydrocarbon group, etc. Examples of the linear or branched aliphatic hydrocarbon group include the same groups as described above. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. The alicyclic hydrocarbon group may be polycyclic The group may be a monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As the monocycloalkane, a carbon number of 3 to 6 is preferred, and specific examples thereof include cyclopentane and cyclohexane.

The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane preferably has 7 to 12 carbon atoms. Specific 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 a monocyclic or polycyclic ring. The number of carbon atoms of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring.

Specific examples of the aromatic hydrocarbon group include a group (arylene group or heteroarylene group) obtained by removing two hydrogen atoms from the aromatic hydrocarbon ring or aromatic heterocyclic ring; A group obtained by removing two hydrogen atoms from a ring aromatic compound (such as biphenyl, fluorene, etc.); and a group (aryl or hetero group) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring. An aryl group in which one hydrogen atom is substituted with an alkylene group (for example, benzyl, phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2 -Naphthylethyl and other arylalkyl groups further removed from the aryl group 1 Hydrogen atom). The number of carbon atoms of the alkylene group bonded to the aforementioned aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

The divalent hydrocarbon group may have a substituent. The linear or branched aliphatic hydrocarbon group of the divalent hydrocarbon group may or may not have a substituent. Examples of the substituent include a fluorine atom, a fluoroalkyl 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 including a ring in the structure as the 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, most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. The alkoxy group as the aforementioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, or a tert-butoxy group. Best methoxy, ethoxy. Examples of the halogen atom of the substituent include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. A fluorine atom is more preferred. Examples of the halogenated alkyl group of the substituent include a group in which part or all of the hydrogen atoms of the alkyl group are substituted by the halogen atom. In the alicyclic hydrocarbon group, a part of the carbon atoms constituting the ring structure may be substituted with a substituent containing a hetero atom. As the hetero atom-containing substituent, -O-, -C (= O) -O-, -S-, -S (= O) _2- , and -S (= O) ₂ -O- are preferred.

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

About divalent linking groups containing heteroatoms:

The hetero atom in the divalent linking group containing a hetero atom means 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. Among divalent linking groups containing a hetero atom, as the preferred examples of the linking group, -O-, -C (= O) -O-, -C (= O)-, -OC (= O ) -O-; -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-(H can be alkyl, fluorenyl, etc. substituents); -. S -, - S (= O) 2 -, - S (= O) 2 -O-, the general formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 -C (= O) -O-, -C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] _{m ”} -Y ²² -or -Y ²¹ -OC (= O) A group represented by -Y ^22- [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m ”is an integer of 0 to 3. ]Wait. When the aforementioned divalent linking group containing a hetero atom is -C (= O) -NH-, -NH-, -NH-C (= O) -O-, -NH-C (= NH)-, where H may be substituted by a substituent such as an alkyl group or a fluorenyl group. The number of carbon atoms of the substituent (alkyl group, fluorenyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. -Y ²¹ -OY ^22- , -Y ²¹ -O-, -Y ²¹ -C (= O) -O-, -C (= O) -OY ²¹ -,-(Y ²¹ -C (= O) Y ²¹ and Y ^{22 in} -O] _{m "} -Y ²² -or -Y ²¹ -OC (= O) -Y ²² -are each independently a divalent hydrocarbon group which may have a substituent. As the divalent hydrocarbon group, The same group as the "divalent hydrocarbon group which may have a substituent" mentioned in the description of the said divalent linking group is mentioned. Y ^{21 is} preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, still more preferably a linear alkylene group having 1 to 5 carbon atoms, and particularly preferably a methylene group. Or ethylene. Y ^{22 is} preferably a linear or branched aliphatic hydrocarbon group, and more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and most preferably a methyl group. base. In the base represented by the formula-[Y ²¹ -C (= O) -O] _{m "} -Y ^22- , m" is an integer of 0 to 3, preferably an integer of 0 to 2, and more preferably 0 or 1 , Particularly preferably 1. That is, the group represented by the formula-[Y ²¹ -C (= O) -O] _{m "} -Y ²² -is particularly preferably the group represented by the formula -Y ²¹ -C (= O) -OY ^22- . Among them, It is preferably a group represented by the formula-(CH ₂ ) _{a '} -C (= O) -O- (CH ₂ ) _b'- . In the formula, a 'is an integer of 1 to 10, and preferably 1 to 8 Is an integer of 1 to 5, more preferably 1 or 2, and most preferably 1. b 'is an integer of 1 to 10, preferably an integer of 1 to 8, and more preferably 1 to 5 The integer is more preferably 1 or 2, and most preferably 1. Among them, R ^EP is a group containing an epoxy group, and preferably a glycidyl group.

As the Novolacs epoxy resin (Anv), a resin containing a structural unit represented by the following general formula (anv1) can be suitably 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 the formula (anv1), the alkyl groups having 1 to 5 carbon atoms of R ^a22 and R ^a23 are the same as the alkyl groups having 1 to 5 carbon atoms of R ^a11 and R ^a12 in the aforementioned formula (anv0). The halogen atom of R ^a22 and R ^a23 is preferably a chlorine atom or a bromine atom. In the formula (anv1), R ^EP and in the formula (anv0) R ^EP Likewise, preferably a glycidyl group.

Specific examples of the constituent units represented by the aforementioned formula (anv1) are shown below.

The Novolacs epoxy resin (Anv) may be a resin made of only the aforementioned structural unit (anv1), and a resin having a structural unit (anv1) and other structural units is preferred. As another structural unit, the structural unit represented by the following general formula (anv2)-(anv3), respectively is mentioned.

(In the formula, R ^a24 is a hydrocarbon group which may have a substituent. 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. R ^a27 is a group containing An epoxy group or a hydrocarbon group which may have a substituent.)

In the formula (anv2), R ^a24 is a hydrocarbon group which may have a substituent. Examples of the hydrocarbon group which may have a substituent include a linear or branched alkyl group and a cyclic hydrocarbon group. The carbon number of the linear alkyl group is preferably 1 to 5, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl or n-butyl is preferred, and methyl or ethyl is more preferred.

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

When R ^a24 is a cyclic hydrocarbon group, the hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and may be a polycyclic group or a monocyclic group. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a monocyclic alkane is preferred. The monocycloalkane is preferably an alkane having 3 to 6 carbon atoms, and specific examples thereof include cyclopentane and cyclohexane. As the polycyclic group aliphatic hydrocarbon group, a group obtained by removing one hydrogen atom from a polycyclic alkane is preferable, and as the polycyclic alkane, an alkane having 7 to 12 carbon atoms is preferable, and specifically, an example Adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like are produced.

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 a monocyclic or polycyclic ring. The carbon number of the aromatic ring is preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of the aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocyclic rings in which a part of carbon atoms constituting the aromatic hydrocarbon ring is substituted with a hetero atom. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. Specific examples of the aromatic heterocyclic ring include a pyridine ring and a thiophene ring. Specific examples of the aromatic hydrocarbon group in R ^a24 include a group (aryl or heteroaryl) obtained by removing one hydrogen atom from the aromatic hydrocarbon ring or aromatic heterocyclic ring; A group obtained by removing one hydrogen atom from an aromatic compound (e.g., biphenyl, fluorene, etc.) of the above aromatic ring; a group in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocyclic ring is substituted with an alkylene group (e.g., , Benzyl, phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, arylalkyl such as 1-naphthylethyl, 2-naphthylethyl, etc.) and the like. The number of carbon atoms of the alkylene group bonded to the aromatic hydrocarbon ring or the aromatic heterocyclic ring is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

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

In the formula (anv3), R ^a27 is a group containing an epoxy group or an optionally substituted hydrocarbon group. As the group of the above formula (anv0) of the epoxy group-containing R ^EP of the same R ^a27, R ^a27 may be the same as the hydrocarbon group having a substituent group and R ^a24.

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

Moreover, as another structural unit which can replace the structural unit represented by the said general formula (anv1), a polycycloalkane structural unit is mentioned besides the structural unit represented by said formula (anv2)-(anv3). As such a polycycloalkane constituent unit, a constituent unit having 7 to 12 carbon atoms is preferred. Specific examples include an adamantane constituent unit, a norbornane constituent unit, an isobornane constituent unit, and tricyclodecane. Constituent units, tetracyclododecane constituent units, and the like.

Novolacs epoxy resin (Anv) When (anv1) has other constituent units, the proportion of each constituent unit in the resin (Anv) is not particularly limited, and it is a constituent unit having an epoxy group with respect to the total of all constituent units constituting the resin (Anv). The total is preferably 10 to 90 mole%, more preferably 20 to 80 mole%, and still more preferably 30 to 70 mole%.

Examples of commercially available Novolacs epoxy resins (Anv) include JER-152, JER-154, JER-157S70, JER-157S65, (above, manufactured by Mitsubishi Chemical Corporation), EPICLONN-740, EPICLONN-740, EPICLONN-770, EPICLONN-775, EPICLONN-660, EPICLONN-665, EPICLONN-670, EPICLONN-673, EPICLONN-680, EPICLONN-690, EPICLONN-695, EPICLONHP5000, EPICLONHP7200 (above, DIC (shares) System), EOCN-1020 (above, Nippon Kayaku Co., Ltd.) and so on.

(2) Bisphenol 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 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and na ³¹ is an integer of 1 to 50.)

In the formula (abp1), the alkyl groups having 1 to 5 carbons of R ^a31 and R ^a32 are the same as the alkyl groups having 1 to 5 carbons as R ^a11 and R ^a12 in the aforementioned formula (anv0). Among them, R ^a31 and R ^{a32 are} preferably a hydrogen atom or a methyl group. R ^EP in the aforementioned formula (anv0) R ^EP Similarly, preferred glycidyl group.

Examples of the bisphenol epoxy resin (Abp) include JER-827, JER-828, JER-834, JER-1001, JER-1002, JER-1003, JER-1055, JER-1007, and JER- 1009, JER-1010 (above, manufactured by Mitsubishi Chemical Corporation), EPICLON860, EPICLON1050, EPICLON1051, EPICLON1055 (above, manufactured by DIC), etc .; as the bisphenol F-type epoxy resin, JER-806, JER-807, JER-4004, JER-4005, JER-4007, JER-4010 (above, manufactured by Mitsubishi Chemical (stock)), EPICLON830, EPICLON835 (above, manufactured by DIC (stock)), LCE-21, RE-602S (Above, made by Nippon Kayaku Co., Ltd.) and so on.

(3) Alicyclic epoxy resin (A1)

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

(Wherein R ¹ and R ² each independently represent 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 Each independently represents a single bond or a divalent linking group.)

In formula (A1), R ¹ and R ² each independently represent 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. In this embodiment, the "organic group which may have an alicyclic epoxy group" includes a group containing only an alicyclic epoxy group (organic group) in addition to a combination of an alicyclic epoxy group and an organic group. group).

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

The organic groups of R ¹ and R ² may have an alicyclic epoxy group, and at least one of R ¹ and R ² may have an alicyclic epoxy group. The organic groups which may have an alicyclic epoxy group as R ¹ and R ² may be the same or different, respectively. As R ¹ and R ² , an organic group in which both of them have an alicyclic epoxy group is preferable, a group in which both of them are formed of an alicyclic epoxy group, and both of them are particularly preferably 1, 2-epoxycyclohexyl.

In the formula (A1), Y ¹ and Y ² each independently represent 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 or an aromatic hydrocarbon group containing a ring in the structure. The aliphatic hydrocarbon group or the aromatic hydrocarbon group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and a carbonyl group. In addition, in the aliphatic hydrocarbon group or the aromatic hydrocarbon group, a part of the carbon atoms and hydrogen atoms constituting the structure may be substituted with a substituent containing a hetero atom. Examples of the hetero atom-containing substituent 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 substituents such as alkyl and fluorenyl.); -S-, -S _{(= O) 2 -, -} S (= O) 2 -O-, the general formula ^{-Y 21 -OY 22 -, - Y} 21 -O -, - Y 21 -C (= O) -O -, - C (= O) -OY ²¹ -,-[Y ²¹ -C (= O) -O] _{m "} -Y ²² -or -Y ²¹ -OC (= O) -Y ²² -Representation [wherein Y ²¹ and Y ²² are each independently a divalent hydrocarbon group which may have a substituent, and are preferably a linear or branched alkylene group. O in the formula is an oxygen atom, and m ”is an integer of 0 to 3. ]Wait.

Y ¹ and Y ² may be the same or different, respectively. When Y ¹ and Y ² are a divalent linking group, the divalent linking group is preferably a linear, branched, or aliphatic hydrocarbon group containing a ring in the structure, and more preferably, it may have The linear or branched aliphatic hydrocarbon group having a substituent is more preferably a linear or branched alkylene group which may have a substituent. The carbon number of the aliphatic hydrocarbon group and the alkylene group is preferably 1 to 30, more preferably 1 to 10, and even more preferably 1 to 3. As Y ¹ and Y ² , a single bond, methylene, ethylene, or propylene is preferred, and a single bond or methylene is more preferred. Particularly, Y ¹ is a single bond and Y ² is methylene. .

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

(Wherein R ¹ and R ² are the same as above, Y ⁰² is a single bond or a divalent linking group, n ¹ and n ⁴ are each independently an integer of 0 to 3, n ² is an integer of 0 to 10, and n ³ 0 or 1).

In the formulae (A1-1) to (A1-2), R ¹ and R ² are the same as above, preferably an organic group having an alicyclic epoxy group in both, and more preferably an alicyclic ring in both of them Oxygen. In the formulae (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 those of Y ¹ and Y ² . Among these, a single bond or a linear or branched chain having a substituent or an aliphatic hydrocarbon group containing a ring in the structure is preferred. In the formulae (A1-1) to (A1-2), n ¹ and n ⁴ are each independently an integer of 0 to 3, and preferably 0 or 1. In the formulae (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 the formulae (A1-1) to (A1-2), n ³ is 0 or 1, and preferably 0.

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

Examples of commercially available products of the alicyclic epoxy compound include Celloxide 2021, 2021P, 2081, 2083, and 2085 (manufactured by Daicel Chemical Industry Co., Ltd.), and the like are preferable examples.

(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. A polyfunctional alicyclic epoxy resin (A2) is a compound which does not belong to the said (A1) component. The component (A2) may be a low-molecular compound or a polymer compound, and a polymer compound is preferred. (A2) The component is a polyfunctional epoxy compound with more than a bifunctionality, Preferably it is a trifunctional or more functional epoxy compound. As the component (A2), a compound represented by the following formula (A2-1) is preferable in terms of excellent chemical resistance and light resistance.

(In the formula, R ¹¹ is a residue obtained by removing an active hydrogen group from an organic compound having q active hydrogen groups. N ¹¹ , n ¹² , ..., and n ^q each independently represent an integer from 0 to 100, sum represents an integer of 1 ~ 100.q .A 1 ~ 100 having a substituent R ¹² oxycyclohexane skeleton or a substituent R ¹² is oxo norbornene skeleton, and represented by the following formula (a1 ) Or (a2)).

(In the formula, R ^{12 is} each independently a group represented by the following formulae (a11) to (a13), and the compound represented by the formula (A2-1) contains one or more groups represented by (a11). Formula (a1) The bond represented by (a2) in the wavy line is bonded to R ¹¹ in the compound represented by formula (A2-1), and the bond marked with * is in the compound represented by formula (A2-1) Hydrogen atom (H) in the bond).

(R ¹³ represents an alkyl group, an alkyl carbonyl group, or an aryl carbonyl group. The group represented by the formulae (a11) to (a13) is bonded to the wavy line with the group represented by the formulae (a1) and (a2). Bond).

In the aforementioned formula (A2-1), R ¹¹ is a residue obtained by removing an active hydrogen group from an organic compound having an active hydrogen group. The "organic compound having an active hydrogen group" as a precursor thereof may be exemplified. Produce alcohols, phenols, carboxylic acids, amines, thiols and so on.

The alcohol may be a monohydric alcohol or a polyhydric alcohol. Specific examples include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, and octanol; aromatic alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, and triethyl alcohol. Glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, neopentyl glycol, hydroxypivalic acid Polyols such as neopentyl glycol ester, cyclohexanedimethanol, glycerol, diglycerin, polyglycerol, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, and the like. Examples of the phenols include phenol, cresol, catechol, pyrogallol, hydroquinone, hydroquinone monomethyl ether, bisphenol A, bisphenol F, and 4,4'-dihydroxydibenzoyl Ketone, bisphenol S, phenolic resin, cresol Novolacs resin, etc. 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, and pyromellitic acid. Polyacrylic Phthalic acid, isophthalic acid, terephthalic acid, etc. In addition, compounds having both a hydroxyl group and a carboxyl group, such as lactic acid, citric acid, and hydroxyhexanoic acid, can also be mentioned. Examples of the amines include monomethylamine, dimethylamine, monoethylamine, diethylamine, propylamine, monobutylamine, dibutylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, and dodecane Methylamine, 4,4'-diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethylenediamine, xylylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine Wait. Examples of the thiols include thiols such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and benzene mercaptan; ethylene glycol dimercaptopropionate, trimethylolpropane trimercaptopropionate, Pentaerythritol tetramercaptopropionate and the like, mercaptopropionic acid or a polyol ester of mercaptopropionic acid; etc.

In addition, as the organic compound having an active hydrogen group, polyvinyl alcohol, polyvinyl acetate partial hydrolysate, 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, poly Propylene polyol, poly 1,4-butanediol, etc.

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-cyclohexene methanol, and tetrahydrophthalic acid. The above-mentioned organic compounds having an active hydrogen group may be used alone or in combination of two or more kinds.

In the aforementioned formula (A2-1), n ¹¹ , n ¹² ,. ． ． And n ^q each independently represent an integer from 0 to 100, and the total is 1 to 100. In addition, q represents an integer from 1 to 100. Among them, n ¹¹ , n ^12,. ． ． And n ^q are each independently preferably an integer of 2 to 10, more preferably an integer of 3 to 6. In addition, n ¹¹ , n ^12,. ． ． The sum of N and ^Q is preferably 4 to 30, and more preferably 4 to 20. When the sum is 4 or more, the crosslinking density after curing can be increased, and the hardness can be increased. In addition, by setting the sum to 30 or less, solubility in a solvent can be improved, and operability can be improved.

In the formula (A2-1), A represents a substituent having a group of R ¹² oxycyclohexane skeleton or a substituent R ¹² is oxo norbornene skeleton, and in the formula (a1) or (a2). A is preferably represented by the aforementioned formula (a1). The q As may be the same or different.

The epoxy compound represented by the aforementioned formula (A2-1) must contain one or more groups represented by the aforementioned formula (a11), and the more it is, the more preferable it is. On the other hand, the smaller the number of groups represented by the aforementioned formula (a13), the more preferable it is.

The epoxy compound represented by the aforementioned formula (A2-1) can be produced by using 4-vinylcyclohexane as an initiator using an organic compound having an active hydrogen group as described in Japanese Patent Publication No. 7-119270. Ring-opening polymerization of a mixture of ene-1-oxide or 5-vinylbicyclo [2.2.1] hept-2-ene-2-oxide and a compound having one epoxy group, That is, a polyether resin having a vinyl side chain and a cyclohexane skeleton, or a vinyl side chain and a norbornene skeleton is epoxidized with peroxyacetic acid, hydrogen peroxide, or the like. As a commercially available product, EHPE3150 (the average of n ¹¹ to n ^q is 15) manufactured by Daicel Chemical Industry Co., Ltd. can be cited as a preferable example.

In addition, a composition for forming a separation layer is prepared by using an alicyclic epoxy resin (A1) and a polyfunctional alicyclic epoxy resin (A2) in combination. At the time, the blending ratio of the (A1) component and the (A2) component is (A1) / (A2) = 70/30 ~ 51/49 (mass ratio), and more preferably 70/30 ~ 60/40 (mass ratio) . By setting the blending ratio as described above, the melt viscosity of the obtained composition for forming a separation layer can be in a preferable range described later. Thereby, the composition for forming a separation layer can be applied so that a film thickness may become uniform. In addition, a separation layer having high chemical resistance can be formed. As a commercially available epoxy resin in which an alicyclic epoxy resin (A1) and a polyfunctional alicyclic epoxy resin (A2) are used in combination, for example, EHPE3150CE manufactured by Daicel Chemical Industry Co., Ltd. is mentioned as a preferable example.

(5) Acrylic resin (Aac) with epoxy group

As the polymerizable resin component having an epoxy group, for example, an acrylic resin having an epoxy group obtained by copolymerizing at least an unsaturated carboxylic acid and a compound having an epoxy group and an ethylenically unsaturated double bond can be used. (Aac).

Examples of unsaturated carboxylic acids include monocarboxylic acids such as (meth) acrylic acid and butenoic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; and the like Anhydrides of dicarboxylic acids; etc. Among these, (meth) acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and ease of obtaining. These unsaturated carboxylic acids may be used alone or in combination of two or more.

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

In addition, in this specification, "a compound which has an ethylenically unsaturated double bond" is called "unsaturated compound."

In acrylic resins with epoxy groups, derived from unsaturated carboxylic acid The proportion of the structural unit (structural unit having a carboxyl group) of the acid 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 butenoic acid; dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, and itaconic acid; Anhydrides of carboxylic acids; etc. Among these, (meth) acrylic acid and maleic anhydride are preferred from the viewpoints of copolymerization reactivity, alkali solubility of the obtained resin, and ease of obtaining. These unsaturated carboxylic acids may be used alone or in combination of two or more.

The compound having an epoxy group and an ethylenically unsaturated double bond may be a compound having no alicyclic epoxy group, or a compound having an alicyclic epoxy group, and more preferably a compound having an alicyclic epoxy group. .

Examples of the compound having an epoxy group other than an alicyclic epoxy group and an ethylenically unsaturated double bond include glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, ( (Methyl) 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, etc. Epoxy alkyl acrylates; α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, α-ethyl acrylate 6,7-epoxy Α-alkyl acrylate alkylene oxides such as heptyl esters; glycidyl ethers of o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether; etc. . Among these, from the viewpoints of copolymerization reactivity and strength of the cured resin, glycidyl (meth) acrylate, 2-methyl glycidyl (meth) acrylate, and (meth) are preferred. 6,7-epoxyheptyl acrylate, o-vinyl benzyl glycidyl ether, m-vinyl Benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether.

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

Specifically, as a compound which has an epoxy group which is an alicyclic epoxy group, and an ethylenically unsaturated double bond, the compound represented by following formula (a4-1)-(a4-16) is mentioned, for example. Among them, in order to make the composition for forming a separation layer have a moderate curability, compounds represented by the following formulae (a4-1) to (a4-6) are preferable, and the following formulae (a4-1) to (a4-4) are more preferable. Represented compounds.

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, R ^a5 represents a divalent hydrocarbon group having 1 to 10 carbon atoms, and n represents 0 to 10 Integer. R ^{a4 is} preferably a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, and hexamethylene. methyl. As R ^a5 , for example, methylene, ethylene, propylene, tetramethylene, ethylethylene, pentamethylene, hexamethylene, phenylene, cyclohexylene,- CH ₂ -Ph-CH _2- (Ph stands for phenylene).

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

In the epoxy resin having an epoxy group, a structural unit derived from an unsaturated compound having an epoxy group (a structural unit having an epoxy group) is used. The proportion is preferably 5 to 90% by mass, more preferably 15 to 85% by mass, and particularly preferably 50 to 85% by mass. By being in the aforementioned range, the acrylic resin having an epoxy group can be appropriately cured.

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

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

Specifically, as a compound which has an alicyclic group and an ethylenically unsaturated double bond, the compound represented by following formula (a5-1)-(a5-8) is mentioned, for example. Among them, in order to make the composition for forming a separation layer have a moderate curability, compounds represented by the following formulae (a5-3) to (a5-8) are preferable, and the following formulae (a5-3) and (a5- 4) A compound represented by [].

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 an alkyl group having 1 to 5 carbon atoms. R ^{a7 is} preferably a single bond, a linear or branched alkylene group, such as methylene, ethylene, propylene, tetramethylene, ethylethylene, and pentamethylene , Hexamethylene. R ^{a8 is} preferably, for example, a methyl group or an ethyl group.

The proportion of the constituent units 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 more preferably 5 to 30% by mass.

The acrylic resin having an epoxy group may be obtained by further copolymerizing a compound other than the foregoing. Examples of such other compounds include (meth) acrylates, (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) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, and tertiary (meth) acrylate Linear or branched alkyl (meth) acrylates such as octyl esters; chloroethyl (meth) acrylate, 2,2-dimethylhydroxypropyl (meth) acrylate, (formyl) 2-hydroxyethyl acrylate, trimethylolpropane mono (meth) acrylate, benzyl (meth) acrylate, furfuryl (meth) acrylate, and the like.

Examples of (meth) acrylamide include (meth) acrylamide, N-alkyl (meth) acrylamide, N-aryl (meth) acrylamide, N, N-diamine Alkyl (meth) acrylamide, N, N-aryl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl-N-formyl (Meth) acrylamide and the like.

Examples of the allyl compound include allyl acetate, Allyl hexanoate, allyl octanoate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, Allyl esters such as allyl lactate; allyloxyethanol; etc.

Examples of vinyl ethers include hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, and ethoxyethyl vinyl ether , Chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethylbutyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether , Alkyl vinyl ethers such as dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether; Vinyl aryl ethers such as vinyl phenyl ether, vinyl tolyl ether, vinyl chlorophenyl ether, vinyl-2,4-dichlorophenyl ether, vinyl naphthyl ether, and vinyl anthryl ether; Wait.

Examples of the vinyl esters include vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valerate, vinyl hexanoate, Vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxyacetate, vinyl butoxyacetate, vinylphenylacetate, vinylacetacetate, vinyl lactate, Vinyl-β-phenylbutyrate, vinyl benzoate, vinyl salicylate, vinyl chlorobenzoate, vinyl tetrachlorobenzoate, vinyl naphthalate and the like.

Examples of the styrenes include styrene; methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, and diethyl Styrene, isopropylstyrene, butylstyrene, hexylstyrene, cyclohexylstyrene, decylstyrene, benzylstyrene, chloromethylstyrene, trifluoromethylstyrene, ethoxymethyl Alkylstyrenes such as methylstyrene, ethoxymethylstyrene; alkoxystyrenes such as methoxystyrene, 4-methoxy-3-methylstyrene, and dimethoxystyrene; Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo- Halostyrene such as 4-trifluoromethylstyrene, 4-fluoro-3-trifluoromethylstyrene; etc.

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 ethylenically unsaturated double bonds]

The polymerizable resin component having an ethylenically unsaturated double bond may be a low-molecular compound, a homopolymer, or a copolymer as long as it has an ethylenically unsaturated double bond sufficient to be cured by heating or exposure in one molecule. Polymer and other polymers. Among these, specific examples of the more polymerizable resin component having an ethylenically unsaturated double bond are shown below.

(1) Low molecular compounds with ethylenically unsaturated double bonds

For a low-molecular compound having an ethylenically unsaturated double bond, typically, a polyfunctional monomer and a monofunctional monomer having an ethylenically unsaturated double bond may be mentioned. The polyfunctional monomer is A condensate obtained by condensing (meth) acrylic acid with a polyhydric alcohol or polycarboxylic acid, or having a hydroxyl group Or an unsaturated polymer such as an amine group and a mercapto group, or an amine, an addition polymer obtained by addition polymerization with a polyhydric alcohol or a polycarboxylic acid via an isocyanate group or an epoxy group.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, and propylene glycol di (methyl). Acrylate, polypropylene glycol di (meth) acrylate, butanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate , Trimethylolpropane tri (meth) acrylate, glycerol di (meth) acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, pentaerythritol di (methyl) ) Acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 2,2-bis (4- (Meth) acryloxyoxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2-hydroxy-3- (methyl ) Acrylfluorenyloxypropyl (meth) acrylate, ethylene glycol diglycidyl ether di (meth) acrylate, diethylene glycol diglycidyl ether (Meth) acrylate, diglycidyl phthalate di (meth) acrylate, glycerol triacrylate, glycerol polyglycidyl ether poly (meth) acrylate, urethane (meth) acrylate Urethane (meth) acrylate (ie, toluene diisocyanate, trimethylhexamethylene diisocyanate or hexamethylene diisocyanate and 2-hydroxyethyl (meth) acrylate reactant), methylene Di (meth) acrylamide, (meth) acrylamide methylene ether, polycondensate of polyhydric alcohol and N-methylol (meth) acrylamide And other polyfunctional monomers, 1,3,5-tripropenylhexahydro-1,3,5-triazine (triacrylformal) and the like. These polyfunctional monomers can be used alone or in combination of two or more.

Examples of the monofunctional monomer include (meth) acrylamide, hydroxymethyl (meth) acrylamide, methoxymethyl (meth) acrylamide, and ethoxymethyl (methyl (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-butylacrylamidosulfonic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, (meth) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropyl phthalate, glycerol mono (meth) acrylate, Tetrahydrofurfuryl (meth) acrylate, dimethylamino (meth) acrylate, (meth) acrylic acid Glycidyl ester, 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3-tetrafluoropropyl (meth) acrylate, (methyl of phthalic acid derivatives) ) Acrylic half esters and the like. These monofunctional monomers can be used alone or in combination of two or more.

(2) Copolymer resin with ethylenic unsaturated group

For a polymerizable resin component having an ethylenically unsaturated double bond, A copolymer resin having an ethylenically unsaturated double bond can be used. Examples of such a copolymer resin having an ethylenically unsaturated double bond include an ethylenic double bond introduced into a side chain of an acrylic resin skeleton composed of (meth) acrylic acid and (meth) acrylic acid ester. (Meth) acrylic resin and the like.

Examples of the polymerizable resin component having an ethylenically unsaturated group include a carboxyl group of a resin obtained by copolymerizing at least an unsaturated compound containing an unsaturated carboxylic acid and an epoxy group, and an unsaturated group containing an epoxy group. A resin obtained by reacting an epoxy group of a saturated compound; or an epoxy group of a resin obtained by copolymerizing at least an unsaturated compound containing an unsaturated carboxylic acid and an epoxy group with a carboxyl group of an unsaturated carboxylic acid And the obtained resin. That is, as a resin obtained by copolymerizing an unsaturated carboxylic acid and an unsaturated compound containing an epoxy group, one of the above-mentioned forms of the acrylic resin (Aac) having an epoxy group is mentioned.

In addition, as a method of introducing an ethylenically unsaturated double bond into an acrylic resin skeleton, as described above, the method is not limited to the method of introducing an ethylenically unsaturated double bond through a carboxylic acid and an epoxy group of the acrylic resin skeleton form. For example, an ethylenically unsaturated double bond may be introduced by an acrylic resin having a carboxylic acid group, a hydroxyl group, an amine group, an amidine group, a thiol group, and the like, and an ethylenic group having a side chain. The unsaturated double bond reacts with monomers such as a carboxylic acid group, a hydroxyl group, an amine group, an amidine group, and a thiol group, such as a polyfunctional isocyanate or a polyfunctional epoxy resin.

More specifically, the (meth) acrylic resin to which an ethylenic double bond is introduce | transduced may be a homopolymer or copolymer of (meth) acrylic acid ester which has an ethylenically unsaturated double bond and an epoxy group.

In addition, in the polymerizable resin component having an ethylenically unsaturated double bond, the proportion of the structural unit (a structural unit having an epoxy group) derived from an unsaturated compound containing an epoxy group is preferably 5 to 90% by mass. , More preferably 15 to 75% by mass. By being in the aforementioned range, the separation layer can be appropriately cured.

The mass average molecular weight of the polymerizable resin component having an ethylenically unsaturated double bond is preferably 2,000 to 50,000, and more preferably 5,000 to 30,000. By being in the aforementioned range, the composition for forming a separation layer can obtain desired coating workability.

[3. Siloxane containing a crosslinkable group]

The polymerizable resin component may be a cross-linkable group-containing siloxane (Asi).

In the present specification, the so-called crosslinkable group-containing siloxane (Asi) is represented by the following formula (Asi0), and represents a crosslinkable group having an epoxy group and a vinyl group on a side chain of the siloxane skeleton. compound of.

-(SiO _3/2 (R ¹ )) _m- (SiO _3/2 (R ² )) _n- (Asi0)

(Here, R ¹ is a crosslinkable group, and R ^{2 is} selected from the group consisting of an alkyl group, an aryl group, or an aromatic group. M and n represent the structural units of the polysiloxane containing the above-mentioned subscript relative to all the structural units. Ear percentage, n + m = 100%, n> 0).

For epoxy siloxane, the photo-cationic polymerization initiator or thermal cationic polymerization initiator can be used to cross-link and polymerize the epoxy groups to form a polymer.

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

(In the formula, R ^c1 is a group containing an epoxy group, an oxetanyl group, a vinyl group, and a (meth) acrylfluorenyl group, R ^c2 is an alkyl group or an aryl group, and the subscripts m and n represent the aforementioned polysilicon. The percentage of moles of the structural units with the subscript in the oxane relative to all the structural units, m is 50 to 90 mole%, n is 10 to 50 mole%, where the sum of m and n is 100 moles. ear%).

Specific examples of the crosslinkable group-containing silicone include polymer E, polymer F represented by the following formula, and trade names X-22-2046 and KF manufactured by Shin-Etsu Silicone Co. Inc. -102 etc:

Polymer E: epoxy-modified siloxane represented by the following formula (Asi2) (mass average molecular weight: 1000 to 20,000)

(In formula (Asi2), the subscripts m1 and n1 represent the mole percentages of the structural units with these subscripts relative to all the structural units in the polymer E, m1 = 50 ~ 90 mole%, n1 = 10 ~ 50 mole Ear%. Among them, the sum of m1 and n1 is 100 mole%).

Polymer F: epoxy-modified siloxane represented by the following formula (Asi3) (mass-average molecular weight: 1000 to 20,000)

(In formula (Asi3), the subscripts m2, n2, and n3 represent the mole percentages of the structural units with these subscripts relative to all the structural units in polymer F, m2 = 50 ~ 90 mole%, n2 = 1 ~ 10 mole%, n3 = 5 ~ 50 mole%, where the sum of m2, n2, and n3 is 100 mole%).

[Polymerization Initiator]

The polymerization initiator is any compound that can cure a polymerizable resin component having a polymerizable group such as an epoxy group or an ethylenically unsaturated double bond. Just fine. Examples of the polymerization initiator capable of curing the polymerizable resin component having the polymerizable group include a thermal cationic polymerization initiator, a photocationic polymerization initiator, and the like. In addition, for example, a thermal radical polymerization initiator and a photo radical polymerization initiator are mentioned. Hereinafter, a thermal cationic polymerization initiator, a photocationic polymerization initiator, a thermal radical polymerization initiator, and a photoradical polymerization initiator will be described in detail.

(1) Thermal cationic polymerization initiator

The composition for forming a separation layer according to the first embodiment contains a thermal cationic polymerization initiator as a polymerization initiator. In addition, among such thermal cationic polymerization initiators, a polymerization initiator that generates heat using heat is sometimes referred to as a thermal acid generator. In the composition for forming a separation layer, during the heat curing treatment, the polymerization of the polymerizable group can be promoted by the action of cations generated by heat. Hereinafter, the compound which can be used as a thermal cationic polymerization initiator is demonstrated in detail.

(cation)

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

(In the above (h01), Rh ⁰ 1 to Rh ⁰⁴ are each independently an organic group selected from the group consisting of free hydrogen, an alkyl group having 1 to 20 carbon atoms, and an aryl group, and the aryl group may have a substituent. At least one of Rh ⁰¹ to Rh ⁰⁴ is an aryl group).

(In the above (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. The aryl group may have a substituent, and Rh ⁰⁵ to (At least one of Rh ⁰⁷ is aryl).

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 the above-mentioned hr-1, R ^hc01 may be hydrogen, a hydroxyl group, and an alkyl group having 1 to 10 carbons. The alkyl group having 1 to 10 carbons may be separated by an ether bond or an ester bond with (hr-1) The phenyl group is bonded. In addition, hr-1 in Rh ⁰¹ to Rh ⁰⁷ may be a substituent different from each other).

As a preferable form of the cation part represented by general formula (h01), the following cation part is mentioned.

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

Moreover, as a preferable form of the cation part shown by General formula (h02), the following cation part is mentioned.

(Anion part)

Examples of the anion portion in the thermal cationic polymerization initiator include a hexafluorophosphate anion, a trifluoromethanesulfonic acid anion, a perfluorobutanesulfonic acid anion, a tetrakis (pentafluorophenyl) borate anion, and the like.

Examples of commercially available thermal cationic polymerization initiators 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 (Sanxin Chemical industry (stock) system) and so on. In addition, CI-2921, CI-2920, CI-2946, CI-3128, CI-2624, CI-2639, CI-2064 (made by Japan Soda Co., Ltd.), CP-66, CP- 77 ((share) ADEKA), FC-520 (3M company) 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, CXC-1613, CXC-1739, CXC-1751, CXC-1766, CXC-1763, CXC-1736, CXC-1756, CXC-1821, CXC-1802-60 (KING INDUSTRY Company system) and so on. Among the foregoing, triflate or hexafluorophosphate is preferred, and triflate is more preferred.

The temperature for generating the acid by the thermal cationic polymerization initiator is preferably at least the temperature used for pre-baking the support on which the composition for forming a separation layer is coated, and specifically, 110 ° C or more. It is more preferably 130 ° C or higher.

The blending amount of the thermal cationic polymerization initiator is preferably 0.01% by weight or more and 20% by weight or less, more preferably 1% by weight or more and 10% by weight or less with respect to the solid content of the composition for forming a separation layer. 5% by weight to 10% by weight. When the blending amount of the thermal acid generator is 0.1% by weight or more, not only the polymerizable resin component can be appropriately polymerized, but also the cured product of the polymerizable resin component can be fired to form a suitable absorption wavelength of 600 nm Light sintered body in the following range.

(2) Photocationic polymerization initiator

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

(In the formula, R ^b01 to R ^b04 are each independently a fluorine atom or an aryl group which may have a substituent. R ^b05 is a fluorine atom or a fluoroalkyl group which may have a substituent. A plurality of R ^b05 may be the same or different from each other. Q is an integer of 1 or more, and Q ^{q + is} each independently a q-valent organic cation).

[(B0) ingredients]

The component (B0) is one or more cationic polymerization initiators selected from the group consisting of a compound represented by the general formula (b0-1) and a compound represented by the general formula (b0-2). These two compounds can produce stronger acids through exposure. Therefore, the composition for forming a separation layer having a component (B0) can appropriately cure the polymerizable resin component having an epoxy group through exposure.

In formula (b0-1), R ^b01 to R ^b04 are each independently a fluorine atom or an aryl group which may have a substituent. The aryl group which may have a substituent in R ^b01 to R ^b04 has a carbon number of preferably 5 to 30, more preferably 5 to 20, still more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples include naphthyl, phenyl, and anthryl. Phenyl is preferred because it is easily available. An aryl group may have a substituent. The substituent is not particularly limited, but is preferably a halogen atom, a hydroxyl group, or a hydrocarbon group (preferably a linear or branched alkyl group, and the number of carbon atoms is preferably 1 to 5), and more preferably a halogen atom or carbon number of 1 to 5 The halogenated alkyl group is particularly preferably a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. The aryl group having a fluorine atom is preferred because the polarity of the anion portion can be increased. Among them, as R ^b01 to R ^b04 in the formula (b0-1), a fluorine-substituted phenyl group is preferred, and a perfluorophenyl group is particularly preferred.

Preferred specific examples of the anion part of the compound represented by the formula (b0-1) include tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ); tetra [(tri Fluoromethyl) 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 ] ^- ) etc. . Among them, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ^- ) is particularly preferred.

In Formula (b0-2), R ^b05 is a fluorine atom or a fluoroalkyl group may have a substituent group, a plurality of R ^b05 may be the same or different each.

The carbon number of the fluoroalkyl group which may have a substituent as R ^b05 is preferably from 1 to 10, more preferably from 1 to 8, and even more preferably from 1 to 5. Specifically, a group obtained by substituting a part or all of hydrogen atoms in the alkyl group having 1 to 5 carbon atoms in the above-mentioned alkyl group having 1 to 5 carbon atoms in the description of R ^a22 and R ^a23 may be mentioned. Among them, R ^{b05 is} preferably a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and still more preferably a fluorine atom or a trifluoromethyl group. Or pentafluoroethyl.

The anion part of the compound represented by the formula (b0-2) is preferably a structure represented by the following general formula (b0-2a).

(In the formula, R ^bf05 is a fluoroalkyl group which may have a substituent, and nb ¹ is an integer of 1 to 5).

In the formula (b0-2a), R ^bf05 , that is, a fluoroalkyl group having a substituent, is the same as the fluoroalkyl group which may have a substituent listed in the aforementioned R ^b05 . In formula (b0-2a), nb ^{1 is} preferably 1 to 4, more preferably 2 to 4, and most preferably 3.

In the formulae (b0-1) to (b0-2), q is an integer of 1 or more, and Q ^{q +} is a q-valent organic cation. Preferred examples include sulfonium cations and iodonium cations. Particularly preferred are the following general formulas ( ca-1) ~ (ca-5) organic cations.

(Wherein R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² each independently represent an aryl group, a heteroaryl group, an alkyl group or an alkenyl group which may have a substituent, and R ²⁰¹ to R ²⁰³ , R ²⁰⁶ to R ²⁰⁷ R ²¹¹ to R ²¹² may be bonded to each other to form a ring together with a sulfur atom in the formula. R ²⁰⁸ to R ²⁰⁹ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ²¹⁰ is an aromatic group which may have a substituent. Group, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a cyclic group containing -SO ₂ -which may have a substituent, and L ²⁰¹ represents -C (= O)-or C (= O ) -O-, Y ²⁰¹ each independently represents an arylene group, an alkylene group, or an alkenylene group, x is 1 or 2, and W ²⁰¹ represents a (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 preferred. ^Examples of the heteroaryl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² include a group in which a part of carbon atoms constituting the aryl group is substituted with a hetero atom. Examples of the hetero atom include an oxygen atom, a sulfur atom, and a nitrogen atom. Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from 9H-thioxanthene; and examples of the substituted heteroaryl group include one hydrogen atom removed from 9H-thioxan-9-one Get the base and so on. The alkyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² is a linear or cyclic alkyl group, and an alkyl group having 1 to 30 carbon atoms is preferred. The alkenyl group in R ²⁰¹ to R ²⁰⁷ and R ²¹¹ to R ²¹² preferably has 2 to 10 carbon atoms. Examples of the substituent that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have include an alkyl group, a halogen atom, a halogenated alkyl group, a carbonyl group, a cyano group, an amine group, a bridging oxy group (= O), An aryl group is a group represented by the following formulae (ca-r-1) to (ca-r-10).

(In the formula, ^{R'201 is} each independently a hydrogen atom, a cyclic group which may have a substituent, a chain-shaped alkyl group which may have a substituent, or a chain-shaped alkenyl group which may have a substituent.)

^R'201 is a cyclic group which may have a substituent, a chain-like alkyl group which may have a substituent, or a chain-like alkenyl group which may have a substituent.

Cyclic radicals which may have substituents:

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. In addition, the aliphatic hydrocarbon group may be saturated or unsaturated, and usually it is preferably saturated.

R 'is an aromatic hydrocarbon group having a hydrocarbon group ²⁰¹ an aromatic ring. The number of carbon atoms in the aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, still more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this carbon number does not include the number of carbon atoms in a substituent. As the R 'in the aromatic ring of the aromatic hydrocarbon group having ^201, specifically, include benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or a part of carbon atoms constituting the aromatic ring is substituted with such hetero atoms are An aromatic heterocyclic ring or a ring obtained by substituting a part of hydrogen atoms constituting such an aromatic ring or an aromatic heterocyclic ring with a bridging oxygen group or the like. Examples of the hetero atom in the aromatic heterocyclic ring include an oxygen atom, a sulfur atom, and a nitrogen atom. As R ^'201 is an aromatic hydrocarbon group, specifically include a group removed a hydrogen atom from the obtained aromatic ring (aryl: e.g., phenyl, naphthyl, anthryl, etc.), the aromatic A group in which one hydrogen atom of a ring is substituted with an alkylene group (for example, benzyl, phenylethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl An arylalkyl group such as an alkyl group), a group obtained by removing a hydrogen atom from a ring (such as anthraquinone, etc.) in which a part of the hydrogen atoms constituting the aromatic ring is substituted with a bridging oxy group, etc. 9H-thioxanthene, 9H-thioxan-9-one, etc.) and a group obtained by removing one hydrogen atom. The number of carbon atoms of the alkylene group (an alkyl chain in an arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

^Examples of the cyclic aliphatic hydrocarbon group in R'201 include an aliphatic hydrocarbon group containing a ring in the structure. Examples of the aliphatic hydrocarbon group containing a ring in this structure include an alicyclic hydrocarbon group (a group obtained by removing one hydrogen atom from an aliphatic hydrocarbon ring), and an alicyclic hydrocarbon group is bonded to a linear or branched chain. A group obtained by the end of the aliphatic hydrocarbon group, a group in which an alicyclic hydrocarbon group is present in the chain of a linear or branched aliphatic hydrocarbon group, and the like. The carbon number of the alicyclic hydrocarbon group is preferably 3 to 20, and more preferably 3 to 12. 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 a monocyclic alkane. The monocycloalkane is preferably an alkane having 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 a polycyclic alkane, and the polycyclic alkane is preferably an alkane having 7 to 30 carbon atoms. Among them, the polycycloalkane is more preferably a polycyclic alkane having a crosslinked ring system, such as adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, and the like; Polycyclic alkanes having a polycyclic skeleton such as a cyclic group of a steroid skeleton having a condensed ring system.

Wherein, as R ^'201 is a cyclic aliphatic hydrocarbon group, preferably removing at least one hydrogen atom from a monocyclic alkane or cycloalkane group obtained, removing one more hydrogen atom from a polycyclic alkane The obtained groups are particularly preferably adamantyl and norbornyl, and most preferably adamantyl.

The carbon number of the linear or branched aliphatic hydrocarbon group which can be bonded to the alicyclic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 ~ 3. As the linear aliphatic hydrocarbon group, a linear alkylene group is preferred, and specifically, methylene [-CH _2- ], ethylene [-(CH ₂ ) _2- ], and trimethylene [-(CH ₂ ) _3- ], tetramethylene [-(CH ₂ ) _4- ], pentamethylene [-(CH ₂ ) _5- ], and the like. The branched aliphatic hydrocarbon group is preferably a branched alkylene group. Specific examples include -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, and -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 -etc. alkyl methylene ; -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 -and other alkylethylene groups; -CH (CH ₃ ) CH ₂ CH ₂ -and -CH ₂ CH (CH ₃ ) CH ₂ -and other alkyltrimethylene groups;- CH (CH ₃ ) CH ₂ CH ₂ CH _2- , -CH ₂ CH (CH ₃ ) CH ₂ CH _2- , and the like alkylene groups such as alkyl tetramethylene and the like. The alkyl group in the alkylalkylene group is preferably a linear alkyl group having 1 to 5 carbon atoms.

A chained alkyl group which may have a substituent:

As a 'chain alkyl group R ²⁰¹ may be straight or branched chain alkyl group of any one. As the linear alkyl group, the carbon number is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specific examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, and tridecyl Alkyl, isotridecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecyl, heptadecyl, octadecyl, undecyl, eicosyl, Twenty-one alkyl, behenyl and the like.

As the branched alkyl group, the number of carbons is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specific examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, and 3-methylbutyl. , 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, and the like.

Alkenyl chain which may have a substituent:

As the R 'chain alkenyl group ^201, may be linear or branched in any one of the carbon atoms preferably from 2 to 10, more preferably from 2 to 5, more preferably from 2 to 4 , Particularly preferably 3. Examples of the linear alkenyl group include a vinyl group, an allyl group (allyl), and a butenyl group. Examples of the branched alkenyl group include 1-methylvinyl group, 2-methylvinyl group, 1-methacryl group, and 2-methacryl group. As the chain alkenyl group, among the foregoing, a linear alkenyl group is preferred, a vinyl group and a propenyl group are more preferred, and a vinyl group is particularly preferred.

As the cyclic group R ^'201, the chain alkyl or alkenyl substituent group, for example, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, nitro group, amino group, a bridge An oxy group, a cyclic group in the aforementioned R ' ²⁰¹ , and the like.

Among them, R ′ ^{201 is} preferably a cyclic group which may have a substituent, and a chain-like 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 with a sulfur atom in the formula, a hetero atom such as a sulfur atom, an oxygen atom, a nitrogen atom, and a carbonyl group can be separated. Functional groups such as, -SO-, -SO _2- , -SO _3- , -COO-, -CONH-, or N (R _N )-(the R _N is an alkyl group having 1 to 5 carbon atoms) are bonded. As the formed ring, for a ring containing a sulfur atom in the formula in its ring skeleton, a 3 to 10-membered ring including a sulfur atom is preferred, and a 5- to 7-membered ring is particularly preferred. Specific examples of the formed ring include a thiophene ring, a thiazole ring, a benzothiophene, a thioanthracene ring, a benzothiophene, a dibenzothiophene, a 9H-thioxanthene ring, a thioxanthone ring, a thioxanthene ring, A phenoxathia ring, a tetrahydrothienium ring, a tetrahydrothianium ring, and the like.

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. In the case of an alkyl group, they may be bonded to each other to form ring.

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

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

^Examples of the arylene group in Y ²⁰¹ include a group obtained by removing one hydrogen atom from the aryl group listed as the aromatic hydrocarbon group in R ′ ²⁰¹ . Examples of the alkylene group and alkenylene group in Y ²⁰¹ include those obtained by removing one hydrogen atom from the groups listed as the chain alkyl group and chain alkenyl group in R ′ ²⁰¹ . base.

In the aforementioned formula (ca-4), x is 1 or 2. W ²⁰¹ is a (x + 1) valence, that is, a divalent or trivalent linking group. The divalent linking group in W ²⁰¹ is preferably a divalent hydrocarbon group which may have a substituent, and is preferably the same group as the divalent hydrocarbon group which may have a substituent listed in R ^EP in the aforementioned formula (anv0). The divalent linking group in W ²⁰¹ may be any of linear, branched, and cyclic, and is preferably cyclic. Among them, a group in which two carbonyl groups are combined at both ends of the arylene group, or a group composed of only an arylene group is preferred. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is particularly preferred. ^Examples of the trivalent linking group in W ²⁰¹ include a group obtained by removing one hydrogen atom from the divalent linking group in W ²⁰¹ , and the divalent linking group obtained by further bonding the divalent linking group. The base and so on. As the trivalent linking group in W ²⁰¹ , a group having two carbonyl groups bonded to an arylene group is preferred.

Specific examples of preferred cations represented by the above formula (ca-1) include cations represented by the following formulae (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 examples given as the substituents that R ²⁰¹ to R ²⁰⁷ and R ²¹⁰ to R ²¹² may have).

Moreover, as a cation represented by said formula (ca-1), the cation represented by the following general formula (ca-1-25)-(ca-1-36), respectively is preferable.

(In the formula, R ' ²¹¹ is an alkyl group, and R ^hal is a hydrogen atom or a halogen atom).

As a preferable cation represented by said formula (ca-2), a diphenyl iodonium cation, a bis (4-tert-butylphenyl) iodonium cation, etc. are mentioned specifically ,.

Specific examples of preferred cations represented by the above formula (ca-4) include cations represented by the following formulae (ca-4-1) to (ca-4-2).

In addition, as the cation represented by the aforementioned formula (ca-5), cations represented by the following general formulae (ca-5-1) to (ca-5-2) are preferred, respectively.

(Wherein R ' ²¹¹ is an alkyl group).

Among the foregoing, the cation part [(Q ^{q +} ) _{1 / q} ] is preferably a cation represented by the general formula (ca-1), and more preferably, it is represented by the formulas (ca-1-1) to (ca-1-36) ).

Moreover, among such photocationic polymerization initiators, a polymerization initiator that generates an acid by light is sometimes referred to as a photoacid generator.

As for the (B0) component, the above-mentioned photoacid generator may be used alone or in combination of two or more kinds. The content ratio of the (B0) component is preferably 0.01 to 20 parts by mass, and more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polymerizable resin component having an epoxy group in the composition for forming a separation layer of the present invention. , More preferably 0.2 to 5 parts by mass, Particularly preferred is 0.5 to 2 parts by mass. In the composition for forming a separation layer of the present invention, the content ratio of the (B0) component in the photocationic polymerization initiator is not particularly limited, and can be appropriately determined depending on the structure of the (B0) component, the acid derived from the anion part, and the like. Specifically, the content ratio of the (B0) component in the photocationic polymerization initiator is preferably 20 to 99.999% by mass, more preferably 30 to 99.99% by mass, still more preferably 40 to 99.9% by mass, and particularly preferably 60. ~ 99.9% by mass, preferably 90 ~ 99.6% by mass. By setting the content ratio of the (B0) component to the aforementioned range, the strength of the plurality of acids generated by the polymerization initiator through exposure can be moderated as a whole, and the polymerizable resin component can be appropriately cured.

The content of the photocationic polymerization initiator is preferably 0.01 to 60 parts by mass, more preferably 0.05 to 30 parts by mass, relative to 100 parts by mass of the polymerizable resin component having an epoxy group in the composition for forming a separation layer. It is more 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, after curing the polymerizable resin component and firing, the light transmittance in the separation layer can be reduced, and ideal laser reactivity can be obtained.

(3) Thermal radical polymerization initiator

Examples of the thermal radical polymerization initiator include a peroxide and an azo-based polymerization initiator. These thermal radical polymerization initiators generate radicals by heating, and polymerize a polymerizable monomer by the radicals.

Examples of the peroxide include ketone peroxide, ketal peroxide, hydrogen peroxide, dialkyl peroxide, peroxide ester, and peroxide. Carbonate and ketal peroxide. Specific examples include acetamidine peroxide, dicumyl peroxide, tert-butyl peroxide, tert-butyl cumene peroxide, propylammonium peroxide, benzoylperoxide (BPO), 2 -Benzamidine chloroperoxide, 3-Benzylhydrazine perchlorate, 4-Benzylhydrazine perchlorate, 2,4-Dichlorobenzyl peroxide, 4-Bromomethylbenzyl peroxide, Peroxide Laurel oxide, potassium persulfate, diisopropyl peroxycarbonate, tetrahydronaphthalene hydroperoxide, 1-phenyl-2-methylpropyl-1-hydrogen peroxide, tert-butyl perphenyl triacetate , Tert-butyl hydroperoxide, tert-butyl performate, tert-butyl peroxyacetate, tert-butyl perbenzoate, tert-butyl perphenyl acetate, tert-butyl permethoxy 4-methoxyacetate, and per-N- Tert-butyl (3-methylphenyl) carbamate, dicumyl peroxide, tert-butylperoxy-2-ethylhexyl monocarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate Esters, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane and 1,1-bis (t-butylperoxy) cyclohexane.

As a commercially available peroxide, for example, a trade name "PERCUMYL (registered trademark)", a trade name "PERBUTYL (registered trademark)", and a trade name "PEROCTA (registered trademark)" made by Japan Oil & Fat Co., Ltd. , "PEROYL (registered trademark)" and "PERHEXA (registered trademark)".

Examples of the azo-based polymerization initiator include 2,2'-azobispropane, 2,2'-dichloro-2,2'-azobispropane, and 1,1'-azo (methyl Ethyl) diacetate, 2,2'-azobis (2-methylamidopropane) hydrochloride, 2,2'-azobis (2-aminopropane) nitrate, 2,2 '-Azobisisobutane, 2,2'-azobisisobutyramide, 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylpropionate methyl Ester), 2,2'-dichloro-2,2'-azobisbutane, 2,2'-azobis (2-methyl Butyronitrile), 2,2'-azobisisobutyric acid dimethyl ester, 1,1'-azobis (1-methylbutyronitrile-3-sulfonate), 2- (4-methyl (Phenylazo) -2-methylmalononitrile, 4,4'-azobis (4-cyanovaleric acid), 3,5-dihydroxymethylphenylazo-2-allyl allyl Dinitrile, 2,2'-azobis (2-methylvaleronitrile), 4,4'-azobis (4-cyanovalerate dimethyl), 2,2'-azobis (2 , 4-dimethylvaleronitrile), 1,1'-azobis (cyclohexanenitrile), 2,2'-azobis (2-propylbutyronitrile), 1,1'-azobis (Cyclohexanenitrile), 2,2'-azobis (2-propylbutyronitrile), 1,1'-azobis (1-chlorophenylethane), 1,1'-azobis (1-cyclohexanecarbonitrile), 1,1'-azobis (1-cycloheptanenitrile), 1,1'-azobis (1-phenylethane), 1,1'-couple Azabiscumene, 4-nitrophenylazobenzyl cyanoacetate, phenylazodiphenylmethane, phenylazotriphenylmethane, 4-nitrophenylazotriphenyl Methane, 1,1'-azobis (1,2-diphenylethane), poly (bisphenol A-4,4'-azobis (4-cyanovalerate)), and poly (quad Ethylene 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, more preferably 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the polymerizable monomer. Thereby, a polymerizable resin component having an ethylenically unsaturated double bond can be appropriately polymerized. The thermal radical polymerization initiator may be blended into the composition for separation layer formation by a known method immediately before the composition for formation of separation layer is used. The thermal radical polymerization initiator may be added to the composition for forming a separation layer after being diluted in an addition solvent to be described later.

The 1-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.

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. The time taken for the polymerizable resin component of the ethylenically unsaturated double bond to polymerize and gel. Thereby, the operation time when an adhesive composition is apply | coated to a support body can be extended. In addition, 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. The support composition is coated on the support and heated. When the diluent solvent is removed, radicals can be generated at the same time, and the polymerization of the polymerizable resin component is preliminarily initiated. From the viewpoint of extending the operable time, the half-life temperature and the half-life temperature of the thermal radical polymerization initiator are preferably higher. In addition, from the viewpoint of rapid gelation, the one-half-life temperature and the one-hour half-life temperature of the thermal radical polymerization initiator are preferably 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 blending amount of the thermal radical polymerization initiator may be appropriately adjusted according to the theoretical active oxygen amount.

(4) Photo radical polymerization initiator

The composition for forming a separation layer can polymerize a polymerizable resin component through a photoradical polymerization initiator. In addition, a photoradical polymerization initiator is used as In the case of a polymerization initiator, if the adhesive composition is packaged so as to maintain a light-shielding state, the composition for forming a separation layer can be manufactured in a state where a photo radical polymerization initiator is blended.

Specific examples of the photo radical polymerization initiator include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropane 1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1-one, 2,2-dimethoxy-1,2-diphenylethane -1-one, bis (4-dimethylaminophenyl) ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one, O-ethylamido-1- [6- (2-methylbenzoyl (Fluorenyl) -9-ethyl-9H-oxazol-3-yl] acetaldehyde oxime, 2,4,6-trimethylbenzylidene diphenylphosphine oxide, 4-benzylidene-4 ' -Methyldimethylsulfide, 4-dimethylaminobenzoic acid, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylamino Butyl benzoate, 4-dimethylamino-2-ethylhexyl benzoate, 4-dimethylamino-2-isoamyl benzoate, benzyl-β-methoxyethyl acetal , Benzophenone dimethyl ketal, 1-phenyl-1,2-propanedione-2- (O- (Oxycarbonyl) oxime, methyl ortho-benzoyl benzoate, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 1-chloro-4 -Propoxythioxanthone, thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthine, 2-ethylanthraquinone, octa Octamethyl anthraquinone, 1,2-benzoanthraquinone, 2,3-diphenylanthraquinone, azobisisobutyronitrile, benzamidine peroxide, cumene hydroperoxide, 2- Mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole Azole, 2- (o-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (o-chlorophenyl) -4,5-bis (methoxyphenyl) imidazole dimer, 2 -(O-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazole dimer, 2- (p-methoxy (Phenyl) -4,5-diphenylimidazole dimer, 2,4,5-triarylimidazole dimer, benzophenone, 2-chlorobenzophenone, 4,4'-bis (di (Methylamino) benzophenone (i.e., ketone ketone), 4,4'-bis (diethylamino) benzophenone (i.e., ethyl ketone ketone), 4,4'-dichlorobenzophenone Ketone, 3,3-dimethyl-4-methoxybenzophenone, benzoin, benzoin, benzoin methyl ether, benzoin ether, benzoin isopropyl ether, benzoin Butyl ether, benzoin isobutyl ether, benzoin tert-butyl ether, acetophenone, 2,2-diethoxyacetophenone, p-dimethylacetophenone, p-dimethylamino Phenylacetone, dichloroacetophenone, trichloroacetophenone, p-tert-butylacetophenone, p-dimethylaminoacetophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichlorobenzene Ethyl ketone, α, α-dichloro-4-phenoxyacetophenone, thioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone , Dibenzocycloheptenone, amyl 4-dimethylaminobenzoate, 9-phenylacridine, 1,7-bis- (9-acridyl) heptane, 1,5-di- ( 9-acridyl) pentane, 1,3-bis- (9-acridyl) propane, p-methoxytriazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2 -Methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-2-yl) vinyl] -4,6-bis (trichloromethyl) ) -Hytriazine, 2- [2- (furan-2-yl) vinyl] -4,6-bis (trichloromethyl) -himetriazine, 2- [2- (4-diethylamine Phenyl-2-methylphenyl) vinyl] -4,6-bis (trichloromethyl) -triazine, 2- [2- (3,4-dimethoxyphenyl) vinyl]- 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethyl Oxystyryl) -4,6-bis (trichloromethyl) -triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) ) -Mesytriazine, 2,4-di-trichloromethyl-6- (3-bromo-4-methoxy) phenyl-mesytriazine, 2,4-di-trichloromethyl-6 -(2-bromo-4-methoxy) phenyl-mesytriazine, 2,4-di-trichloromethyl-6- (3-bromo-4-methoxy) styrylphenyl-mesh Triazine, 2,4-di-trichloromethyl-6- (2-bromo-4-methoxy) styrylphenyl-mesytriazine, and the like. As the photoradical polymerization initiator, commercially available products such as "IRGACURE OXE02", "IRGACURE OXE01", "IRGACURE 369", "IRGACURE 651", and "IRGACURE 907" (trade names: all manufactured by BASF Corporation) can be used. ), And "NCI-831" (brand name: ADEKA).

The blending amount of the photo radical polymerization initiator is preferably 0.1 part by weight or more and 20 parts by weight or less, more preferably 1 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the polymerizable monomer.

[3. Other ingredients]

The composition for forming a separation layer according to the embodiment may include a surfactant and a diluent in addition to the polymerizable component and the polymerization initiator described above.

(1) Surfactant

The composition for forming a separation layer may contain a surfactant. Examples of the surfactant include a silicone-based surfactant and a fluorine-based surfactant. As the silicone-based surfactant, specifically, 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 (by BYKChemie) and the like. As the fluorine-based surfactant, specifically, F-114, F-177, F-410, F-411, F-450, F-493, F-494, F-443, F-444, F can be used. -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); PF-636, PF-6320, PF-656, PF-6520 of the POLYFOX series (Manufactured by OMNOVA).

The surfactant may be used singly or in combination of two or more kinds. The content of the surfactant is preferably 0.01 to 10 parts by mass, more preferably 0.02 to 2 parts by mass, and still more preferably 0.03 to 1 part by mass based on 100 parts by mass of the polymerizable resin component. When the composition for forming a separation layer is coated on the support through the above range, a separation layer with high flatness can be formed.

(2) Diluted solvent

The composition for forming a separation layer according to one embodiment preferably contains a diluent solvent. As long as the diluent is a polymerizable resin component and a polymer The solvent of the initiator is not limited, and the solvents shown below can be suitably used.

Examples of the diluting solvent include linear hydrocarbons such as hexane, heptane, octane, nonane, methyloctane, decane, undecane, dodecane, and tridecane; carbon number 4 ~ 15 branched hydrocarbons, such as cyclic hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, naphthalene, decalin, tetrahydronaphthalene; p-menthane, o-menthane, m-menthane, di Phenylmentane, 1,4-terpinene, 1,8-terpinene, pinane, norbornane, pinane, pinane, pinane, longifolene, geraniol, nerol, aromatic Camphor, citral, citronellol, menthol, isomenthol, neomenthol, alpha-terpineol, beta-terpineol, gamma-terpineol, terpinen-1-ol, terpinene 4-alcohol, terpineol dihydroacetate, 1,4-eucalyptol, 1,8-eucalyptol, borneol, carvone, ionone, thujone, camphor, d-pinene, l-fluorene Terpene-based solvents such as olefins and diterpenes; lactones such as γ-butyrolactone; acetone, methyl ethyl ketone, cyclohexanone (CH), methyl n-pentanone, methyl isopentanone, 2- Ketones such as heptone; Polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; ethylene glycol monoacetate Compounds having an ester bond, such as diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; monomethyl ethers or monoethyl ethers of the aforementioned polyols or the aforementioned compounds having an ester bond Polyol derivatives such as monoalkyl ethers such as monopropyl ether, monobutyl ether, or compounds having an ether bond such as monophenyl ether (Among these, propylene glycol monomethyl ether acetate ( PGMEA), propylene glycol monomethyl ether (PGME)); cyclic ethers like dioxane, or methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate , Methoxybutyl acetate, methyl pyruvate, propane Esters such as ethyl ketoate, methyl methoxypropionate, ethyl ethoxypropionate; anisole, ethyl benzyl ether, tolyl methyl ether, diphenyl ether, dibenzyl ether, Aromatic organic solvents such as phenyl ether and butylphenyl 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.

<Laminated body 10 (first embodiment)>

As shown in FIG. 1, a laminate 10 according to one embodiment (first embodiment) of the present invention is formed by laminating a substrate 1 and a support plate 2 with 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 an embodiment. Therefore, the laminate includes a separation layer having high chemical resistance. Therefore, a laminated body produced using the composition for forming a separation layer according to one embodiment is also within the scope of the present invention.

[Substrate 1]

The substrate 1 can be used for processes such as thinning and mounting while being supported by the support plate 2. In addition, for the substrate 1, for example, a structure such as a integrated circuit or a metal bump can be mounted. The substrate 1 may be a typical silicon wafer substrate, but it is not limited, and a substrate formed of an optional material such as a ceramic substrate, a thin film substrate, or a flexible substrate may be used.

[Support plate 2]

The support plate (support body) 2 is a support body for supporting the substrate 1, and is separated by The layer 3 is bonded to the substrate 1. Therefore, as the support plate 2, it is only necessary to have the strength necessary to prevent the substrate 1 from being broken or deformed during processes such as thinning, transportation, and mounting of the substrate 1. The support plate 2 only needs to be capable of transmitting light for modifying the separation layer 4. From these viewpoints, as the support plate 2, a support made of glass, silicon, or an acrylic resin can be used.

[Next to layer 3]

The adhesive layer 3 is a layer for bonding the substrate 1 and the support plate 2, and is formed of an adhesive for bonding the substrate 1 and the support plate 2.

The adhesive for forming the adhesive layer 3 contains other components such as a thermoplastic resin, a diluent, and additives. Here, as the thermoplastic resin contained in the adhesive, that is, the thermoplastic resin contained in the adhesive layer 3, any resin having adhesiveness may be used. For example, a hydrocarbon resin, an acrylic-styrene resin, and Malaya are more preferably used. An amine resin, an elastomer resin, a polyfluorene resin, or the like, or a resin obtained by combining these and the like. Hereinafter, the thermoplastic resin contained in the adhesive layer 3 in this embodiment is demonstrated.

(Hydrocarbon resin)

A hydrocarbon resin has a hydrocarbon skeleton and is a resin formed by polymerizing a monomer composition. Examples of the hydrocarbon resin include a cycloolefin-based polymer (hereinafter, sometimes referred to as "resin (A)") and at least one selected from the group consisting of a terpene resin, a rosin-based resin, and a petroleum resin. Resin (hereinafter, sometimes referred to as "resin (B)") and the like are not limited thereto.

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

Examples of the cycloolefin-based monomer included in the monomer component constituting the resin (A) include bicyclics such as norbornene and norbornadiene, dicyclopentadiene, and hydroxydicyclopentadiene. Tricyclics, tetracyclics such as dodecene, pentacyclics such as cyclopentadiene trimers, heptads such as tetracyclopentadiene, or alkyl groups of these polycyclics (methyl, (Ethyl, propyl, butyl, etc.) substitutions, alkenyl (vinyl, etc.) substitutions, alkylidene (ethylidene, etc.) substitutions, aryl (phenyl, tolyl, naphthyl, etc.) substitutions Things. Among these, a norbornene-based monomer selected from the group consisting of norbornene, tetracyclododecene, or these alkyl substituents is particularly preferable.

The monomer component constituting the resin (A) may contain other monomers that can be copolymerized with the above-mentioned cycloolefin-based monomer, and, for example, preferably contains an olefin monomer. Examples of the olefin monomer include ethylene, propylene, 1-butene, isobutylene, 1-hexene, and α-olefin. The olefin monomer may be linear or branched.

In addition, as a monomer component constituting the resin (A), a cycloolefin monomer is preferably contained from the viewpoint of high heat resistance (low thermal decomposition, low thermal weight loss). The proportion of the cyclic olefin monomer is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 20 mol% or more with respect to the entire monomer component constituting the resin (A). In addition, the proportion of the cyclic olefin monomer is not particularly limited with respect to the entire monomer component constituting the resin (A). From the viewpoints of properties and stability over time in a solution, it is preferably 80 mol% or less, and more preferably 70 mol% or less.

The monomer component constituting the resin (A) may contain a linear or branched alkene monomer. From the viewpoint of solubility and flexibility, the ratio of the olefin monomer is preferably 10 to 90 mol%, more preferably 20 to 85 mol% with respect to the overall monomer component constituting the resin (A), and more preferably It is preferably 30 to 80 mol%.

In addition, for the resin (A), for example, a resin having no polar group, such as a resin formed by polymerizing monomer components of a cycloolefin-based monomer and an olefin monomer, suppresses gas generation at high temperatures. Aspects are better.

The polymerization method, polymerization conditions, and the like when polymerizing the monomer components are not particularly limited, and may be appropriately set in accordance with ordinary methods.

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

(In the chemical formula (ad2), n is an integer of 0 or 1 to 3).

As such a cycloolefin copolymer, APL 8008T, APL 8009T, and APL 6013T (all manufactured by Mitsui Chemicals Co., Ltd.) can be used.

Examples of commercially available products that can be used as the resin (A) include, for example, "TOPAS" manufactured by Polyplastics Corporation, "APEL" manufactured by Mitsui Chemicals Corporation, "ZEONOR" manufactured by "Zeon Corporation", and "ZEONEX", "ARTON" made by JSR Corporation, etc.

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 when the laminate is exposed to a high-temperature environment can be further suppressed.

The resin (B) is at least one resin selected from the group consisting of a terpene-based resin, a rosin-based resin, and a petroleum resin. Specific examples of the terpene-based resin include a terpene resin, a terpene phenol resin, a modified terpene resin, a hydrogenated terpene resin, a 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 petroleum resins include aliphatic or aromatic petroleum resins, hydrogenated petroleum resins, modified petroleum resins, alicyclic petroleum resins, and coumarone. Indole petroleum resin, etc. Among these, a hydrogenated terpene resin and a hydrogenated petroleum resin are more preferable.

The softening point of the resin (B) is not particularly limited, but is preferably 80 to 160 ° C. When the softening point of the resin (B) is 80 to 160 ° C, the laminated body can be suppressed from being softened when exposed to a high-temperature environment without causing defective bonding.

The weight average molecular weight of the resin (B) is not particularly limited, but is preferably 300 to 3,000. If the weight average molecular weight of the resin (B) is 300 or more In this case, the heat resistance becomes sufficient, and the amount of outgassing in a high-temperature environment decreases. 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-based solvent becomes good. Therefore, the residue of the adhesive layer on the substrate after removing the separation support can be quickly dissolved. The weight average molecular weight of the resin (B) in the present embodiment is a molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC).

As the resin, a resin obtained by mixing the resin (A) and the resin (B) can be used. By mixing, heat resistance becomes favorable. For example, as a mixing ratio of the resin (A) and the resin (B), (A) :( B) = 80: 20 to 55:45 (mass ratio) is excellent because of good heat resistance and flexibility in a high temperature environment.

(Acrylic-styrene resin)

Examples of the acrylic-styrene resin include resins obtained by polymerizing styrene or a styrene derivative with a (meth) acrylate or the like as a monomer.

Examples of the (meth) acrylate include a (meth) acrylic acid alkyl ester having a chain structure, a (meth) acrylic acid ester having an aliphatic ring, and a (meth) acrylic acid having an aromatic ring. Acrylate. 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 acid having an alkyl group having 1 to 14 carbon atoms. Alkyl esters, etc. Examples of the acrylic long-chain alkyl ester include n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, and n-icodecyl Acrylic or methacrylic alkyl groups ester. The alkyl group may be branched.

Examples of the acrylic alkyl ester having an alkyl group having 1 to 14 carbon atoms include a conventionally known acrylic alkyl ester used for an acrylic adhesive. Examples of the alkyl group include methyl, ethyl, propyl, butyl, 2-ethylhexyl, isooctyl, isononyl, isodecyl, dodecyl, lauryl, and tridecyl And other alkyl esters of acrylic or methacrylic acid.

Examples of the (meth) acrylate having an aliphatic ring include cyclohexyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-adamantyl (meth) acrylate, and (meth) Norbornyl acrylate, isobornyl (meth) acrylate, tricyclodecyl (meth) acrylate, tetracyclododecyl (meth) acrylate, dicyclopentyl (meth) acrylate, etc., more preferably Isobornyl methacrylate, dicyclopentyl (meth) acrylate.

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

(Maleimide resin)

Examples of the maleimide-based resin include resins obtained by polymerizing the following monomers: N-methylmaleimide, N-ethylmaleimide, and N-n-propyl Maleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-sec-butylmaleimide, N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexyl Maleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N-laurylmaleimide, N-stearylmaleimide, etc. Maleimide with alkyl groups; N-cyclopropylmaleimide, N-cyclobutylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide Imines, N-cycloheptylmaleimide, N-cyclooctylmaleimide, etc. Maleimides having aliphatic hydrocarbon groups; N-phenylmaleimide, N-m-methanine Aromatic maleimides having an aryl group, such as N-phenylphenylmaleimide, N-o-methylphenylmaleimide, N-p-methylphenylmaleimide, and the like.

(Elastomer)

The elastomer preferably includes 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 carbons, an alkoxy group having 1 to 5 carbons, an alkoxyalkyl group having 1 to 5 carbons, ethoxyl, carboxyl, and the like. The content of the styrene unit is more preferably within a range of 14% by weight or more and 50% by weight or less. The weight average molecular weight of the elastomer is preferably in the range of 10,000 or more and 200,000 or less.

When 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, it is easy to dissolve in a hydrocarbon-based solvent (solvent) described later. Therefore, the adhesive layer can be more easily and quickly removed. In addition, when the content of the styrene unit and the weight average molecular weight are within the above ranges, when a wafer substrate is subjected to a resist photolithography step, a resist solvent (for example, PGMEA, PGME, etc.) exposed thereto, Acid (hydrofluoric acid Etc.) and alkali (TMAH, etc.) exhibit excellent resistance.

The (meth) acrylate described above may be further mixed with the elastomer.

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

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

As the elastomer, if the content of the styrene unit is in the range of 14% by weight to 50% by weight and the weight average molecular weight of the elastomer is in the range of 10,000 to 200,000, various elastomers can be used. Examples include polystyrene-poly (ethylene / propylene) block copolymer (SEP), styrene-isoprene-styrene block copolymer (SIS), and styrene-butadiene-styrene Block copolymers (SBS), styrene-butadiene-butene-styrene block copolymers (SBBS), and their hydrides, styrene-ethylene-butene-styrene block copolymers (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 styrene-ethylene-ethylene-propylene-styrene block copolymer (Septon V9461 (KURARAY CO., LTD.), Septon V9475 (KURARAY CO., LTD.)) The styrene block is a reactive cross-linked styrene-ethylene-butene-styrene block copolymer (reactive polystyrene-based hard block, Septon V9827 (manufactured by Kuraray Co., Ltd.)), poly Styrene-poly (ethylene-ethylene / propylene) block-polystyrene block copolymer (SEEPS-OH: terminal hydroxyl modified) For example, an elastomer having a content of a styrene unit and a weight average molecular weight within the above range can be used.

In addition, the elastomer is more preferably a hydride. If it is a hydride, stability to heat improves, and modification such as decomposition and polymerization is unlikely to occur. In addition, it is more preferable from the viewpoint of solubility in a hydrocarbon-based solvent and resistance to a resist solvent.

The elastomer is more preferably an elastomer of a block polymer having styrene at both ends. This is because higher heat resistance can be exhibited by embedding styrene having high thermal stability at both ends.

More specifically, the elastomer is more preferably a hydrogenated product of a block copolymer of styrene and a conjugated diene. Improved thermal stability, and difficult to modify such as decomposition and polymerization. In addition, by embedding styrene having high thermal stability at both ends, higher heat resistance can be exhibited. In addition, it is more preferable from the viewpoint of solubility in a hydrocarbon-based solvent and resistance to a resist solvent.

As commercially available products which can be used as an elastomer contained in the adhesive constituting the adhesive layer 3, for example, "SEPTON (trade name)" by KURARAY CO., LTD, and "HYBRAR (product by KURARAY CO., LTD)" can be mentioned. ")," TUFTEC (trade name) "made by Asahi Kasei Co., Ltd.," DYNARON (trade name) "made by JSR Co., Ltd., etc.

The content of the elastomer included in the adhesive constituting the adhesive layer 3 is, for example, based on the total amount of the adhesive composition being 100 parts by weight, preferably within a range of 50 parts by weight to 99 parts by weight, and more preferably 60 The range is more than 70 parts by weight and preferably less than 95 parts by weight, and preferably within the range of 70 parts by weight to 95 parts by weight. By being in the above range, the substrate and the support can be appropriately bonded while maintaining heat resistance.

In addition, a plurality of types of elastomers may be mixed. That is, the adhesive constituting the adhesive layer 3 may include a plurality of types of elastomers. In addition, at least one of the plurality of types of elastomers may include a styrene unit as a structural unit of the main chain. In addition, if the content of at least one of the plurality of types of elastomers is in the range of 14% by weight or more and 50% by weight or less, or the weight average molecular weight is in the range of 10,000 or more and 200,000 or less, Such elastomers are also within the scope of the present invention. In addition, when a plurality of types of elastomers are included in the adhesive constituting the adhesive layer 3, it can be adjusted so that the content of the styrene unit in the result after mixing falls within the aforementioned range. For example, if SEPTON (trade name) Septon4033 manufactured by Kuraray Co., Ltd. with a styrene unit content of 30% by weight and SEPTON (trade name) Septon2063 with a styrene unit content of 13% by weight is used in a 1: 1 weight Specific mixing means that the styrene content is 21 to 22% by weight based on the total elastomer contained in the adhesive, and therefore it is 14% by weight or more. In addition, for example, when a 10% by weight component of a styrene unit and a 60% by weight component are mixed at a weight ratio of 1: 1, it becomes 35% by weight, which is within the aforementioned range. The present invention may take such a form. In addition, it is preferable that a plurality of types of elastomers included in the adhesive constituting the adhesive layer 3 all contain a styrene unit within the aforementioned range, and the weight average molecular weight is within the aforementioned range.

Also, it is preferable to use a photocurable resin (for example, a UV curable tree). Resin other than resin) forms the adhesive layer 3. By using a resin other than the photocurable resin, it is possible to prevent residues from being generated around the minute unevenness of the substrate 1 after the adhesive layer 3 is peeled off or removed. The adhesive constituting the adhesive layer 3 is particularly preferably an adhesive that does not dissolve in any solvent but dissolves in a specific solvent. This is because it can be removed by dissolving the adhesive layer 3 in a solvent, and it is not necessary to apply a physical force to the substrate 1. When the adhesive layer 3 is removed, the adhesive layer 3 can be easily removed without breaking or deforming the substrate 1, even if the substrate 1 has a reduced strength.

(Polyfluorene-based resin)

The adhesive for forming the adhesive layer 3 may include a polyfluorene-based resin. By forming the adhesive layer 3 through a polyfluorene-based resin, it is possible to produce a laminate that can dissolve the adhesive layer in a subsequent step and peel the support from the substrate even if the laminate is processed at a high temperature. If the adhesive layer 3 contains a polyfluorene resin, for example, the laminate can be suitably used even in a high-temperature step in which the laminate is annealed at a high temperature equal to or higher than 300 ° C.

The polyfluorene-based resin has a structure formed by a structural unit represented by the following general formula (ad3) and at least one type of constituent unit among the structural units represented by the following general formula (ad4).

(Wherein R ^C3 , R ^C4, and R ^C5 in general formula (ad3) and R ^C3 and R ^C4 in general formula (ad4) are each independently selected from the group consisting of phenylene, naphthylene, and anthracenyl In the group, X ′ is an alkylene group having 1 to 3 carbon atoms).

For the polyfluorene-based resin, the substrate 1 and the support plate 2 are bonded together via at least one of a polyfluorene structural unit represented by the formula (ad3) and a polyether fluorene structural unit represented by the formula (ad4). A laminated body can be formed in which even if the substrate 1 is processed under high temperature conditions, the insolubilization of the adhesive layer 3 due to decomposition, polymerization, or the like can be prevented. In addition, if the polyfluorene resin is a polyfluorene resin composed of a polyfluorene constituent unit represented by the above formula (ad3), the polyfluorene resin is stable even when heated to a higher temperature. Therefore, it is possible to prevent residues caused by the adhesion layer on the substrate 1 after cleaning.

The weight average molecular weight (Mw) of the polyfluorene resin is preferably in a range of 30,000 or more and 70,000 or less, and more preferably in a range of 30,000 or more and 50,000 or less. When the weight average molecular weight (Mw) of the polyfluorene-based resin is in a range of 30,000 or more, an adhesive composition that can be used at a high temperature of, for example, 300 ° C or more can be obtained. In addition, if the weight average molecular weight (Mw) of the polyfluorene-based resin is within a range of 70,000 or less, it can be well dissolved through a solvent. That is, a good solvent can be obtained Well removed adhesive composition.

(Other ingredients)

The adhesive constituting the adhesive layer 3 may include other substances having a miscibility within a range that impairs the essential characteristics. For example, various additives commonly used such as additional resins, plasticizers, adhesion promoters, stabilizers, colorants, thermal polymerization inhibitors, and surfactants, which are used to improve the performance of the adhesive, can be further used. The adhesive can also be used by diluting it with the diluting solvent described in the above (1) Dilution solvent column.

[Separation layer 4]

The separation layer 4 is a layer that can be formed using the composition for forming a separation layer according to the embodiment, and the layer is formed of a fired body formed by firing a cured product that is passed through a polymerization initiator. It is obtained by hardening the polymerizable resin component contained in the separation layer formation composition. The separation layer 4 can be appropriately modified by absorbing the light irradiated through the support plate 2 by making it a fired body formed using the composition for forming a separation layer.

As used herein, the term “fired body” refers to a fired body formed by firing a cured product. The cured product is obtained by polymerizing and curing the above-mentioned polymerizable resin component through a polymerization initiator. . The firing system is formed by firing a cured product of a polymerizable resin component and a polymerization initiator in an atmospheric environment, that is, an environment where oxygen is present, and at least a part of the cured product is carbonized. The inventors of the present application have found that such a fired body can be formed with high chemical resistance and can be appropriately absorbed. A separation layer of light having a wavelength in the range of 600 nm.

The thickness of the separation layer 4 is, for example, more preferably in a range of 0.05 μm or more and 50 μm or less, and still more preferably in a range of 0.3 μm or more and 1 μm or less. When the thickness of the separation layer 4 is in the range of 0.05 μm or more and 50 μm or less, the short-time light irradiation and low-energy light irradiation can cause desired modification of the separation layer 4. In addition, from the viewpoint of productivity, the thickness of the separation layer 4 is particularly preferably within a range of 1 μm or less.

In addition, in this specification, the "modification" of the separation layer refers to a phenomenon in which the separation layer can be broken by a small external force, or a state in which the adhesion force of the layer in contact with the separation layer is reduced. As a result of the modification of the separation layer by absorbing light, the separation layer loses its strength or adhesiveness before light irradiation. That is, by absorbing light, the separation layer becomes brittle. The so-called modification of the separation layer may be a phenomenon in which the separation layer undergoes decomposition, change in three-dimensional configuration, or dissociation of functional groups due to absorbed light energy. Modification of the separation layer occurs as a result of absorbing light.

Thereby, for example, the separation layer can be broken only by lifting up the support plate through modification, and the support plate can be easily separated from the substrate. More specifically, for example, one of the substrate and the support plate in the laminate is fixed to a mounting table via a support separating device or the like, and the other is held via an adsorption pad (suction portion) or the like provided in the adsorption means. The support plate can be separated from the substrate by lifting up, or the substrate can be separated from the support plate by applying a force by holding a chamfered portion of the peripheral edge portion of the support plate with a separation plate including a clamp (claw portion) or the like. . In addition, for example, The separation device peels the support plate from the substrate in the laminate, and the peeling means supplies a peeling liquid for peeling the adhesive. The peeling solution is supplied to at least a part of the peripheral end portion of the adhesive layer in the laminate through this peeling means, so that the adhesive layer in the laminate can swell, and the substrate can be concentrated on the separation layer from the part where the adhesive layer swells to the separation layer. Apply force to the support plate. Therefore, the substrate and the support plate can be well separated.

The force applied to the laminated body may be appropriately adjusted according to the size of the laminated body, and is not limited. For example, if the laminated body has a diameter of about 300 mm, the substrate and the supporting plate can be appropriately adjusted by applying a force of about 0.1 to 5 kgf. Ground separation.

In the laminated body 10, another layer may be formed between the separation layer 4 and the support plate 2. In this case, the other layers may be made of a light-transmitting material. This makes it possible to appropriately add a layer that imparts desired properties and the like to the laminated body 10 without preventing light from entering the separation layer 4. The wavelength of light that can be used differs depending on the type of material constituting the separation layer 4. Therefore, the material constituting the other layers does not need to transmit light of a full wavelength, and can be appropriately selected from materials that can transmit light of a wavelength that can modify the material constituting the separation layer 4.

In addition, the separation layer 4 is preferably formed only of a material having a structure that absorbs light, but the separation layer 4 may be formed by adding a material that does not have a structure that absorbs light as long as the essential characteristics of the present invention are not impaired.

In addition, the surface of the separation layer 4 on the side opposite to the bonding layer 3 is preferably a flat surface (no unevenness is formed), so that the separation layer 4 can be easily formed and can be uniformly bonded during bonding.

As the light irradiated to the separation layer 4, for example, a YAG laser, a ruby laser, a glass laser, a YVO ₄ laser, an LD laser, and an optical fiber laser are appropriately used depending on the wavelength that can be absorbed by the fired body forming the separation layer 4. Solid laser such as laser; liquid laser such as pigment laser; gas laser such as CO ₂ laser, excimer laser, Ar laser, He-Ne laser; laser light such as semiconductor laser, free electron laser , Or non-laser light. The wavelength capable of modifying the sintered body is not limited, and for example, light having a wavelength in a range of 600 nm or less can be used.

<Manufacturing method of laminated body (second embodiment)>

The manufacturing method of the laminated body by one Embodiment (1st Embodiment) of this invention is demonstrated in detail using 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, a step of forming an adhesion layer on a substrate 1, and a step of forming an adhesion layer 3. A lamination step of laminating the substrate 1 and the support plate 2 with the barrier layer 3 and the separation layer 4. Moreover, as for the laminated body 10 formed by the one embodiment and the manufacturing method of the laminated body, as a separate process, the separation process of separating the support plate 2 from the laminated body 10 is implemented.

[Separation layer forming step]

The separation layer forming step is a step of forming the separation layer 4 modified by absorbing light. In the separation layer forming step, a separation layer is formed by applying the composition for forming a separation layer according to the embodiment on the support plate 2. The method for applying the composition for forming a separation layer to the support plate 2 is not particularly limited, and examples Examples include spin coating, dipping, roller blade, spray coating, and slit coating.

In the separation layer forming step, the diluent solvent is removed from the composition for forming a separation layer applied to the support plate 2 by being placed in a heated environment or a reduced pressure environment. Thereafter, in the separation layer formation step, the polymerizable resin component contained in the composition for separation layer formation is polymerized via a polymerization initiator in an inert gas atmosphere such as nitrogen or an atmospheric environment through exposure or heating to form polymerization. Hardened resin component. After that, the cured product of the polymerizable resin component is fired in an atmospheric environment. The temperature for firing the cured product is 250 ° C or higher, preferably 300 ° C or higher, and more preferably 400 ° C or higher. When the temperature for firing the cured product is 250 ° C. or higher, a separation layer that can absorb light in a wavelength range of 600 nm or less can be favorably formed. The upper limit of the firing temperature is not particularly limited, but is 800 ° C or lower, and preferably 600 ° C or lower.

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

[Next layer forming step]

In the subsequent layer forming step, an adhesive layer 3 is formed on the substrate 1. As shown in FIG. 1, the above-mentioned adhesive is applied on the substrate 1. Next, the temperature was raised while baking stepwise to remove the diluent solvent from the adhesive, thereby forming the adhesive layer 3.

[Lamination step]

The lamination 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 lamination step, as shown in FIG. 1, the surface on which the adhesion layer 3 is formed on the substrate 1 and the surface on which the separation layer 4 is formed on the support plate 2 are bonded. A method of laminating and pressing under vacuum.

Moreover, in the manufacturing method of the laminated body of embodiment, as long as a substrate, an adhesion layer, a separation layer, and a support are laminated | stacked in this order, the order of each step is not specifically limited.

[Other steps]

For the substrate 1 in the laminate 10 produced in the lamination step, for example, an element can be mounted by performing an etching process, a photolithography process, and the like after the thinning step is performed. Since the separation layer 4 is formed of a fired body formed using the composition for forming a separation layer according to one embodiment, it has high chemical resistance. Therefore, in the etching process, the photolithography process, and the like, it is possible to appropriately prevent the separation layer 4 from being damaged due to chemicals or the like.

In addition, as shown in FIG. 1, the laminate 10 on which the element is mounted on the substrate 1 is irradiated with light of a predetermined wavelength through the support plate 2. This allows the separation layer 4 formed of the fired body to be appropriately modified by absorbing the laser light. Therefore, the substrate 1 and the support plate 2 in the laminate 10 can be smoothly separated.

<About a laminated body of another embodiment (second embodiment)>

The laminated body of this invention is not limited to the said embodiment. For example, the laminated body according to the second embodiment is a laminated body formed by laminating a substrate, an adhesive layer, a separation layer, and a support in this order, and the substrate is slightly sealed by a sealing material through an element. The obtained sealing substrate has a structure including a wiring layer (rewiring layer).

For semiconductor devices, fan-in technologies such as fan-in WLP (Fan-in Wafer Level Package) in which the terminals at the ends of the bare wafer are relocated in the wafer area, and on-wafer Fan-out technology such as a fan-out type WLP (Fan-out Wafer Level Package) in which terminals are relocated outside the area is known. In particular, the fan-out technology is applied to a fan-out PLP (Fan-out Panel Level Package) packaged by arranging semiconductor elements on a panel, in order to achieve integration, thinness, and These miniaturization technologies have attracted much attention. The laminate according to one embodiment includes a separation layer having high chemical resistance to various chemicals (which is used to form a wiring layer on a sealing substrate). Therefore, laminates in fan-out WLP and fan-out PLP are also within the scope of the present invention.

[Substrate]

The sealing substrate includes a wiring layer on which the component is mounted, a component, and a sealing material that seals the component. The sealing substrate is preferably provided with 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 composed of wiring connected to an element, and may have a single-layer or multi-layer structure. In one embodiment, the wiring layer may be formed on a dielectric body (for example, a photosensitive resin such as silicon oxide (SiOx), a photosensitive epoxy resin, or the like) through a conductive body (for example, aluminum, copper, titanium, nickel, Metals such as gold and silver, and alloys such as silver-tin alloys are used to form wirings, but the invention is not limited thereto.

(element)

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

(Sealing material)

As the sealing material, for example, a sealing material containing epoxy resin can be used. The sealing material is preferably not provided separately for each element, but integrally seals all the plurality of elements mounted on the wiring layer.

[Support]

The support body only needs to have the strength required to prevent damage or deformation of each component of the sealing substrate when the sealing substrate is formed. In addition, the support is formed of a material that passes light of a wavelength that may be The separation layer formed on the support is modified. In the field of semiconductor device technology, for the purpose of further high-density integration and improving production efficiency, in addition to increasing the size of the circular support plate 2, the use of large-sized panels having a quadrangular shape in plan view has also been studied. Support. Such a method of manufacturing a semiconductor device by using a large quadrangular panel as a support is known as a PLP (Panel Level Package) technology, and can be implemented by a fan-out technology. In the PLP technology, a panel made of a material such as glass or silicon can be suitably used for a panel used as a support.

<About the manufacturing method of the laminated body of other embodiment (2nd Embodiment)>

The manufacturing method of the laminated body of this invention is not limited to the manufacturing method of the laminated body concerning the said embodiment (1st Embodiment) based on the so-called WLP (wafer level package) technology as shown in FIG. For example, the manufacturing method of the laminated body concerning another embodiment is a manufacturing method of the laminated body formed as follows: a barrier bonding layer and a separation layer modified by irradiation with light, the wiring layer provided with a mounting element, the said The element is formed by laminating a sealing substrate with a sealing material that seals the element on a support that supports the sealing substrate. The manufacturing method includes a step of forming a separation layer. In the step, the support is coated on the support. The cloth contains a composition for forming a separation layer of a polymerizable resin component and a polymerization initiator, and the polymerizable resin component is polymerized by heating or exposure, and the polymerized resin component after the polymerization is fired to form the separation layer. An adhesive layer forming step of forming an adhesive layer on the aforementioned separation layer; and forming a sealing substrate on the aforementioned adhesive layer Step of forming a sealed substrate.

Since the separation layer forming step is the same as the separation layer forming step in the method for producing a laminated body according to the above-mentioned embodiment, description thereof will be omitted. In addition, in the adhesive layer forming step, the adhesive layer is the same as the above-mentioned embodiment except that the adhesive layer is formed on the separation layer formed on the support, and therefore description thereof is omitted.

[Sealed substrate forming step]

In the sealing substrate forming step, a wiring layer forming step, a mounting step, a sealing step, and a thinning step are sequentially performed, thereby forming a sealing substrate on the adhesive layer.

[Wiring layer forming step]

In the wiring layer forming step, a wiring layer is formed on the adhesive layer.

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

Next, a wiring is formed on the dielectric layer via a conductor such as a metal. As a method of forming the wiring, for example, a known semiconductor step method such as a photolithography process (resist photolithography) or an etching process can be used.

In this manner, a photolithography process, an etching process, and the like are performed. At this time, the separation layer is exposed to an acid such as hydrofluoric acid, a base such as TMAH, and a resist solvent. In particular, in the fan-out technology, cyclopentanone, cyclohexanone, and the like can be 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, the separation layer can prevent dissolution or peeling due to exposure to acids, alkalis, and resist solvents. Thereby, a wiring layer can be suitably formed on a support body.

[installation steps]

In the mounting step, components are mounted on the wiring layer. The component can be mounted on the wiring layer using, for example, a chip mounter.

[Sealing step]

In the sealing step, the element is sealed via a sealing material. It is not particularly limited, and for reference, for example, while the sealing material is heated to a temperature of 100 ° C. or higher, a high-viscosity state is maintained, and a molding-type injection molding is used.

[Thinning step]

In the thinning step, the sealing material is thinned. Thereby, a sealing substrate including a wiring layer can be appropriately formed on the adhesive layer.

Moreover, in the manufacturing method of the laminated body of this embodiment, processes, such as formation of a bump on a sealing material, and formation of an insulation layer, can be performed after a thinning process.

[About the manufacturing method of the laminated body of a modification]

The manufacturing method of the laminated body of this invention is not limited to the said embodiment. For example, the manufacturing method of the laminated body concerning a modification is a mounting board | substrate, a sealing process, a thinning process, and the sealing board formation process included in the manufacturing method of the laminated body concerning 2nd Embodiment in order, and The wiring layer formation step has such a configuration. In this configuration, a sealing substrate can be appropriately formed on a separation layer having high chemical resistance.

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

[Example] <Evaluation of light transmittance and laser reactivity of 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 the visible light transmittance of the separation layer formed using each composition for forming a separation layer was evaluated. Next, the separation layer in each of the laminates was evaluated by irradiating laser light to the separation layers in the laminates produced using the respective composition for forming a separation layer.

[Preparation of composition for forming separation layer]

First, JER157S70 (Novolacs epoxy resin, manufactured by Mitsubishi Chemical Corporation) was diluted with a mixed solvent (1: 1 (weight ratio)) of PGMEA and PGME to make the concentration 30% by weight. Thus, a solution was prepared. Next, 10 parts by weight of PAG290 was added to 100 parts by weight of JER157S70 in the solution under light-shielding conditions 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 bare glass support to which the composition for forming a separation layer is applied is heated at 90 ° C. for 180 seconds, and further heated at 150 ° C. for 180 seconds to remove the solvent contained in the separation layer . Then, 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 conditions of 250 ° C. and 15 minutes in the air. In addition, the remaining one piece was fired under the conditions of 400 ° C. and 15 minutes in the atmospheric environment. Thus, in Example 1, two types of separation layers having different firing conditions were formed. The separation layer of Example 1 had a film thickness of 1.8 μm.

[Evaluation of transmittance]

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

[Evaluation of laser reactivity]

The laser reactivity was evaluated by irradiating a laser beam with a wavelength of 532 nm to a fired separation layer at 400 ° C. under conditions of a scanning speed of 6500 mm / sec, a frequency of 40 kHz, an output power of 20 A, and an irradiation pitch of 140 μm. The state of the trace of the laser light irradiated to the separation layer was evaluated through a microscope VHX-600 (manufactured by Keyence), and thus the laser reactivity was evaluated. In addition, as a criterion for evaluating laser reactivity, if the area occupied by traces of laser light is 50% or more, it is evaluated as "A", if it is less than 50%, it is evaluated as "B", and if there are no traces of laser light, Evaluation is "C". Thereby, the detachability of the support in the laminate was evaluated in a simulated manner.

[Examples 2 to 17]

By the same procedure as in Example 1, the composition for forming a separation layer of Examples 2 to 17 was prepared. The details of the polymerizable resin components and polymerization initiators used in Examples 2 to 17 are shown below. In addition, the composition of the polymerizable resin component, the polymerization initiator, and the surfactant in the adhesive compositions of Examples 1 to 17 are shown in Tables 1 to 9 below.

(Polymerizable resin component)

． Novolacs 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, obtained by blending a polyfunctional alicyclic epoxy resin represented by the following formula (3) and an alicyclic epoxy resin represented by the formula (4) at a weight ratio of 50:50, (Made by Daicel Chemical Industry Co., Ltd.)

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

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

． Novolacs epoxy resin with naphthalene skeleton (EPICLON HP5000, also manufactured by DIC Corporation)

． Acrylic monomer (DPHA, manufactured by Shin Nakamura Chemical Co., Ltd.) represented by the following formula (7)

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

(Polymerization initiator)

． Photocationic polymerization initiator represented by the following formula (9) (PAG290, manufactured by BASF Corporation [0333]

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

． Gwangyang pear polymerization initiator (410CS, manufactured by San-Apro Ltd.) represented by the following formula (11)

． Thermal cationic polymerization initiator TAG2689 (thermal acid generator: quaternary ammonium blocked, KING INDUSTRY (Company system)

． Thermal cationic polymerization initiator TAG2690 (Thermal acid generator: quaternary ammonium salt capping type, manufactured by King Industries)

． Thermal cationic polymerization initiator TAG2678 (thermal acid generator: quaternary ammonium salt capping type, manufactured by King Industries)

． Dialkyl peroxide (thermal radical polymerization initiator: manufactured by Nippon Oil & Fat Co., Ltd., "Percumyl D (trade name))

Based on the composition and evaluation results of the composition for forming a separation layer shown in Tables 1 to 6 below, it was confirmed that the composition of each composition for forming a separation layer, the firing conditions, and the irradiation conditions of the laser light were different. trend.

[Evaluation of photocationic polymerization initiator]

The composition for forming a separation layer of Examples 1 to 3 was evaluated for a photocationic polymerization initiator (photopolymerization initiator). The evaluation results are shown in Table 1 below.

As shown in Table 1, in the composition for forming a separation layer of Examples 1 to 3, when any photocationic polymerization initiator was used, it was confirmed that light having a wavelength of 532 nm can be formed with low transmittance and laser light. A highly reactive separation layer. In addition, in each of the separation layers of Examples 1 to 3, the separation layer fired at 400 ° C exhibited a lower transmittance of light at a wavelength of 532nm and a laser reactivity as compared with the case of firing at 250 ° C. Higher trend.

[Evaluation of thermal polymerization initiator]

The composition for forming a separation layer of Examples 4 to 6 was evaluated for a thermal polymerization initiator. In addition, in the composition for forming a separation layer of Example 7, an epoxy-modified siloxane was used as a polymerizable resin component to evaluate the thermal polymerization initiator. The evaluation results of Examples 4 to 6 are shown in Table 2 below.

As shown in Table 2, it was confirmed that the photoradical polymerization initiator in the composition for forming a separation layer of Examples 1 to 3 was changed to heat. In the composition for forming a separation layer of Examples 4 to 6 of the composition of the polymerization initiator, 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, it was confirmed that in the composition for forming a separation layer of Examples 4 to 6, by blending a surfactant PF656, the coating workability was improved, and a smooth separation layer was formed on the glass support.

[Evaluation of epoxy resin]

For Examples 7 to 12, compositions for forming a separation layer containing different types of epoxy resins were evaluated. The evaluation results of Examples 7 to 12 are shown in Table 3 below.

As shown in Table 3, it was confirmed that in the separation layers of Examples 7 to 11, not only the case of JER157S70, but also the use of bisphenol-type epoxy resin, oxetane-type epoxy resin, and dicyclopentane. In the case of a diene-type epoxy resin and an epoxy resin having a naphthalene skeleton, the High laser-reactive separation layer. From this, it was confirmed that in the composition for forming a separation layer, an epoxy resin having various skeletons such as an aromatic skeleton and an aliphatic skeleton can be used as the polymerizable resin component. In addition, it was confirmed that in the composition for forming a separation layer of Example 12 in which the composition of the polymerizable resin composition was changed to epoxy-modified siloxane, the transmittance at a wavelength of 532 nm was higher than that of the other examples. A high value, but it is also possible to form a separation layer having laser reactivity.

[Evaluation of the blending amount of the thermal polymerization initiator]

Regarding the composition for forming a separation layer of Examples 4 and 13 to 15, the blending amount of the thermal polymerization initiator TAG-2689 was changed, and the light transmittance and laser reactivity of the separation layer were evaluated. The evaluation results of the blending amount of the thermal polymerization initiator are shown in Table 4 below.

As shown in Table 4, in the composition for forming a separation layer of Example 4 and Examples 13 to 15, the following tendency was shown: the lower the blending amount of TAG-2689 as a thermal polymerization initiator, the wavelength is 532 nm Light The higher the transmittance. In addition, the smaller the blending amount of TAG-2689, the greater the distance between the traces of laser light rays. From the above-mentioned trends, it was confirmed that in the composition for forming a separation layer, a polymerization initiator is an important factor for forming a fired body having a high laser reactivity.

[Evaluation of the transmittance and laser reactivity of the film 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 Example 9, and the light transmittance to each separation layer and the laser Reactivity was evaluated. The evaluation results are shown in Table 5 below.

As shown in Table 5, it can be confirmed that although the separation layers of Examples 9 and 9-1 to 9-3 show a trend that the thinner the film thickness, the higher the transmittance of light with a wavelength of 532 nm, High laser reactivity can be obtained in one separation layer.

[Evaluation of laser reactivity against changes in laser light output power]

For the separation layers of Examples 4, 7, and 9-2, the irradiation lightning was changed The output power of the ray is evaluated to evaluate the laser reactivity. The firing conditions of each separation layer were 400 ° C. The laser irradiation conditions were the same as the laser reactivity evaluation conditions except that the laser output power was changed under the conditions of 20A, 22A, and 24A. The evaluation results are shown in Table 6 below.

As shown in Table 6, any of the separation layers in Examples 4, 7, and 9-2 was able to obtain high laser reactivity. Here, for each of the separation layers of Examples 4, 7, and 9-2, the following tendency was confirmed: the higher the output power of the irradiated laser light, the larger the trace of the laser light formed on the separation layer, the The width of the traces is smaller. In addition, as for the separation layer of Example 7 having a low transmittance of light having a wavelength of 532 nm, the width of each trace compared to the separation layers of Examples 4 and 9-2 was different. (Pitch) is larger. From the above results, it was confirmed that, for a high-transmittance separation layer, laser reactivity can be adjusted by adjusting the output power of laser light and the irradiation pitch.

[Evaluation of the firing temperature of the separation layer]

The composition for forming a separation layer of Example 4 was used to change the firing temperature to form a separation layer, 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 the separation layers of Examples 4 and 4-1, sufficient traces of laser light irradiation were confirmed. However, when the separation layers of Examples 4 and 4-1 were compared, the light transmittance of the separation layer of Example 4 with a high firing temperature was lower, and a larger trace of laser light irradiation was confirmed. Therefore, regarding the temperature at which the separation layer was fired, when considering the results of the transmittance of Reference Example 4-2 and examining it, it was confirmed that a higher temperature is preferable, and a temperature higher than 300 ° C is preferable. temperature.

[Evaluation of acrylic resin component]

As Examples 16 and 17, an acrylic monomer and an acrylic polymer (acrylic resin component) were used to prepare a composition for forming a separation layer. The separation layer formed using the composition for forming a separation layer described above was evaluated for light transmittance and laser reactivity at a wavelength of 532 nm.

The separation layer using the acrylic resin 1 of Example 17 in Table 8 below was produced in the following manner. 8% by weight of a PM solution of TAG-2689 was blended so that the concentration of TAG-2689 was 5% by weight with respect to 100% by weight of the solid content of the acrylic resin 1, so that the solid content of the acrylic resin 1 was 26.5 A base of the composition for forming a separation layer by weight. Next, PF656 was blended in an amount of 0.05 parts by weight based on 100 parts by weight of the base, thereby preparing a composition for forming a separation layer of Example 17.

As in Example 1, the composition for forming a separation layer of Example 17 was spin-coated on a bare glass support at 1000 rpm for 10 seconds, and then the bare glass support was fired at 400 ° C under atmospheric conditions. After 15 minutes, the separation layer of Example 17 was formed. The laser irradiation conditions were the same as those in Example 1. The evaluation results are shown in Table 8 below.

As shown in Table 8, it was confirmed that the acrylic resin and acrylic polymer can be used as the polymerizable resin component in the composition for forming a separation layer in Examples 16 and 17. In addition, 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, it was confirmed that in the case of any of the polymerizable resin components of the radical polymerization system and the cationic polymerization system, laser reactivity can be formed by polymerizing and firing using a polymerization initiator suitable for each polymerizable resin component. High separation layer.

[Evaluation of chemical resistance]

The separation layer forming compositions of Examples 4 and 11 were used to form separation layers having different firing temperatures, and the chemical resistance of each separation layer was evaluated. As the evaluation of chemical resistance, chemical resistance to propylene glycol monomethyl ether acetate (PGMEA), N-methyl-2-pyrrolidone, and cyclopentanone was evaluated at 25 ° C for 10 minutes; and Chemical resistance to a resist stripping solution ST120 (manufactured by Tokyo Yingka Kogyo Co., Ltd.) at 60 ° C for 30 minutes.

In addition, 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 (with a thickness of 1 μm) using C ₄ F ₈ as a reaction gas under conditions of a flow rate of 400 sccm, a pressure of 700 mTorr, a high-frequency power of 2500 W, and a film formation temperature of 240 ° C.

Chemical resistance is evaluated visually and will be formed in The case where the separation layer on the glass support did not swell or peel was evaluated as "A", and the case where at least one of swelling and peeling was confirmed was evaluated as "C". The evaluation results of the chemical resistance of the separation layers of Example 4, Example 11, and Comparative Example 1 are shown in Table 9 below.

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 without being affected by the firing temperature. In addition, it was confirmed that the separation layer formed by using the composition for forming a separation layer of Examples 4 and 9 can obtain high chemical resistance without being affected by the type of the peeling liquid and the like compared with the separation layer of Comparative Example 1.

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 for chemical resistance under the same conditions as in Examples 4 and 9. As a result, similarly to the separation layers of Examples 4 and 9, it was confirmed that the separation layers of Examples 1 to 3, 5 to 8, and 10 to 17 were more resistant to the types of peeling liquid and the like than the separation layers of Comparative Example 1. Achieve high chemical resistance.

[Evaluation of adhesion]

The separation layer of Example 4 and the separation layer of Comparative Example 1 were evaluated for the adhesion of the adhesion layer. The evaluation conditions are shown below.

(Production of sample)

A 12-inch silicon substrate was coated with the composition for forming a separation layer of Example 4 and fired at a temperature of 400 ° C to form a separation layer (thickness: 1.8 μm). A fluorocarbon separation layer of Comparative Example 1 was formed on a 12-inch silicon substrate (thickness: 1 μm) under the same conditions. After that, TZNR (registered trademark) -A4012 (manufactured by Tokyo Chemical Industry Co., Ltd.) was spin-coated on each of the above-mentioned separation layers, and baked at 90 ° C, 160 ° C, and 220 ° C for 4 minutes each to form an adhesion layer. (Thickness 50 μm). A bonding 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 replaced with TZNR (registered trademark) -A4017 (manufactured by Tokyo Chemical Industry Co., Ltd.).

Next, for each sample, the adhesive layer was cut into a band shape of 10 mm width via a cutter. Next, the angle (also called the peeling angle) between the adhesive layer and the substrate was kept constant at 90 °, and at the same time, the band-shaped adhesive layer was vertically pulled up at a speed of 200 mm / sec with respect to the silicon substrate, and the adhesive layer The layer is peeled from the silicon substrate. The adhesion between the separation layer and the adhesive layer was evaluated based on the adhesive strength (g / cm, also referred to as peel strength) at this time. When the bonding strength is 20 g / cm or more, it is determined that there is sufficient adhesiveness. In addition, After that, the laser light was irradiated under the same conditions as in the above [Evaluation of Laser Reactivity], each separation layer was modified, and then the bonding strength was measured and compared with the bonding strength before the laser light was irradiated. The evaluation results are shown in Table 10 below.

As shown in Table 10, compared with the separation layer of Comparative Example 1, the adhesion of the separation layer of Example 4 and the adhesion layer formed using each adhesive was higher. In addition, the adhesion strength of the separation layer in Example 4 after laser irradiation was 0 g / cm, and it was judged that the irradiation of the laser light caused the adhesion layer to be substantially peeled.

The separation layer formed using the composition for forming a separation layer of Examples 1 to 3 and 5 to 17 was evaluated for adhesion under the same conditions as in Example 4. As a result, it was confirmed that the separation layers of Examples 1 to 3 and 5 to 9 had higher adhesion to TZNR (registered trademark) -A4012 and A4017 than the separation layers of Comparative Example 1.

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

Industrial availability

The present invention is applicable to manufacturing steps of miniaturized semiconductor devices.

Claims (13)

A composition for forming a separation layer, which is a composition for forming a separation layer for forming the aforementioned separation layer in a laminate, the laminate system interposing an adhesive layer and a separation layer modified by irradiation with light, The substrate is laminated with a light-transmitting support, and is characterized by including a polymerizable resin component and a polymerization initiator. The composition for forming a separation layer according to claim 1, wherein the polymerizable resin component is a polymerizable resin component having an epoxy group, an epoxy-modified siloxane, and a polymer having an ethylenically unsaturated double bond. At least one of the groups formed by the sexual resin component. The composition for forming a separation layer according to claim 2, wherein the polymerizable resin component is a polymerizable resin component having an epoxy group. The composition for forming a separation layer according to any one of claims 1 to 3, wherein the polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator. A laminated body is a laminated body formed by laminating a substrate and a light-transmitting support layer with a separation layer and a separation layer modified by irradiation with light, characterized in that the separation layer is initiated by polymerization. A fired body of a cured product obtained by polymerizing a polymerizable resin component with an agent. The laminated body according to claim 5, wherein the polymerizable resin component is selected from a polymerizable resin component having an epoxy group, an epoxy-modified siloxane, and a polymerizable resin component having an ethylenically unsaturated double bond. At least one of the groups. The laminate according to claim 5, wherein the aforementioned polymerizable resin component It is a polymerizable resin component having an epoxy group. The laminate according to any one of claims 5 to 7, wherein the aforementioned polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator. A method for manufacturing a laminate, which is a method for manufacturing a laminate by laminating a substrate and a light-transmitting support through an adhesive layer and a separation layer modified by irradiation with light, characterized in that: It includes a step of forming a separation layer, applying a composition for forming a separation layer containing a polymerizable resin component and a polymerization initiator to any one of the substrate and the support, and applying the composition through heating or exposure. The polymerizable resin component is polymerized, and the polymerizable resin component after the polymerization is fired to form the separation layer and a lamination step, the separation substrate and the adhesion layer are separated, and the substrate on which the separation layer is formed is formed. Alternatively, the support, and the substrate on which the separation layer is not formed and the other of the support are laminated. A method for manufacturing a laminate, which is a method for manufacturing a laminate in which a sealing substrate is laminated on a support that supports the sealing substrate via a bonding layer and a separation layer modified by irradiation with light. The sealing substrate includes a wiring layer on which the component is mounted, the component, and a sealing material that seals the component. The sealing substrate includes a step of forming a separation layer, and coating the support with a polymerizable resin component and polymerizing the component. The composition for forming the separation layer of the initiator polymerizes the polymerizable resin component through heating or exposure, and fires the polymerized resin component after polymerization to form the separation layer, and A subsequent 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 9 or 10, wherein the aforementioned polymerizable resin component is selected from the group consisting of a polymerizable resin component having an epoxy group, an epoxy-modified siloxane, and an ethylenically unsaturated double bond. At least one of the group consisting of a polymerizable resin component. The manufacturing method of the laminated body of Claim 9 or 10 whose said polymerizable resin component is a polymerizable resin component which has an epoxy group. The method for producing a laminated body according to claim 9 or 10, wherein the aforementioned polymerization initiator is a thermal polymerization initiator or a photopolymerization initiator.